WO2009069965A2 - Biaxially oriented laminated film for wrapping food articles and method of manufacturing same - Google Patents
Biaxially oriented laminated film for wrapping food articles and method of manufacturing same Download PDFInfo
- Publication number
- WO2009069965A2 WO2009069965A2 PCT/KR2008/007042 KR2008007042W WO2009069965A2 WO 2009069965 A2 WO2009069965 A2 WO 2009069965A2 KR 2008007042 W KR2008007042 W KR 2008007042W WO 2009069965 A2 WO2009069965 A2 WO 2009069965A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- biaxially oriented
- laminated film
- oriented laminated
- film
- acid
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 235000013305 food Nutrition 0.000 title description 5
- 239000004645 polyester resin Substances 0.000 claims description 30
- 229920001225 polyester resin Polymers 0.000 claims description 30
- 229920006122 polyamide resin Polymers 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- 229920002292 Nylon 6 Polymers 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 13
- -1 dipropanediol Chemical compound 0.000 claims description 12
- 239000004840 adhesive resin Substances 0.000 claims description 11
- 229920006223 adhesive resin Polymers 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012802 nanoclay Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 2
- 241001595840 Margarites Species 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052626 biotite Inorganic materials 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000005025 cast polypropylene Substances 0.000 claims description 2
- 229910001919 chlorite Inorganic materials 0.000 claims description 2
- 229910052619 chlorite group Inorganic materials 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229910052629 lepidolite Inorganic materials 0.000 claims description 2
- 229910052630 margarite Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 41
- 239000007789 gas Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 239000010954 inorganic particle Substances 0.000 description 7
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920003313 Bynel® Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 2
- 239000000006 Nitroglycerin Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229960003711 glyceryl trinitrate Drugs 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 102100027446 Acetylserotonin O-methyltransferase Human genes 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 101000936718 Homo sapiens Acetylserotonin O-methyltransferase Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
-
- 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
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
- B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- 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
- B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
-
- 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
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Definitions
- the present invention relates to a biaxially oriented laminated film for wrapping food articles, and a method of manufacturing thereof.
- a wrapping material for food products is required to have satisfactory gas
- Japanese Laid-open Patent Publication No. 1997-289288 discloses a transparent film having excellent gas and water barrier properties, which comprises two layers composed of two or more kinds of inorganic oxides sequentially stacked on one side of a biaxially oriented nylon base film.
- this film tends to undergo undesirable cracking and suffers from processing difficulties due to the tendency of the nylon-6 film to absorb moisture.
- Japanese Laid-open Patent Publication Nos. 1996-296138 and 1987-056675 disclose methods for improving gas barrier properties by depositing inorganic oxides on a transparent plastic film. However, they also suffer from the problem of cracking and poor surface characteristics for printing.
- Japanese Laid-open Patent Publication No. 2004-351874 discloses a method of manufacturing a transparent barrier film composed essentially of two polyamide (PA) e.g. nylon-6 layers disposed on both sides of a resin layer essentially consisting of an ethylene-vinylalcohol (EVOH) copolymer. Although this method provides improved barrier properties of nylon-6 film, the problem of moisture absorptivity of nylon-6 and ethylene-vinylalcohol copolymer remains unsolved.
- PA polyamide
- EVOH ethylene-vinylalcohol
- a method of manufacturing a biaxially oriented laminated film comprising:
- polyester resin (B) which satisfies the above equation are melt-extruded using a T-die to form a two or more layered laminate, and then the laminate is rapidly cooled using a cooling roll to prepare a cast sheet.
- the polyester resin used in the present invention may be prepared by copolymerizing a diol component with a diacid component.
- diol component examples include ethylene glycol (EG), 1,3 -propanediol (1,3-PDO), neopentyl glycol (NPG), dipropanediol (DPDO), diethylene glycol (DEG), triethylene glycol (TEG), polyethylene glycol (PEG, weight average molecular weight 200 ⁇ 100,000), 1,4-butanediol (1,4-BDO), 2-methyl-l,2-pro ⁇ anediol (MPDO), 1,4- cyclohexanedimethanol (1,4-CHDM), and propylene glycol.
- EG ethylene glycol
- 1,3-propanediol 1,3-propanediol
- NPG neopentyl glycol
- DPDO dipropanediol
- DEG diethylene glycol
- TEG triethylene glycol
- PEG polyethylene glycol
- MPDO 2-methyl-l,2-pro ⁇ anediol
- diacid component examples include terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, axelaic acid, sebacic acid, and ester derivatives thereof.
- polyamide resin used in the present invention examples include nylon-6, nylon-66, and nylon-MXD6.
- the barrier properties of the biaxially oriented laminated film can be improved depending on the kind of polyamide resin used.
- the polyester resin has a glass transition temperature of which is in the range of -5 0 C to +10 ° C based on that of the polyamide resin used.
- the glass transition temperature of the polyester resin of the outer layer is lower by 5 ° C than that of the polyamide resin of the inner layer, there arises the problem that the polyester resin constituting the outer layers undergoes crystallization during the preheating process, and breaks during the drawing process to makes it difficult to form a film.
- the polyamide resin inner layer undergoes crystallization at the preheating temperature at which the polyester resin is drawn to make it difficult to form a film.
- the outermost layer of the film be made of a polyester resin having a low moisture absorptivity, excellent printability, and workability.
- inorganic particles may be added to the polyester resin as a slippage promoter (lubricant) before melt-extruding.
- examples of such inorganic particles include silica gel, calcium carbonate, and alumina, having an average particle size of 0.01 to 10 ⁇ m.
- the inorganic particles may be added to the polyester resin in an amount appropriate in consideration of the optical characteristics of the film to be manufactured. For example, when a film having excellent transparency is to be manufactured, inorganic particles having a small particle size are mixed with inorganic particles having a large particle size at a proper mixing ratio, and then added to the polyester resin such that the amount of the inorganic particles is 0.04 to 0.07 wt% based on the total amount of polymer. Further, when 0.5 wt% or more of inorganic particles having an average particle size of 5 ⁇ m or more are added thereto, a film having low gloss may be obtained. Further, a relatively large amount of titanium dioxide (TiO 2 ) particles may be added to obtain a white film having improved whiteness, or a relatively large amount of silica gel particles may be added to improve the surface characteristics of the film.
- TiO 2 titanium
- an adhesive resin layer may be disposed between the polyamide resin layer and the polyester resin layer in order to improve the adhesion therebetween. That is, the adhesive resin layer is disposed between the polyamide resin layer and polyester resin layer, and then coextruded together with the polyamide resin layer and polyester resin layer to prepare a cast sheet.
- the prepared cast sheet has a five-layered structure of (B)-(C)-(A)- (C)-(B).
- the adhesive resin layer be made of a resin which can tightly bind the polyester resin and polyamide resin layers together and maintain transparency after drawing.
- Bynel manufactured by DuP ont Corp.
- DuP ont Corp. may be used as such an adhesive resin to prepare the adhesive resin layer.
- the cast sheet according to the present invention may be prepared through lamination of several nano layers, in which case, the adhesivity between the layers is excellent, and the use of the adhesive resin layer (C) may not be required.
- the resulting melt-extruded cast sheet is preheated at a temperature which is 5 to 20 ° C higher than the glass transition temperature (Tg) the a polyamide resin for 1 to 10 seconds, and the preheated sheet is subjected to a drawing process.
- Tg glass transition temperature
- the preheating time of the cast sheet is less than 1 second, it is difficult to supply a sufficient amount of heat necessary for uniformly drawing the laminate.
- the preheating time is more than 10 seconds, polymers constituting the respective layers may be crystallized, which makes it difficult to form a film.
- the preheating and drawing temperature of the cast sheet is 5 ° C or higher than the Tg of a polyamide resin
- the drawing stress of the polyamide resin increases excessively, and to make it difficult to form a film.
- the polyester resin of the outer layer of the cast sheet becomes crystallized during the preheating process, which makes it difficult to form a film having uniform thickness.
- the drawing process may be performed in both the transverse and longitudinal directions.
- the sheet is preferably drawn 1 to 4 times in the transverse direction and the longitudinal direction, respectively.
- one side or both sides of the film may be corona-treated or chemically coated.
- the film may be treated before it is drawn in the transverse and longitudinal directions, or may be treated before it is drawn in the transverse and longitudinal directions and then wound.
- a finished film may be treated using an off-line coating method.
- the film may be in-line coated before it is drawn in the transverse and longitudinal directions, or the finished film may be coated off-line.
- a predetermined amount of nano-clay particles having a plate(flake)-like structure may be added to at least one of the polyamide resin and polyester resin.
- the nano-clay particles may be added at the time of the preparation of the polyamide resin and polyester resin or before the melt- extruding of the laminate.
- the nano-clay particles having flake-type structure include biotite, lepidolite, kaolinite, halloysite, montmorillonite, margarite, talc, chlorite, and the like.
- one side or both sides of the laminate and the monoaxially or biaxially oriented film may be coated with nano-clay, SiOx, or Al 2 Ox (wherein, x is 1, 2 or 3) particles.
- the present invention comprises the biaxially oriented laminated film for wrapping manufacture by the method.
- the present invention comprises a wrapping material manufactured by combining the biaxially oriented laminated film with a substrate using a thermal adhesive resin layer on at least one side thereof, and it may be used in the post- treatment of forming the biaxially oriented laminated film into an envelope shaped film through a thermal adhesion method.
- the thermal adhesive resin layer may be made of linear low-density polyethylene (LLDPE) or cast polypropylene (CPP).
- the laminate thus obtained was coextruded with a T-die to prepare a cast sheet having a five-layered structure of (B)-(C)-(A)-(C)-(B).
- the cast sheet thus obtained was drawn at a draw ratio of 2.8 in the longitudinal direction using a drawing roll kept at 55 ° C and a cooling roll kept at 25 ° C .
- the resulting sheet was preheated to 50 ° C for 3 seconds, and drawn at a draw ratio of 3.2 in the transverse direction at 60 ° C using a tenter.
- the resulting oriented film was heat set at 190 °C, cooled, and subjected to 10% relaxation at 150 ° C , to obtain a biaxially oriented film having a thickness of 15 ⁇ m.
- Comparative Example 1 The procedure of Example 1 was repeated except for preheating the sheet to 50 ° C for 12 seconds before drawing in the transverse direction to obtain a film.
- Example 2 The procedure of Example 1 was repeated except for preheating and drawing in transverse direction at 65 0 C to obtain a film.
- Example 2 The procedure of Example 1 was repeated except for preheating and drawing in transverse direction at 65 0 C to obtain a film.
- Tg polytetramethylene terephthalate
- the cast sheet thus obtained was drawn at a draw ratio of 3 in the longitudinal directions using a drawing roll kept at 85 ° C and a cooling roll kept at 25 ° C .
- the resulting sheet was preheated to 90 ° C for 5 seconds, and drawn at a draw ratio of 3.5 in the transverse direction at 95 ° C using a tenter.
- the resulting oriented film was heat set at 210 ° C, cooled, and subjected to 3.5 % relaxation at 150 0 C , to obtain a biaxially oriented film having a thickness of 15 ⁇ m.
- Example 1 The procedure of Example 1 was repeated except for using nylon-6 nanocomposite resin (M 103 ODH, manufactured by Unitika Ltd.) containing plate- like nano-clay particles in place of Nylon 6, to obtain a biaxially oriented film having a thickness of 15 ⁇ m.
- nylon-6 nanocomposite resin M 103 ODH, manufactured by Unitika Ltd.
- Oxygen transmission rate (OTR)
- a sample film was cut to a size of 15 cm x 15 cm based on the JIS L 1096 standards.
- the cut film was mounted on a gas transmission rate (GTR) tester manufactured by Toyoseki Ltd., and the amount of oxygen passed through the cut film during a predetermined time was measured to determine the oxygen transmission rate (unit: cc/m 2 /atm/day) of the cut film, using a computer program.
- GTR gas transmission rate
- the water vapor transmission rate (unit: g/m 2 /day) of a sample film was measured based on ASMT F 372 standards using a moisture meter (PERMATRAN-W (model name), manufactured by Mocon Ltd.).
- PTT polytrimethylene terephthalate
- PA-6 nylon-6
- PBT polytetramethylene terephthalate
- PET polyethylene terephthalate
- AA(5)-co-PTT PTT copolymerized with 5 mol% of adipic acid
- PA-MXD6 nylon-MXD6 (prepared by the condensation and polymerization of methaxylene diamine and adipic acid)
- PA-Composite nylon-6 resin (nylon-6 nanocomposite) containing plate- like nano-clay particles
- OTR oxygen transmission rate
- the biaxially oriented laminated film for wrapping according to the present invention is superior to the conventional films in terms of water and gas barrier properties, toughness such as flex and pinhole resistance, and workability such as printability and bondability, and controlling the water and gas barrier properties.
Abstract
The present invention relates to a biaxially oriented laminated film for wrapping and a method of manufacturing the same. The inventive biaxially oriented laminated film exhibits excellent performance characteristics in terms of water and gas barrier properties, flex and pinhole resistance, and workability.
Description
BIAXIALLY ORIENTED LAMINATED FILM FOR WRAPPING FOOD ARTICLES AND METHOD OF MANUFACTURING SAME
FIELD OF THE INVENTION
The present invention relates to a biaxially oriented laminated film for wrapping food articles, and a method of manufacturing thereof.
BACKGROUND OF THE INVENTION
A wrapping material for food products is required to have satisfactory gas
/water barrier properties and tear-resistance for the preservation of the food during storage and transportation. Accordingly, there have been conducted a number of studies to develop such materials having the above-mentioned properties, as well as transparency and tolerability for microwave use.
For example, Japanese Laid-open Patent Publication No. 1997-289288 discloses a transparent film having excellent gas and water barrier properties, which comprises two layers composed of two or more kinds of inorganic oxides sequentially stacked on one side of a biaxially oriented nylon base film. However, this film tends to undergo undesirable cracking and suffers from processing difficulties due to the tendency of the nylon-6 film to absorb moisture.
Further, Japanese Laid-open Patent Publication Nos. 1996-296138 and 1987-056675 disclose methods for improving gas barrier properties by depositing inorganic oxides on a transparent plastic film. However, they also suffer from the problem of cracking and poor surface characteristics for printing.
Furthermore, Japanese Laid-open Patent Publication No. 2004-351874 discloses a method of manufacturing a transparent barrier film composed essentially of two polyamide (PA) e.g. nylon-6 layers disposed on both sides of a resin layer essentially consisting of an ethylene-vinylalcohol (EVOH) copolymer. Although this method provides improved barrier properties of nylon-6 film, the problem of moisture absorptivity of nylon-6 and ethylene-vinylalcohol copolymer remains unsolved.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a biaxially oriented laminated film for wrapping having excellent performance characteristics in terms of water and gas barrier properties, flex and pinhole resistance, and workability. In accordance with one aspect of the present invention, there is provided a method of manufacturing a biaxially oriented laminated film, comprising:
(1) melt-extruding a polyamide resin (A) and a polyester resin (B) which satisfying the following equation, to form a two or more layered laminate, and rapidly cooling the laminate to prepare a cast sheet: Tg(A) - 50C < Tg(B) < Tg(A) + 10 °C wherein Tg(A) is the glass transition temperature (0C) of the polyamide resin, and Tg(B) is the glass transition temperature ("C) of the polyester resin; and
(2) preheating and biaxially drawing the cast sheet at a temperature which is 5 to 20 °C higher than Tg(A) for 1 to 10 seconds. In accordance with another aspect of the present invention, there is provided a biaxially oriented laminated film manufactured by the method.
In accordance with still another aspect of the present invention, there is provided a wrapping material including the biaxially oriented laminated film.
DETAILED DESCRIPTION OF THE INVENTION
A method of manufacturing a biaxially oriented laminated film according to an embodiment of the present invention includes:
(1) melt-extruding a polyamide resin (A) and a polyester resin (B) which satisfying the following equation, to form a two or more layered laminate, and rapidly cooling the laminate to prepare a cast sheet: Tg(A) - 5 °C < Tg(B) < Tg(A) + 10 °C wherein Tg(A) is the glass transition temperature (°C) of the polyamide resin, and Tg(B) is the glass transition temperature ("C) of the polyester resin; and
(2) preheating and biaxially drawing the cast sheet at a temperature which is 5 to 20 °C higher than Tg(A) for 1 tolO seconds.
In order to manufacture the inventive biaxially oriented laminated film, polyamide resin (A) and polyester resin (B), which satisfies the above equation are melt-extruded using a T-die to form a two or more layered laminate, and then the laminate is rapidly cooled using a cooling roll to prepare a cast sheet. The polyester resin used in the present invention may be prepared by copolymerizing a diol component with a diacid component. Examples of the diol component include ethylene glycol (EG), 1,3 -propanediol (1,3-PDO), neopentyl glycol (NPG), dipropanediol (DPDO), diethylene glycol (DEG), triethylene glycol (TEG), polyethylene glycol (PEG, weight average molecular weight 200 ~ 100,000), 1,4-butanediol (1,4-BDO), 2-methyl-l,2-proρanediol (MPDO), 1,4- cyclohexanedimethanol (1,4-CHDM), and propylene glycol. Examples of the
diacid component include terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, axelaic acid, sebacic acid, and ester derivatives thereof.
Examples of the polyamide resin used in the present invention include nylon-6, nylon-66, and nylon-MXD6. The barrier properties of the biaxially oriented laminated film can be improved depending on the kind of polyamide resin used.
It is preferred that the polyester resin has a glass transition temperature of which is in the range of -50C to +10 °C based on that of the polyamide resin used. For example, as in the case of the present invention where the polyamide resin is used to form an inner layer and the polyester resin is used to form outer layers, when the glass transition temperature of the polyester resin of the outer layer is lower by 5 °C than that of the polyamide resin of the inner layer, there arises the problem that the polyester resin constituting the outer layers undergoes crystallization during the preheating process, and breaks during the drawing process to makes it difficult to form a film. Further, when the glass transition temperature of the polyester resin is higher by 10 °C than that of the polyamide resin, the polyamide resin inner layer undergoes crystallization at the preheating temperature at which the polyester resin is drawn to make it difficult to form a film. In case a film having a three or more layered laminate structure is manufactured using the method according to the present invention, it is preferred that the outermost layer of the film be made of a polyester resin having a low moisture absorptivity, excellent printability, and workability. In this case, in order to increase the post- workability of the outermost layer after drawing and heat set, inorganic particles may be added to the polyester resin as a slippage promoter (lubricant) before melt-extruding. Examples of such inorganic particles include
silica gel, calcium carbonate, and alumina, having an average particle size of 0.01 to 10 μm. The inorganic particles may be added to the polyester resin in an amount appropriate in consideration of the optical characteristics of the film to be manufactured. For example, when a film having excellent transparency is to be manufactured, inorganic particles having a small particle size are mixed with inorganic particles having a large particle size at a proper mixing ratio, and then added to the polyester resin such that the amount of the inorganic particles is 0.04 to 0.07 wt% based on the total amount of polymer. Further, when 0.5 wt% or more of inorganic particles having an average particle size of 5 ^m or more are added thereto, a film having low gloss may be obtained. Further, a relatively large amount of titanium dioxide (TiO2) particles may be added to obtain a white film having improved whiteness, or a relatively large amount of silica gel particles may be added to improve the surface characteristics of the film.
Further, generally, since the adhesivity between a polyamide resin layer and a polyester resin layer is low, an adhesive resin layer may be disposed between the polyamide resin layer and the polyester resin layer in order to improve the adhesion therebetween. That is, the adhesive resin layer is disposed between the polyamide resin layer and polyester resin layer, and then coextruded together with the polyamide resin layer and polyester resin layer to prepare a cast sheet. For example, when the adhesive resin layer (C) is disposed between the polyamide resin layer (A) and polyester resin layer (B) and is then coextruded together with the polyamide resin layer (A) as an inner layer and the polyester resin layers (B) to as outer layers, the prepared cast sheet has a five-layered structure of (B)-(C)-(A)- (C)-(B). It is preferred that the adhesive resin layer be made of a resin which can tightly bind the polyester resin and polyamide resin layers together and maintain transparency after drawing. Bynel (manufactured by DuP ont Corp.) may be used
as such an adhesive resin to prepare the adhesive resin layer.
It must be noted that the cast sheet according to the present invention may be prepared through lamination of several nano layers, in which case, the adhesivity between the layers is excellent, and the use of the adhesive resin layer (C) may not be required.
Subsequently, the resulting melt-extruded cast sheet is preheated at a temperature which is 5 to 20 °C higher than the glass transition temperature (Tg) the a polyamide resin for 1 to 10 seconds, and the preheated sheet is subjected to a drawing process. When the preheating time of the cast sheet is less than 1 second, it is difficult to supply a sufficient amount of heat necessary for uniformly drawing the laminate. In contrast, when the preheating time is more than 10 seconds, polymers constituting the respective layers may be crystallized, which makes it difficult to form a film.
Further, when the preheating and drawing temperature of the cast sheet is 5 °C or higher than the Tg of a polyamide resin, the drawing stress of the polyamide resin increases excessively, and to make it difficult to form a film. In contrast, when the cast sheet is preheated and drawn at a temperature 20 °C higher than the Tg of the polyamide resin, the polyester resin of the outer layer of the cast sheet becomes crystallized during the preheating process, which makes it difficult to form a film having uniform thickness.
The drawing process may be performed in both the transverse and longitudinal directions. In the drawing process, the sheet is preferably drawn 1 to 4 times in the transverse direction and the longitudinal direction, respectively.
Additionally, in order to improve the printability, coating adhesion, deposition strength and antistatic properties of the inventive films, one side or both sides of the film may be corona-treated or chemically coated. In case of the
corona treatment, the film may be treated before it is drawn in the transverse and longitudinal directions, or may be treated before it is drawn in the transverse and longitudinal directions and then wound. Further, a finished film may be treated using an off-line coating method. For the chemical coating treatment, the film may be in-line coated before it is drawn in the transverse and longitudinal directions, or the finished film may be coated off-line.
Further, in order to improve the gas barrier properties of the film according to the present invention, a predetermined amount of nano-clay particles having a plate(flake)-like structure may be added to at least one of the polyamide resin and polyester resin. In this case, the nano-clay particles may be added at the time of the preparation of the polyamide resin and polyester resin or before the melt- extruding of the laminate. Examples of the nano-clay particles having flake-type structure include biotite, lepidolite, kaolinite, halloysite, montmorillonite, margarite, talc, chlorite, and the like. Furthermore, in order to improve the gas barrier properties of the film according to the present invention, one side or both sides of the laminate and the monoaxially or biaxially oriented film may be coated with nano-clay, SiOx, or Al2Ox (wherein, x is 1, 2 or 3) particles.
The present invention comprises the biaxially oriented laminated film for wrapping manufacture by the method.
Further, the present invention comprises a wrapping material manufactured by combining the biaxially oriented laminated film with a substrate using a thermal adhesive resin layer on at least one side thereof, and it may be used in the post- treatment of forming the biaxially oriented laminated film into an envelope shaped film through a thermal adhesion method. The thermal adhesive resin layer may be made of linear low-density polyethylene (LLDPE) or cast polypropylene (CPP).
The following Examples are now given for the purpose of illustration only, and are not intended to limit the scope of the invention.
Example 1
A laminate was prepared using a Nylon 6 (glass transition temperature(Tg) = 45 °C) film (A) as an inner layer, two polytrimethylene terephthalate (Tg = 42 "C) films (B) as outer layers, and two Bynel resin films (C)(DuPont Corp.) as adhesive layers disposed between the inner and the outer layers. The laminate thus obtained was coextruded with a T-die to prepare a cast sheet having a five-layered structure of (B)-(C)-(A)-(C)-(B).
The cast sheet thus obtained was drawn at a draw ratio of 2.8 in the longitudinal direction using a drawing roll kept at 55 °C and a cooling roll kept at 25 °C . The resulting sheet was preheated to 50 °C for 3 seconds, and drawn at a draw ratio of 3.2 in the transverse direction at 60 °C using a tenter. The resulting oriented film was heat set at 190 °C, cooled, and subjected to 10% relaxation at 150 °C , to obtain a biaxially oriented film having a thickness of 15 μm.
Comparative Example 1 The procedure of Example 1 was repeated except for preheating the sheet to 50 °C for 12 seconds before drawing in the transverse direction to obtain a film.
Comparative Example 2
The procedure of Example 1 was repeated except for preheating and drawing in transverse direction at 650C to obtain a film.
Example 2
The procedure of Example 1 was repeated except for using adipic acid- copolymerized polytrimethylene terephthalate (Tg = 38 "C) ^produced by copolymerizing a diacid component comprising 5 mol% of adipic acid and 95 mol% of terephthalic acid with 1,3 -propanediol in place of Nylon 6, to obtain a biaxially oriented film having a thickness of 15 μm.
Example 3 The procedure of Example 1 was repeated except for using polytetramethylene terephthalate (Tg = about 38 °C) in place of polytrimethylene terephthalate, to obtain a biaxially oriented film having a thickness of 15 μm.
Example 4 Nylon-MXD6 (Tg = about 81 "C)(A) and polytrimethylene naphthalate (Tg
= 78 "C)(B) were coextruded using the procedure of Example 1 to prepare a cast sheet
The cast sheet thus obtained was drawn at a draw ratio of 3 in the longitudinal directions using a drawing roll kept at 85 °C and a cooling roll kept at 25 °C . The resulting sheet was preheated to 90 °C for 5 seconds, and drawn at a draw ratio of 3.5 in the transverse direction at 95 °C using a tenter. Then, the resulting oriented film was heat set at 210 °C, cooled, and subjected to 3.5 % relaxation at 1500C , to obtain a biaxially oriented film having a thickness of 15 μm.
Example 5
The procedure of Example 1 was repeated except for using nylon-6
nanocomposite resin (M 103 ODH, manufactured by Unitika Ltd.) containing plate- like nano-clay particles in place of Nylon 6, to obtain a biaxially oriented film having a thickness of 15 μm.
Comparative Example 3
The physical properties of a commercially available polyethylene terephthalate film having a thickness of 15 (M were measured and they were compared with those of the films manufactured in Examples of the present invention.
Comparative Example 4
The physical properties of a commercially available nylon-6 film having a thickness of 15 (M were measured and they were compared with those of the firms manufactured in Examples of the present invention.
Experimental Example
The physical properties of the films manufactured in Examples and Comparative Examples were evaluated as follow, and the results are shown in Table 1.
(1) Oxygen transmission rate (OTR)
A sample film was cut to a size of 15 cm x 15 cm based on the JIS L 1096 standards. The cut film was mounted on a gas transmission rate (GTR) tester manufactured by Toyoseki Ltd., and the amount of oxygen passed through the cut film during a predetermined time was measured to determine the oxygen
transmission rate (unit: cc/m2/atm/day) of the cut film, using a computer program.
(2) Water vapor transmission rate (WVTR)
The water vapor transmission rate (unit: g/m2/day) of a sample film was measured based on ASMT F 372 standards using a moisture meter (PERMATRAN-W (model name), manufactured by Mocon Ltd.).
(3) Glass transition temperature (Tg)
Each of the resins used in the Examples and Comparative Examples was melt-extruded under prescribed conditions through a T die, and rapidly cooled on a cooling roll maintained at 30 °C , to prepare a cast sheet having a thickness of 150 to 200 μm. The glass transition temperatures (Tg, "C) of the sheet was measured under a nitrogen atmosphere at a heating rate of 10°C/min using a differential scanning calorimeter (DSC) manufactured by Perkin-Elmer Corp.
(4) Flex and pinhole resistance
A sample film was subjected to a rotational stress test using Gelbo Flex
(Gelbo Inc., USA) at an angle of 450 degree for 500 cycles. Next, the sample film was placed flat on a white paper, whereon an a general solvent nitroglycerin (NC) ink was applied with a doctor blade. The number of ink dots appeared on the white paper was measured as the pin-hole number. An average value derived from 3 repeated tests was used to represent each sample.
Table 1
I
K) I
PTT: polytrimethylene terephthalate
PA-6: nylon-6
PBT: polytetramethylene terephthalate
PTN: polytrimethylene naphthalate PET: polyethylene terephthalate
AA(5)-co-PTT: PTT copolymerized with 5 mol% of adipic acid
PA-MXD6: nylon-MXD6 (prepared by the condensation and polymerization of methaxylene diamine and adipic acid)
PA-Composite: nylon-6 resin (nylon-6 nanocomposite) containing plate- like nano-clay particles
OTR: oxygen transmission rate
WVTR: water vapor transmission rate
As described above, the biaxially oriented laminated film for wrapping according to the present invention is superior to the conventional films in terms of water and gas barrier properties, toughness such as flex and pinhole resistance, and workability such as printability and bondability, and controlling the water and gas barrier properties.
While the invention has been shown and described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims.
Claims
1. A method of manufacturing a biaxially oriented laminated film, comprising: (1) melt-extruding a polyamide resin (A) and a polyester resin (B) which satisfying the following equation, to form a two or more layered laminate, and rapidly cooling the laminate to prepare a cast sheet: Tg(A) - 5 °C < Tg(B) < Tg(A) + 10 °C wherein Tg(A) is the glass transition temperature ("C) of the polyamide resin, and Tg(B) is the glass transition temperature ( °C ) of the polyester resin; and
(2) preheating and biaxially drawing the cast sheet at a temperature which is 5 to 20 °C higher than Tg(A) for 1 to 10 seconds.
2. The method of manufacturing a biaxially oriented laminated film of claim 1, wherein the polyamide resin is selected from the group consisting of nylon-6, nylon-66 and nylon-MXD6.
3. The method of manufacturing a biaxially oriented laminated film of claim 1, wherein the polyester resin is prepared by copolymerizing a diol component selected from the group consisting of ethylene glycol, 1 ,3 -propanediol, neopentyl glycol, dipropanediol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,4-butanediol, 2-methyl-l,2-propanediol, 1,4- cyclohexanedimethanol, and propylene glycol with a diacid component selected from the group consisting of terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, axelaic acid, sebacic acid, and ester derivatives thereof.
4. The method of manufacturing a biaxially oriented laminated film of claim 1, wherein at least one of the polyamide resin and polyester resin contains nano-clay particles.
5. The method of manufacturing a biaxially oriented laminated film of claim 1, further comprising: coating the laminate or the biaxially oriented film with a nano-clay, SiOx, OrAl2Ox (wherein, x is 1, 2 or 3) particles on at least one side thereof.
6. The method of manufacturing a biaxially oriented laminated film of claim 4 or 5, wherein the nano-clay particles are selected from the group consisting of particles of biotite, lepidolite, kaolinite, halloysite, montmorillonite, margarite, talc, and chlorite.
7. A biaxially oriented laminated film for wrapping, which is manufactured by the method of claim 1.
8. A wrapping material manufactured by combining the biaxially oriented laminated film of claim 7 with a substrate using a thermal adhesive resin layer.
9. The wrapping material of claim 8, wherein the thermal adhesive resin layer is made of a linear low-density polyethylene (LLDPE) or a cast polypropylene (CPP).
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| KR1020070121970A KR100928628B1 (en) | 2007-11-28 | 2007-11-28 | Biaxially oriented laminated film for packaging and method for producing same |
| KR10-2007-0121970 | 2007-11-28 |
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| JP2017222087A (en) * | 2016-06-15 | 2017-12-21 | ユニチカ株式会社 | Polyamide-based film and method for producing the same |
| CN107825794A (en) * | 2017-11-17 | 2018-03-23 | 上海紫江新材料科技有限公司 | A kind of top layer is biaxial tension nylon co-extrusion film of polyester and preparation method thereof |
| JP2021088190A (en) * | 2021-02-10 | 2021-06-10 | ユニチカ株式会社 | Polyamide-based film and method for producing the same |
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| CN103112306A (en) * | 2013-02-16 | 2013-05-22 | 王劲松 | Coloring and sand dyeing process for polyvinyl alcohol/water glass composite silicone product |
| KR102516587B1 (en) * | 2021-11-02 | 2023-04-04 | 한국생산기술연구원 | Method for gas barrier membrane with reduced oxygen permeability comprising a step of biaxial stretching |
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| JPH07101010A (en) * | 1993-08-13 | 1995-04-18 | Teijin Ltd | Laminated film for laminating and molding metal plates |
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| KR970008256B1 (en) * | 1993-11-29 | 1997-05-22 | 주식회사 에스.케이.씨 | Molding method for thermoplastic resin film |
| JP2000177004A (en) * | 1998-12-21 | 2000-06-27 | Toray Ind Inc | Production of heat resistant resin-laminated film |
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| JP2017222087A (en) * | 2016-06-15 | 2017-12-21 | ユニチカ株式会社 | Polyamide-based film and method for producing the same |
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| JP2021088190A (en) * | 2021-02-10 | 2021-06-10 | ユニチカ株式会社 | Polyamide-based film and method for producing the same |
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