WO2007145231A1 - 熱収縮性ポリエステル系フィルム、およびその製造方法 - Google Patents
熱収縮性ポリエステル系フィルム、およびその製造方法 Download PDFInfo
- Publication number
- WO2007145231A1 WO2007145231A1 PCT/JP2007/061860 JP2007061860W WO2007145231A1 WO 2007145231 A1 WO2007145231 A1 WO 2007145231A1 JP 2007061860 W JP2007061860 W JP 2007061860W WO 2007145231 A1 WO2007145231 A1 WO 2007145231A1
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- WIPO (PCT)
- Prior art keywords
- film
- heat
- less
- shrinkage
- longitudinal direction
- Prior art date
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000000034 method Methods 0.000 title description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 230000032683 aging Effects 0.000 claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims description 32
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 9
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 229920006257 Heat-shrinkable film Polymers 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 230000008602 contraction Effects 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 230000035882 stress Effects 0.000 description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- -1 polyethylene terephthalate Polymers 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000009966 trimming Methods 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 230000037303 wrinkles Effects 0.000 description 7
- 230000009191 jumping Effects 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000009751 slip forming Methods 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- RKXIRCLSLKEVHQ-UHFFFAOYSA-N CO.C1(CCC(CC1)C(=O)O)C(=O)O Chemical compound CO.C1(CCC(CC1)C(=O)O)C(=O)O RKXIRCLSLKEVHQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- VLTICMVRVQWWIQ-UHFFFAOYSA-N ethyl carbamate;phthalic acid Chemical compound CCOC(N)=O.OC(=O)C1=CC=CC=C1C(O)=O VLTICMVRVQWWIQ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000002603 single-photon emission computed tomography Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/146—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly transversely to the direction of feed and then parallel thereto
-
- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
- B29C61/003—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor characterised by the choice of material
-
- 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
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0049—Heat shrinkable
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to a heat-shrinkable polyester film and a method for producing the same, and more particularly to a heat-shrinkable polyester film suitable for labeling and a method for producing the same.
- a heat-shrinkable plastic film made of rosin is widely used.
- stretched films such as polyvinyl chloride resin, polystyrene resin, polyester resin, etc. are used for polyethylene terephthalate (PET) containers, polyethylene containers, glass containers, etc. Used in various containers for labels, cap seals or collective packaging purposes.
- the polysalt-bulb film has excellent shrinkage properties but low heat resistance. Moreover, it generates salt-hydrogen gas during incineration and causes dioxin. There is.
- a polysalt-bulb resin film is used as a shrinkable label for PET containers, there is also a problem that the label and the container must be separated when the container is recycled.
- Polystyrene films on the other hand, have a good finished appearance after shrinkage, but have poor solvent resistance. Therefore, there is a problem that a special composition ink must be used for printing.
- polystyrene films need to be incinerated at high temperatures, and there is a problem that a large amount of black smoke is generated with an unpleasant odor during incineration.
- polyester films having high heat resistance, easy incineration, and excellent solvent resistance have come to be widely used as shrink labels. With the increase, usage tends to increase.
- a wrapping method has been developed in which a container is closed by covering the periphery of a synthetic resin single-open container such as a lunch box with a belt-like film. Also suitable for such packaging applications. Therefore, demand for films that shrink in the longitudinal direction is expected to increase dramatically in the future.
- a non-stretched film that eliminates the problems of mechanical strength in the direction perpendicular to the main shrinkage direction as described above and develops a function of shrinking in the longitudinal direction is referred to as the longitudinal direction (also referred to as the longitudinal direction).
- Stretch in the longitudinal direction by stretching 2.0 to 5.0 times each in the width direction (also referred to as the transverse direction) and then re-stretching 1.1 times or more in the longitudinal direction.
- a heat-shrinkable polyester film is known in which both the Young's modulus and the Young's modulus in the width direction are adjusted to a predetermined value or more (Patent Document 1).
- Patent Document 1 Japanese Patent Application Laid-Open No. 8-244114
- FIG. 1 is an explanatory view showing the shape of a test piece in the measurement of right-angled tear strength (the unit of length of each part of the test piece in the figure is mm).
- the heat-shrinkable polyester film obtained by the above-described additional test has a poor tearability (so-called perforation opening) when tearing along a perforation perpendicular to the main shrinkage direction. . It was also found that the shrinkage in the longitudinal direction, which is the main shrinkage direction, is not necessarily sufficient and cannot be applied to a wide range of packaging!
- An object of the present invention is to solve the problems of the heat-shrinkable polyester film of Patent Document 1 described above, to have high mechanical strength in the width direction orthogonal to the main shrinkage direction, and to produce a roll-shaped film. It is an object of the present invention to provide a heat-shrinkable polyester film having good perforation openability in which no film tightening occurs and the film roll is difficult to get wrinkled. Furthermore, in addition to the above properties, it is an object of the present invention to provide a heat-shrinkable polyester film that can be applied to applications that require a high shrinkage ratio that is highly shrinkable in the longitudinal direction, which is the main shrinkage direction. Means for solving the problem
- the invention described in claim 1 is characterized in that ethylene terephthalate is a main constituent, and 10 mol% of one or more monomeric components that can be an amorphous component in all polyester resin components. It is a heat-shrinkable polyester-based film that is contained in the above and is formed in a long shape with a constant width and whose main shrinkage direction is the longitudinal direction, and satisfies the following requirements (1) to (4) It is a feature.
- the hot water thermal contraction rate in the longitudinal direction is 15% or more and 80% or less when treated in 90 ° C hot water for 10 seconds.
- Hot water thermal shrinkage in the width direction perpendicular to the longitudinal direction is 0% or more and 17% or less when treated in hot water at 90 ° C for 10 seconds.
- the invention described in claim 2 is the invention described in claim 1, wherein the hot-water heat shrinkage in the longitudinal direction is 15% or more when treated in hot water at 90 ° C for 10 seconds.
- the refractive index in the longitudinal direction is 1.570 or more and 1.590 or less
- the refractive index in the width direction is 1.570 or more and 1.620 or less.
- the invention described in claim 3 is the main component strength of the monomer that can be an amorphous component in all the polyester resin components in the invention described in claim 1 or claim 2. It is one of glycol, 1,4-cyclohexanedimethanol, and isophthalic acid.
- the invention described in claim 4 is the invention described in any one of claims 1 to 3, wherein the longitudinal direction and width after shrinking 10% in the longitudinal direction in warm water at 80 ° C.
- the Elmendorf ratio when measuring the direction Elmendorf tear load is 0.15 or more and 1.5 or less.
- the invention described in claim 5 is the invention described in any one of claims 1 to 4, wherein the per unit thickness after 10% contraction in the longitudinal direction in warm water at 80 ° C. Square tear strength in the width direction is lOONZmm or more and 300NZmm or less
- the invention described in claim 6 is a manufacturing method for continuously manufacturing the heat-shrinkable polyester film according to any one of claims 1 to 5, wherein an unstretched film is After stretching at a magnification of 2.5 times or more and 6.0 times or less in the width direction at a temperature of Tg + 5 ° C or more and Tg + 40 ° C or less with both ends in the width direction held by clips in the tenter After passing through the intermediate zone without carrying out an aggressive heating operation, at a temperature of 100 ° C to 170 ° C 1 Tg + 5 ° C or more Tg after heat treatment for 0 seconds or more and 10.0 seconds or less, after cooling until the film surface temperature reaches 30 ° C or more and 70 ° C or less + Longitudinal direction at a temperature of 80 ° C or less 2.
- the surface temperature of the film is reduced at a cooling rate of 30 ° CZ to 70 ° CZ It is characterized by cooling to 45 ° C or higher and 75 ° C or lower.
- the heat-shrinkable polyester film of the present invention has high mechanical strength in the width direction perpendicular to the main shrinkage direction, and the produced roll-shaped film does not cause winding and the film roll The perforation is easy to open.
- the shrinkage in the longitudinal direction, which is the main shrinkage direction is high. Therefore, the heat-shrinkable polyester film of the present invention can be suitably used as a label for a container such as a bottle, and can be attached to a container such as a bottle very efficiently within a short time.
- heat shrinkage is performed after mounting, a good finish with very little shrinkage due to heat shrinkage can be exhibited.
- the attached label exhibits very good perforation opening.
- dicarboxylic acid component constituting the polyester used in the present invention examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and orthophthalic acid.
- aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid, and alicyclic dicarboxylic acids.
- an aliphatic dicarboxylic acid for example, adipic acid, sebacic acid, decanedicarboxylic acid, etc.
- the content is preferably less than 3 mol%.
- a heat-shrinkable polyester film obtained by using a polyester containing 3% by mole or more of these aliphatic dicarboxylic acids has insufficient film stiffness at high speed.
- the diol component constituting the polyester used in the present invention includes aliphatic diols such as ethylene glycol, 13 propane diol, 14 butane diol, neopentyl glycol, and hexane diol, and 1,4-cyclohexane. And alicyclic diols such as sandimethanol and aromatic diols such as bisphenol A.
- the polyester used for the heat-shrinkable polyester film of the present invention is a cyclic diol such as 1,4-cyclohexanedimethanol, or a diol having 3 to 6 carbon atoms (for example, 1-3 propanediol, Polyester having a glass transition point (Tg) adjusted to 60 to 80 ° C. containing at least one of 1 to 4 butanediol, neopentyl glycol, hexanediol, etc. is preferred! /.
- Tg glass transition point
- the polyester used in the heat-shrinkable polyester film of the present invention has a total of at least one monomer component that can be an amorphous component in 100 mol% of the polyhydric alcohol component in the total polyester resin.
- the amount must be 10 mol% or more, preferably 15 mol% or more, more preferably 17 mol% or more, and particularly preferably 20 mol% or more.
- examples of the monomer that can be an amorphous component include neopentyl dallicol, 1,4-cyclohexanediol, and isophthalic acid.
- a diol having 8 or more carbon atoms for example, octanediol
- a trivalent or more polyvalent alcohol for example, trimethylolpropane, trimethylolpropane.
- Methylolethane, glycerin, diglycerin and the like are preferably not contained.
- the heat-shrinkable polyester film of the present invention was calculated by the following formula 1 from the length before and after shrinkage when treated for 10 seconds in 90 ° C warm water under no load.
- the thermal contraction rate in the longitudinal direction of the film (that is, the thermal contraction rate of hot water at 90 ° C) must be 15% or more and 80% or less.
- Heat shrinkage rate ⁇ (length before shrinkage-length after shrinkage) Z length before shrinkage ⁇ X 100 (%) ⁇ , Formula 1
- the hot water thermal shrinkage in the longitudinal direction at 90 ° C is less than 15%, it is used as a label. In contrast, since the amount of shrinkage is small, the thermal shrinkage rate in the longitudinal direction at 90 ° C exceeds 80%. When used as a label, it is not preferable because the shrinkage tends to occur during heat shrinkage, or so-called “jumping” occurs.
- the lower limit value of the hot water thermal shrinkage in the longitudinal direction at 90 ° C. is preferably 20% or more, more preferably 25% or more, and even more preferably 30% or more.
- the upper limit value of the hot water heat shrinkage in the longitudinal direction at 90 ° C is particularly preferably 75% or less, preferably 70% or less, more preferably 65% or less.
- the film of the present invention when the film of the present invention is preliminarily formed in a cylindrical label whose main shrinkage direction is the circumferential direction and then fitted into a bottle (attached around a bottle or the like), the film at 90 ° C is used.
- the hot water heat shrinkage rate in the long direction is preferably 0% or more and 80% or less.
- the hot water thermal shrinkage in the longitudinal direction at 90 ° C is 40% or less, the shrinkage
- the amount of hot water heat shrinkage in the longitudinal direction at 90 ° C exceeds 80%, it will be used as a label.
- the shrinkage tends to be distorted at the time of heat shrinkage or so-called "flying up" occurs.
- the lower limit value of the hot water heat shrinkage rate in the longitudinal direction at 90 ° C is 45% or more. It is particularly preferably 50% or more and more preferably 55% or more.
- the upper limit value of the hot water thermal contraction rate in the longitudinal direction at 90 ° C is particularly preferably 75% or less, preferably 70% or less, and more preferably 65% or less.
- the above-described use such as fitting of a cylindrical body suitable for a film having a hot water thermal contraction rate force in the longitudinal direction at 90 ° C. of 0% or more and 80% or less may be referred to as a high shrinkage use.
- the hot water heat shrinkage in the longitudinal direction at 90 ° C is 15% or more and less than 40%. Liked to be. When the hot water thermal contraction rate in the longitudinal direction at 90 ° C is less than 15%, the shrinkage amount is small. On the other hand, when the thermal contraction rate of hot water in the long direction at 90 ° C is 40% or more, the label is wound by the body winding method when it is wound by the body winding method. This is not preferable because shrinkage distortion is likely to occur or so-called “jumping” occurs.
- the lower limit value of the hot water heat shrinkage in the longitudinal direction at 90 ° C is particularly preferably 19% or more, more preferably 21% or more, more preferably 17% or more.
- the upper limit value of the hot water thermal contraction rate in the longitudinal direction at 90 ° C. is particularly preferably 38% or less, preferably 36% or less, and more preferably 34% or less.
- the above uses may be referred to as lap round uses.
- the heat-shrinkable polyester film of the present invention was calculated from the length before and after shrinkage according to the above equation 1 when treated for 10 seconds in a 90 ° C warm water under no load condition.
- the heat shrinkage force in the width direction of the film must be 0% or more and 17% or less.
- the hot water thermal shrinkage in the width direction at 90 ° C is less than 0%, a favorable shrinkage appearance cannot be obtained when used as a label on a bottle. If the hot-water heat shrinkage in the width direction exceeds 17%, it is not preferable because it tends to be distorted during heat shrinkage when used as a label.
- the upper limit value of hot water thermal shrinkage in the width direction at 90 ° C is 15% or less, preferably 14% or less, more preferably 13% or less, and further preferably 12% or less Most preferably, it is 11% or less.
- the lower limit value of the hot water heat shrinkage in the width direction at 90 ° C. is considered to be about 0%.
- the heat-shrinkable polyester film of the present invention is obtained by measuring the right-angled tear strength in the width direction per unit thickness by the following method after shrinking 10% in the longitudinal direction in warm water at 80 ° C. It is preferable that the right-angled tear strength in the width direction is between lOONZmm and 300NZmm.
- the film is shrunk 10% in the longitudinal direction in hot water adjusted to 80 ° C, and then sampled as a test piece of a predetermined size according to JIS-K-7128. After that, grasp both ends of the test piece with a universal tensile tester, and measure the strength at the time of tensile fracture in the width direction of the film under the condition of a tensile speed of 200 mmZ. Then, the unit thickness Calculate the right angle tear strength.
- the right-angled tear strength after shrinking 10% in the longitudinal direction in warm water at 80 ° C is less than lOONZmm, it can be easily torn by impact such as dropping during transportation when used as a label On the contrary, if the right-angled tear strength exceeds 300 NZmm, the cutability (ease of tearing) at the initial stage of tearing the label becomes unfavorable.
- the lower limit of the right-angled tear strength is particularly preferably 150 NZmm or more, more preferably 175 NZmm or more, preferably 125 N / mm or more.
- the upper limit of the right-angled tear strength is preferably 275 NZmm or less, more preferably 250 NZmm or less, and even more preferably 225 NZmm or less.
- the heat-shrinkable polyester film of the present invention was subjected to 10% shrinkage in the longitudinal direction in warm water at 80 ° C, and then the Elmendorf bow in the longitudinal direction and the width direction by the following method.
- the Elmendorf ratio which is the ratio of these Elmendorf tear loads, is preferably 0.15 or more and 1.5 or less.
- the film is mounted on a rectangular frame having a predetermined length in a state where the film has been loosened in advance (that is, both ends of the film are held by the frame). Then, the film is contracted by 10% in the longitudinal direction by immersing it in warm water at 80 ° C for about 5 seconds until the loose film becomes tensioned in the frame (until the slack disappears). Then, measure the Elmendorf tear load in the longitudinal and width directions of the film according to JIS-K-7128, and calculate the Elmendorf ratio using Equation 3 below.
- the Elmendorf ratio is less than 0.15, it is not preferable because it is difficult to tear straight along the perforation when used as a label. On the other hand, if the Elmendorf ratio is more than 1.5, it is not preferable because it easily breaks at a position shifted from the perforation.
- the lower limit of the Elmendorf ratio is preferably 0.20 or more, more preferably 0.25 or more. It is especially preferable that it is above.
- the upper limit of the Elmendorf ratio is preferably 1.4 or less, more preferably 1.3 or less, and particularly preferably 2 or less.
- the heat-shrinkable polyester film of the present invention may have a natural shrinkage ratio of 0.05% or more and 1.5% or less after aging for 700 hours in an atmosphere of 40 ° C and 65% RH. is necessary.
- the natural shrinkage rate can be calculated using the following equation 4.
- Natural shrinkage rate ⁇ (Length before aging) Length after aging Z Length before aging ⁇ X 100 (%) ⁇ Equation 4
- the natural shrinkage ratio exceeds 1.5%, it is not preferable because winding tightening occurs when the product wound in a roll shape is stored, and the film roll is easily wrinkled.
- the natural shrinkage rate is preferably as small as possible, but from the viewpoint of measurement accuracy, 0.05% is considered to be the lower limit. Further, the natural shrinkage rate is preferably 1.3% or less, more preferably 1.1% or less, and particularly preferably 1.0% or less.
- the heat-shrinkable polyester film of the present invention needs to have a refractive index in the longitudinal direction of 1.570 or more and 1.620 or less. If the refractive index in the longitudinal direction exceeds 1.620, the solvent adhesiveness when making a label deteriorates, which is not preferable. On the other hand, if it is less than 1.570, it is not preferable because the cut property when used as a label is deteriorated.
- the upper limit of the refractive index in the longitudinal direction is preferably 1.600 or less, preferably 1.595 or less, more preferably 1.593 or less, and particularly preferably 1.590. . On the other hand, the lower limit of the refractive index in the longitudinal direction is preferably 1.575 or more.
- the lower limit of the refractive index in the longitudinal direction is preferably 1.580 or more, more preferably 1.583 or more, and particularly preferably 1.585 or more.
- the refractive index in the longitudinal direction is preferably 1.570 or more and 1.590 or less.
- the upper limit of the refractive index in the longitudinal direction for wrap round applications is preferably 1. 587 or less, particularly preferably 1.585 or less.
- the heat-shrinkable polyester film of the present invention needs to have a refractive index in the width direction of 1.570 or more and 1.620 or less. If the refractive index in the width direction exceeds 1.620, the solvent adhesiveness when labeling is deteriorated, which is not preferable. On the other hand, if it is less than 1.570, it is not preferable because the cut property when used as a label is deteriorated.
- the upper limit of the refractive index in the width direction The value is preferably 1.610 or less, more preferably 1.600 or less, and even more preferably 1.595 or less. Further, the lower limit of the refractive index in the width direction is preferably 1.575 or more, more preferably 1.580 or more.
- the upper limit of the refractive index in the longitudinal direction is preferably 1.590 or less, more preferably 1.588 or less, and particularly preferably 1.586 or less.
- the upper limit of the refractive index in the width direction is preferably 1.610 or less 1. 605 or less Is more preferable.
- the maximum heat shrinkage stress value in the longitudinal direction of the film is 2.5 (MPa) or more and 20 (MPa) or less. If the film is less than the maximum heat shrinkage stress (MPa) in the longitudinal direction of the film, when the label is attached to a container such as a PET bottle and thermally contracted, the label is attached together with the cap when the PET bottle cap is opened. This is not preferable because it may cause a situation where the cap opens and deteriorates the opening of the cap. If the maximum heat shrinkage stress value in the longitudinal direction of the film is too low, shrinkage is insufficient during heat shrinkage, and a good appearance cannot be obtained.
- the lower limit of the maximum heat shrinkage stress value in the longitudinal direction of the film is more preferably 3.0 (MPa) or more, and particularly preferably 3.5 (MPa) or more.
- the upper limit value of the maximum heat shrinkage stress value in the longitudinal direction of the film is particularly preferably 18 (MPa) or less, more preferably 19 (MPa) or less.
- the lower limit of the maximum heat shrinkage stress value in the longitudinal direction of the film is more preferably 6 (MPa) or more, more preferably 7 (MPa ) Or more, and 8 (MPa) or more is particularly preferred! /.
- the upper limit of the maximum heat shrinkage stress value in the longitudinal direction of the film is preferably 7 MPa or less because shrinkage distortion is likely to occur during heat shrinkage after body winding. More preferably, it is 6.5 MPa or less, further preferably 6. OMPa or less, and particularly preferably 5.5 MPa or less.
- the heat-shrinkable polyester film of the present invention preferably has a solvent adhesive strength of 4 (N / 15 mm) or more. If the solvent adhesive strength is less than 4 (NZ 15 mm), the label will be easily peeled off after the heat shrinkage of the label, which is not preferable.
- solvent adhesion strength The degree is more preferably 4.5 (NZI 5 mm) or more, and particularly preferably 5 (NZ I 5 mm) or more. In particular, in the case of high shrinkage, it is preferable to satisfy the above characteristics.
- the heat-shrinkable polyester film of the present invention preferably has a thickness variation of 10% or less in the longitudinal direction. If the thickness unevenness in the longitudinal direction is more than 10%, it is not preferable because printed spots are likely to occur during printing at the time of label production or shrinkage spots after heat shrinkage are likely to occur. Note that the thickness unevenness in the longitudinal direction is 8% or less, more preferably 6% or less.
- the heat-shrinkable polyester film of the present invention does not detect the endothermic curve peak during the melting point measurement in the differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- the thickness of the heat-shrinkable polyester film of the present invention is not particularly limited.
- As the heat-shrinkable film for 1S label 10 to 200 ⁇ m is preferable 20 to: LOO ⁇ m is more preferable.
- the heat-shrinkable polyester film of the present invention forms the unstretched film by melt-extruding the above-described polyester raw material with an extruder, and the unstretched film is biaxially stretched by the method described below. And can be obtained by heat treatment.
- the polyester raw material is preferably dried using a dryer such as a hopper dryer or a pad dryer, or a vacuum dryer. After drying the polyester raw material in this way, it is melted at a temperature of 200 to 300 ° C and extruded into a film using an extruder.
- a dryer such as a hopper dryer or a pad dryer, or a vacuum dryer.
- any existing method such as T-die method or tubular method can be used.
- An unstretched film is obtained by quenching the extruded sheet-like molten resin. Obtainable.
- a method for rapidly cooling the molten resin it is preferable to employ a method of obtaining a substantially unoriented resin sheet by casting the molten resin from a die onto a rotating drum and rapidly solidifying it. it can.
- the obtained unstretched film was stretched in the width direction under a predetermined condition, then heat-treated once, and then stretched in the longitudinal direction under the predetermined condition.
- the heat-shrinkable polyester film of the present invention can be obtained.
- the preferred biaxially stretched 'heat treatment method for obtaining the heat-shrinkable polyester film of the present invention will be described in detail while considering the difference from the conventional biaxially stretched heat-shrinkable polyester film' heat treatment method. explain.
- a normal heat-shrinkable polyester film is produced by stretching an unstretched film in the direction of shrinkage. Although there has been a high demand for heat-shrinkable polyester films that shrink in the longitudinal direction, it is difficult to produce a wide film by simply stretching an unstretched film in the longitudinal direction. Thickness A film with good spots cannot be produced. In addition, if a method in which the film is previously stretched in the width direction and then stretched in the longitudinal direction is employed, the width direction shrinks unnecessarily, or the amount of contraction in the longitudinal direction becomes insufficient.
- JP-A-8-244114 discloses a method of stretching an unstretched film in the longitudinal, lateral and longitudinal order under predetermined conditions in order to improve the mechanical properties in the longitudinal direction.
- the film obtained was subjected to longitudinal wrinkles on the film roll produced with a large natural shrinkage rate, and the perforation was opened. The sex was also poor.
- the reason why it is possible to obtain a film having good perforation cutability and no shrinkage by performing a specific intermediate heat treatment after transverse stretching is not clear, but by performing a specific intermediate heat treatment, We believe that it is possible to reduce the shrinkage stress in the width direction while leaving some molecular orientation in the width direction.
- the lower limit of the heat treatment temperature is preferably 110 ° C. or higher, more preferably 115 ° C. or higher.
- the upper limit of the heat treatment temperature is 165 ° C or less.
- the temperature is preferably 160 ° C. or less.
- the heat treatment time needs to be appropriately adjusted according to the raw material composition within a range of 1.0 second to 10.0 seconds.
- the stretching in the width direction of the unstretched film is performed at a temperature of Tg + 5 ° C or more and Tg + 40 ° C or less in a state where both ends in the width direction are held by clips in the tenter. It should be done so that the magnification is 5 times or more and 6.0 times or less. If the stretching temperature is lower than Tg + 5 ° C, breakage is likely to occur during stretching. On the other hand, if it exceeds Tg + 40 ° C, the thickness unevenness in the width direction becomes worse.
- the lower limit of the transverse stretching temperature is preferably Tg + 10 ° C. or more, more preferably Tg + 15 ° C. or more.
- the upper limit of the transverse stretching temperature is preferably Tg + 35 ° C. or less, more preferably Tg + 30 ° C. or less.
- the lower limit of the transverse stretching ratio is preferably 3.0 times or more, more preferably 3.5 times or more.
- the upper limit of the transverse stretching ratio is preferably 5.5 times or less, more preferably 5.0 times or less.
- the transverse-longitudinal stretching method of the present invention it is necessary to perform an intermediate heat treatment after the transverse stretching as described above, but 0.5% between the transverse stretching and the intermediate heat treatment. It is necessary to pass through an intermediate zone that does not perform an aggressive heating operation for a time of at least 3 seconds but not more than 3.0 seconds. That is, considering production costs, it is preferable to perform transverse stretching and intermediate heat treatment in the same tenter. However, in the production of the film of the present invention, the transverse stretching zone and heat treatment zone in the tenter are strong. It is preferable to provide an intermediate zone between them.
- the hot air from the stretching zone and the heat treatment zone is blocked so that the paper piece hangs almost completely in the vertical direction. I prefer to do it.
- the film after transverse stretching is led to an intermediate zone where force is applied and allowed to pass through the intermediate zone over a predetermined time.
- the time for passing through the intermediate zone is less than 0.5 seconds, the transverse stretching zone is caused by the accompanying flow of the passing film.
- the hot air flows into the heat setting zone, which makes it difficult to control the temperature of the intermediate heat treatment in the heat setting zone.
- the time required to pass through the intermediate zone is sufficient if it is 3.0 seconds, and setting it longer than that is not preferable because it wastes equipment.
- the lower limit of the time for passing through the intermediate zone is preferably 0.7 seconds or more, and more preferably 0.9 seconds or more.
- the upper limit of the time for passing through the intermediate zone is preferably 2.5 seconds or less, and more preferably 2.0 seconds or less.
- the film is not sufficiently stretched at the edge of the film and is not thick (mainly It is preferable to trim the clip gripping portion during transverse stretching. More specifically, the thickness at the edge of the film using a tool such as a cutter at a thickness approximately 1.1 to 1.3 times the thickness of the central portion located at the edge of the left and right edges of the film. It is preferable to cut the portion and remove the thick portion while stretching only the remaining portion in the longitudinal direction.
- it is preferable to cool the film before trimming so that the surface temperature is 50 ° C. or lower.
- trimming can be performed without disturbing the cut surface.
- a round blade having a circumferential cutting edge that can be performed using a normal cutter or the like is used for trimming the film edge, the situation that the edge of the film does not become dull locally does not occur, and the film edge is lengthened. It is preferable because it can continue to cut sharply over a period of time and does not cause a breakage during stretching in the longitudinal direction.
- the cooling rate is 30 ° CZ seconds or more and 70 ° CZ seconds or less. It is preferred to cool the film until the surface temperature is between 45 ° C and 75 ° C. Thus, the natural shrinkage rate can be reduced only by cooling the film at an appropriate speed. If the cooling rate is lower than 30 ° CZ seconds or the surface temperature after cooling is higher than 75 ° C, a low natural shrinkage rate cannot be obtained. On the other hand, if the cooling rate is abruptly exceeding 70 ° CZ seconds, the degree of film shrinkage in the width direction (, ⁇ neck neck-in '') will increase, and the film surface will be easily damaged. This is preferable.
- Tables 1 and 2 show the properties of the raw materials used in the examples and comparative examples, compositions, production conditions of the films in the examples and comparative examples (stretching and heat treatment conditions, etc.), respectively.
- the evaluation method of the film is as follows.
- the film is cut into a 10cm x 10cm square, heat-shrinked in warm water at a specified temperature of ⁇ 0.5 ° C for 10 seconds under no load condition, and then the vertical and horizontal dimensions of the film are measured. Measured, and the thermal shrinkage rate was calculated according to the above formula 1. The direction in which the heat shrinkage rate is large was defined as the main shrinkage direction.
- each sample film was left in an atmosphere of 23 ° C. and 65% RH for 2 hours or more, and then measured.
- ⁇ 9 and Comparative Examples 1 to 3 and 5 were measured for shrinkage in the longitudinal direction and Comparative Example 4 in the width direction), and the natural shrinkage rate was calculated by Equation 4 above.
- a test piece was prepared by sampling in the shape shown in Fig. 1 according to JIS-K-7128 ( In sampling, the longitudinal direction of the test piece was defined as the main shrinkage direction of the film). After that, hold both ends of the test piece with a universal tensile tester (Autograph manufactured by Shimadzu Corporation), and measure the strength at the time of tensile fracture in the width direction of the film under the condition of a tensile speed of 200 mmZ. The right-angle tear strength per unit thickness was calculated using Equation 2 above.
- the film was sampled into a long roll of 30 m length x 40 mm width and measured at a speed of 5 (mZ min) using a continuous contact thickness gauge manufactured by Micron Measuring Instruments Co., Ltd.
- the length direction of the film sample was set as the main shrinkage direction of the film.
- the maximum thickness at the time of measurement was Tmax.
- the minimum thickness was Tmin.
- the average thickness was Tave.
- Thickness unevenness ⁇ (Tmax.—Tmin.) ZTave. ⁇ X 100 (%) ⁇ ⁇ Equation 5
- the stretched film was sealed by applying 1,3-dioxolane and bonding the two together. After that, the seal part is cut to a width of 15 mm in a direction orthogonal to the main shrinkage direction of the film (hereinafter referred to as the orthogonal direction), and it is universally tensioned by Baldwin Co., Ltd.
- a 180 ° peel test was conducted under the condition of a tensile speed of 200 mmZ with the tester STM-50 set. And the tensile strength at that time was made into solvent adhesive strength.
- the heat-shrinkable film was preprinted in three colors with Toyo Ink Mfg. Co., Ltd.'s grass gold and white ink. Then, by sticking both ends of the printed film with zoxolan, a cylindrical label (the main shrinkage direction of the heat-shrinkable film is the circumferential direction, and the outer peripheral length is 1.05 times the outer peripheral length of the bottle to be installed. A certain cylindrical label) was created. After pressing, put the cylindrical label on a 500 ml PET bottle (bore diameter 62 mm, minimum neck diameter 25 mm) and use Fuji Astec Inc steam tunnel (model: SH-1500-L) Passing time 2.5 seconds, label was attached by heat shrinking at zone temperature 80 ° C.
- the neck part was adjusted so that the 40 mm diameter part would be one end of the label.
- the finish after shrinkage was evaluated visually, and the criteria were as follows. ⁇ : No wrinkles, jumps, or insufficient shrinkage occurred, and no color spots were observed. ⁇ : No wrinkles, jumps, or insufficient shrinkage could be confirmed, but some color spots were observed. : Neither jumping up nor insufficient shrinkage has occurred, but spots on the neck are visible
- the heat-shrinkable film is printed with Toyo Ink Mfg. Co., Ltd.'s grass “gold” white ink in three colors, and the printed heat-shrinkable film has a length of 230 mm x width 100 so that the lengthwise direction is vertical. Cut out in mm size. And with a 265ml aluminum bottle can (see Fig. 2, barrel diameter 68 mm, neck diameter minimum 25 mm, neck diameter 1 ⁇ 20 mm with a “neck” provided), While winding the film so that one of the long sides of the cut-out film is along the bottom of the feeling, it is manufactured by the following method at the top, bottom, and center of the short side of the film on the bottle can contact surface side.
- the applied active energy ray (UV) curable adhesive was applied in the form of dots to fix the film to a bottle can.
- the adhesive layer applied to the other edge was sandwiched.
- a can was manufactured.
- the bottle can with a heat-shrinkable label was immediately sent to a steam furnace shrink tunnel 3m long and kept at 92 ° C after passing the label, and allowed to pass for 10 seconds. It was shrunk and stuck to the outer periphery of the bottle can.
- the neck part was adjusted so that the part with a diameter of 40 mm would be one end of the label. Thereafter, the finish after shrinkage was visually evaluated in the following four stages.
- the label was attached to the PET bottle under the same conditions as those described above for the shrinkage finish (cylindrical body fitting). If the label and PET bottle are lightly twisted and the label does not move, it is marked as X. If the label slips out or the label and the bottle are misaligned, the label is marked as X. When a film is directly wrapped around a PET bottle, etc., the edge strength of the film is adhered to the SPET bottle, so the label adhesion property will not be a problem.
- a label with a perforation in advance in a direction perpendicular to the main shrinkage direction was attached to a PET bottle under the same conditions as the above-described measurement conditions for shrinkage finishing (cylindrical fitting).
- the perforations were formed by inserting holes with a length of 1 mm at intervals of 1 mm, and two perforations with a width of 22 mm and a length of 120 mm were provided in the vertical direction (height direction) of the label.
- the cylindrical fitting method preliminary circumferential shrinkage After forming a cylindrical label in the direction, it is inserted into a PET bottle etc. and attached) or a wrap round method (film is directly wrapped around a PET bottle etc. so that the main shrinkage direction is the circumferential direction) If it can be used practically as a heat-shrinkable film by any of the above methods, it will be marked as ⁇ , and in both the tubular body fitting method and the wrapping round method, heat will be applied. X was used if it could not be used practically as a shrinkable film.
- Polyesters used in Examples and Comparative Examples are as follows. [0083] Polyester 1: Ethylene glycol 70 mol 0 I neopentyl glycol 30 mol 0/0 terephthalic acid and force also polyester (IV 0. 72dl / g)
- Polyester 2 Polyethylene terephthalate (IV 0.775dl / g)
- Polyester 3 terephthalic acid units as dicarboxylic acid component 82.5 mol 0 I isophthalic acid unit 17.5 mol% Yorinari, consisting of ethylene glycol as the diol component.
- Polyester 4 polyester composed of ethylene glycol 70 mol 0 I 1, 4 Cyclohexanedicarboxylic methanol 3 to Shikuro 0 mole 0/0 and terephthalic acid (IV 0. 75dl / g)
- the above polyester 1 and polyester 2 were mixed at a weight ratio of 90:10 and charged into an extruder. After pressing, the mixed resin is melted at 280 ° C, T-die force is also extruded, wound around a rotating metal roll cooled to a surface temperature of 30 ° C, and rapidly cooled, so that the thickness of 360 m A stretched film was obtained. At this time, the bow I removal speed (rotation speed of the metal roll) of the unstretched film was about 20 mZmin. The Tg of the unstretched film was 67 ° C. Then, the unstretched film was guided to a tenter (first tenter) in which a transverse stretching zone, an intermediate zone, and an intermediate heat treatment zone were continuously provided.
- a tenter first tenter
- the length of the intermediate zone located between the transverse stretching zone and the intermediate heat treatment zone is set to about 40 cm.
- the hot air from the stretching zone and the hot air from the heat treatment zone are blown so that the piece of paper hangs almost completely in the vertical direction. Blocked.
- a plurality of roll groups are continuously arranged in such a film whose edge is trimmed.
- the film was led to a longitudinal stretching machine, preheated on a preheating roll until the film temperature reached 70 ° C, and then stretched 3 times between stretching rolls set at a surface temperature of 95 ° C. After stretching, the stretched film was forcibly cooled by a cooling roll set at a surface temperature of 25 ° C.
- the surface temperature of the film before cooling was about 75 ° C
- the surface temperature of the film after cooling was about 25 ° C.
- the time required for cooling from 70 ° C to 25 ° C was about 1.0 seconds, and the film cooling rate was 45 ° CZ seconds.
- the cooled film is guided to a tenter (second tenter), heat-treated in an atmosphere of 95 ° C for 2.0 seconds in the second tenter, cooled, and both edges are cut.
- a biaxially stretched film of about 30 m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film.
- Table 3 shows the evaluation results.
- a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that polyester 1 and polyester 2 were mixed at a weight ratio of 70:30 and charged into an extruder. The characteristics of the obtained film were evaluated by the same method as in Example 1. Table 3 shows the evaluation results.
- a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the transverse stretching ratio in the tenter (first tenter) was changed to 5.0 times.
- the thickness of the biaxially stretched heat-shrinkable polyester film was about 24 ⁇ m.
- the properties of the obtained film were evaluated by the same method as in Example 1. Table 3 shows the evaluation results.
- a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the temperature of the intermediate heat treatment in the tenter (first tenter) was changed to 140 ° C.
- the thickness of the biaxially stretched heat-shrinkable polyester film was about 24 ⁇ m.
- the properties of the obtained film were evaluated by the same method as in Example 1. Table 3 shows the evaluation results.
- a heat-shrinkable film was continuously produced by the same method as in Example 1 except that it was changed to 0 times.
- the biaxially stretched heat-shrinkable polyester film had a thickness of about 18 m.
- the characteristics of the obtained film were evaluated by the same method as in Example 1. Table 3 shows the evaluation results.
- a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the temperature of the stretching roll in the longitudinal stretching machine was changed to 92 ° C and the stretching ratio in the longitudinal direction was changed to 7.0 times. .
- the biaxially stretched heat-shrinkable polyester film had a thickness of about 13 m.
- the characteristics of the obtained film were evaluated by the same method as in Example 1. Table 3 shows the evaluation results.
- a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the draw ratio in the longitudinal direction of the machine was changed to 1.5.
- the biaxially stretched heat-shrinkable polyester film had a thickness of about 60 ⁇ m.
- the properties of the obtained film were evaluated by the same method as in Example 1. Table 3 shows the evaluation results.
- a heat-shrinkable film was continuously produced by the same method as in Example 1.
- the biaxially stretched heat-shrinkable polyester film had a thickness of about 60 m.
- the characteristics of the obtained film were evaluated by the same method as in Example 1. Table 3 shows the evaluation results.
- Example 1 In the same manner as in Example 1, except that the transverse stretch ratio in the tenter (first tenter) was changed to 4.5 times and the longitudinal stretch ratio in the longitudinal stretcher was changed to 1.5 times. A heat shrinkable film was continuously produced. The thickness of the biaxially stretched heat-shrinkable polyester film was about 27 ⁇ m. The properties of the obtained film were evaluated by the same method as in Example 1. Table 3 shows the evaluation results. [0096] [Comparative Example 1]
- the above polyester 3 is put into an extruder, melted at 265 ° C, extruded from T Daika, wrapped around a rotating metal roll cooled to a surface temperature of 30 ° C, and rapidly cooled, resulting in a thickness of 360 m
- An unstretched film was obtained.
- the take-up speed of the unstretched film was the same as in Example 1.
- the unstretched film is guided to a longitudinal stretching machine (first longitudinal stretching machine) in which a plurality of roll groups are continuously arranged, preheated on a preheating roll, and then surface temperature of 88 ° C.
- the film was stretched 2.7 times between the stretching rolls set to 1.
- the film stretched in the longitudinal direction is led to a tenter (first tenter) in which a transverse stretching zone and a heat treatment zone are continuously provided, and the transverse stretching zone is 97 ° C at a stretching temperature of 97 ° C. After being stretched by 3.5 times, it was heat treated at 125 ° C in a heat treatment zone. Then, the heat-treated film is guided to a longitudinal stretching machine (second longitudinal stretching machine) in which a plurality of roll groups are continuously arranged, preheated on a preheating roll, and then set to a surface temperature of 98 ° C. Stretched again 1.5 times between the drawn rolls.
- the film stretched again in the longitudinal direction is guided to a tenter (second tenter), heat treated at 85 ° C, cooled, and both edges are cut and removed to give a biaxially stretched film of about 35 / zm.
- the film was continuously formed over a length of 5 mm to obtain a heat-shrinkable polyester film roll.
- Cooling rate 25 ° CZ seconds
- a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that polyester 1 and polyester 2 were mixed at a weight ratio of 40:60 and charged into an extruder.
- the biaxially stretched heat-shrinkable polyester film had a thickness of about 13 m.
- the properties of the obtained film were evaluated by the same method as in Example 1. The evaluation results are shown in Table 3.
- a heat-shrinkable film was continuously produced in the same manner as in Example 1 except that the temperature of the intermediate heat treatment in the tenter (first tenter) was changed to 70 ° C.
- the properties of the obtained film were evaluated by the same method as in Example 1. The evaluation results are shown in Table 3. [0099] [Comparative Example 4]
- a heat-shrinkable film was continuously produced in the same manner as in Comparative Example 1 except that the draw ratio at the time of longitudinal stretching again with the second longitudinal stretching machine was 3.0 times.
- the characteristics of the obtained film were evaluated by the same method as in Example 1. Table 3 shows the evaluation results.
- Example 19 As is clear from Table 3, all the films obtained in Example 19 were not shrinkable in the width direction perpendicular to the main shrinkage direction, which is highly shrinkable in the longitudinal direction, which is the main shrinkage direction. Always low.
- the films obtained in Example 16 all had high solvent adhesive strength, good label adhesion, and good shrinkage finish (cylinder fitting method) with no shrinkage spots.
- the film obtained in Example 79 was excellent in shrink finish (wrapping round method).
- the film obtained in Example 7 has a solvent adhesion strength. The degree was strong.
- the heat-shrinkable polyester films of Examples 1 to 9 had good perforation openability, and did not cause wrinkles on manufactured film rolls with low natural shrinkage. . That is, the heat-shrinkable polyester films obtained in Examples 1 to 9 were all highly practical with high label quality.
- the heat-shrinkable film obtained in Comparative Example 1 had poor label adhesion and perforation openability.
- the heat-shrinkable films obtained in Comparative Examples 2 and 3 both had high heat shrinkage in the film width direction and had poor label adhesion, resulting in shrinkage spots.
- the film obtained in Comparative Example 4 (main shrinkage direction is the width direction) had good shrinkage finish (cylindrical body fitting method), but was poor in perforation openability.
- the film obtained in Comparative Example 5 (the main shrinkage direction is the width direction) had shrinkage spots with a large thermal shrinkage rate in the direction orthogonal to the main shrinkage direction, and the perforation openability was poor. A wrinkle occurred on a film roll produced with a large natural shrinkage. That is, the heat-condensable polyester films obtained in Comparative Examples 1 to 5 were all inferior in quality as labels and low in practicality.
- the heat-shrinkable polyester film of the present invention has excellent cache properties as described above, it can be suitably used for labeling bottles.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/304,531 US7829655B2 (en) | 2006-06-14 | 2007-06-13 | Heat-shrinkable polyester film and process for production thereof |
CN2007800223544A CN101500784B (zh) | 2006-06-14 | 2007-06-13 | 热收缩性聚酯系膜及其制造方法 |
AT07745143T ATE498484T1 (de) | 2006-06-14 | 2007-06-13 | Wärmeschrumpfbare polyesterfolie und herstellungsverfahren dafür |
EP07745143A EP2042294B1 (en) | 2006-06-14 | 2007-06-13 | Heat-shrinkable polyester film and process for production thereof |
DE200760012548 DE602007012548D1 (de) | 2006-06-14 | 2007-06-13 | Wärmeschrumpfbare polyesterfolie und herstellungsverfahren dafür |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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JP2006165212 | 2006-06-14 | ||
JP2006-165212 | 2006-06-14 | ||
JP2006355365 | 2006-12-28 | ||
JP2006-355365 | 2006-12-28 | ||
JP2007154874A JP4411556B2 (ja) | 2006-06-14 | 2007-06-12 | 熱収縮性ポリエステル系フィルム、およびその製造方法 |
JP2007-154874 | 2007-06-12 |
Publications (1)
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WO2007145231A1 true WO2007145231A1 (ja) | 2007-12-21 |
Family
ID=38831745
Family Applications (1)
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PCT/JP2007/061860 WO2007145231A1 (ja) | 2006-06-14 | 2007-06-13 | 熱収縮性ポリエステル系フィルム、およびその製造方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US7829655B2 (ja) |
EP (1) | EP2042294B1 (ja) |
JP (1) | JP4411556B2 (ja) |
KR (1) | KR100991638B1 (ja) |
CN (1) | CN101500784B (ja) |
AT (1) | ATE498484T1 (ja) |
PT (1) | PT2042294E (ja) |
TW (1) | TWI352713B (ja) |
WO (1) | WO2007145231A1 (ja) |
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JP2009227337A (ja) * | 2008-02-29 | 2009-10-08 | Toyobo Co Ltd | ラベル |
US8673414B2 (en) | 2006-08-30 | 2014-03-18 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester film, process for production thereof, and package |
US8685305B2 (en) | 2007-09-25 | 2014-04-01 | Toyo Boseki Kabushiki Kaisha | Process for production of heat-shrinkable polyester film, heat-shrinkable polyester film and packages |
JP2015199909A (ja) * | 2014-04-01 | 2015-11-12 | 東洋紡株式会社 | 熱収縮性ポリエステル系フィルムおよび包装体 |
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- 2007-06-13 EP EP07745143A patent/EP2042294B1/en not_active Not-in-force
- 2007-06-13 WO PCT/JP2007/061860 patent/WO2007145231A1/ja active Application Filing
- 2007-06-13 PT PT07745143T patent/PT2042294E/pt unknown
- 2007-06-13 AT AT07745143T patent/ATE498484T1/de active
- 2007-06-13 CN CN2007800223544A patent/CN101500784B/zh not_active Expired - Fee Related
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- 2007-06-13 US US12/304,531 patent/US7829655B2/en not_active Expired - Fee Related
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Cited By (8)
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US8673414B2 (en) | 2006-08-30 | 2014-03-18 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester film, process for production thereof, and package |
US8685305B2 (en) | 2007-09-25 | 2014-04-01 | Toyo Boseki Kabushiki Kaisha | Process for production of heat-shrinkable polyester film, heat-shrinkable polyester film and packages |
WO2009107591A1 (ja) * | 2008-02-27 | 2009-09-03 | 東洋紡績株式会社 | 白色熱収縮性ポリエステル系フィルム、白色熱収縮性ポリエステル系フィルムの製造方法、ラベル、及び包装体 |
US8728594B2 (en) | 2008-02-27 | 2014-05-20 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable white polyester film, process for producing heat-shrinkable white polyester film, label, and package |
KR101491876B1 (ko) * | 2008-02-27 | 2015-02-09 | 도요보 가부시키가이샤 | 백색 열수축성 폴리에스테르계 필름, 백색 열수축성 폴리에스테르계 필름의 제조방법, 라벨, 및 포장체 |
JP2009227337A (ja) * | 2008-02-29 | 2009-10-08 | Toyobo Co Ltd | ラベル |
JP2015199909A (ja) * | 2014-04-01 | 2015-11-12 | 東洋紡株式会社 | 熱収縮性ポリエステル系フィルムおよび包装体 |
JP2019147954A (ja) * | 2014-04-01 | 2019-09-05 | 東洋紡株式会社 | 熱収縮性ポリエステル系フィルムおよび包装体 |
Also Published As
Publication number | Publication date |
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KR100991638B1 (ko) | 2010-11-04 |
EP2042294A1 (en) | 2009-04-01 |
TWI352713B (en) | 2011-11-21 |
ATE498484T1 (de) | 2011-03-15 |
PT2042294E (pt) | 2011-02-28 |
CN101500784B (zh) | 2012-01-04 |
EP2042294B1 (en) | 2011-02-16 |
US7829655B2 (en) | 2010-11-09 |
JP2008179122A (ja) | 2008-08-07 |
US20090270584A1 (en) | 2009-10-29 |
EP2042294A4 (en) | 2009-12-30 |
JP4411556B2 (ja) | 2010-02-10 |
CN101500784A (zh) | 2009-08-05 |
KR20090034336A (ko) | 2009-04-07 |
TW200806721A (en) | 2008-02-01 |
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