WO2006013633A1 - 多層樹脂フィルム、樹脂被覆金属板、多層樹脂フィルムの製造方法、および樹脂被覆金属板の製造方法 - Google Patents
多層樹脂フィルム、樹脂被覆金属板、多層樹脂フィルムの製造方法、および樹脂被覆金属板の製造方法 Download PDFInfo
- Publication number
- WO2006013633A1 WO2006013633A1 PCT/JP2004/011359 JP2004011359W WO2006013633A1 WO 2006013633 A1 WO2006013633 A1 WO 2006013633A1 JP 2004011359 W JP2004011359 W JP 2004011359W WO 2006013633 A1 WO2006013633 A1 WO 2006013633A1
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- WO
- WIPO (PCT)
- Prior art keywords
- resin
- manifold
- multilayer
- film
- temperature
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 250
- 239000011347 resin Substances 0.000 title claims abstract description 250
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000000155 melt Substances 0.000 claims description 22
- 238000001125 extrusion Methods 0.000 claims description 13
- 238000010030 laminating Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 32
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000007599 discharging Methods 0.000 description 6
- 210000005069 ears Anatomy 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 description 5
- 238000010409 ironing Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 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 4
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000010349 pulsation Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000000704 physical effect Effects 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
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RIZUCYSQUWMQLX-UHFFFAOYSA-N 2,3-dimethylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C RIZUCYSQUWMQLX-UHFFFAOYSA-N 0.000 description 1
- YQPCHPBGAALCRT-UHFFFAOYSA-N 2-[1-(carboxymethyl)cyclohexyl]acetic acid Chemical compound OC(=O)CC1(CC(O)=O)CCCCC1 YQPCHPBGAALCRT-UHFFFAOYSA-N 0.000 description 1
- FKBFLMAMNNKUPJ-UHFFFAOYSA-N 2-hydroxy-3,4-dihydropyrazole Chemical compound ON1CCC=N1 FKBFLMAMNNKUPJ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- NIDZWWNRMZPMLN-UHFFFAOYSA-N [1,4,4-tris(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCC(CO)(CO)CC1 NIDZWWNRMZPMLN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XWENCHGJOCJZQO-UHFFFAOYSA-N ethane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)C(C(O)=O)C(O)=O XWENCHGJOCJZQO-UHFFFAOYSA-N 0.000 description 1
- RWLDAJMGAVDXSH-UHFFFAOYSA-N ethane-1,1,2-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(O)=O RWLDAJMGAVDXSH-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ROTJZTYLACIJIG-UHFFFAOYSA-N pentane-1,3,5-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 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
- 229920000728 polyester Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000037303 wrinkles Effects 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
- B29C48/03—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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24612—Composite web or sheet
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
-
- 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]
- Y10T428/31678—Of metal
Definitions
- Multilayer resin film resin-coated metal plate, method for producing multilayer resin film, and method for producing resin-coated metal plate
- the present invention relates to a multilayer resin film having a small surface irregularity composed of a plurality of resin layers having different melt tension and melt viscosity, a resin-covered metal plate coated with the multilayer resin film, and a multilayer resin film And a method for producing a resin-coated metal sheet.
- a multi-manifold die When a multi-manifold die is used to laminate and laminate a resin obtained by heating and melting such a resin at the same temperature, if the melt viscosity of the resin in contact with P differs, When the heated molten resin is merged as a multilayer resin, the flow of the heated molten resin may be disturbed at the interface between the resin layers, resulting in uneven thickness (unevenness) on the film surface.
- the uneven thickness on the surface of the film is called a flow mark, which is not only visually bad, but also includes drawing and drawing ironing to form a can body, and neck-in (small diameter) processing of the opening at the top of the can. Uniform processing is not possible during implementation, and this may cause the same as the moon break.
- Patent Document 1 discloses a method for preventing the generation of flow marks by selecting and using resins having a small difference in melting point and viscosity when heated and melted. Depending on the physical properties to be used, it is often necessary to select resins having mutually different melting points or viscosities at the time of heating and melting. The method disclosed in this publication is applicable only to extremely limited applications. Can not.
- Patent Document 2 uses a feed block method in which a plurality of heat-melted resin layers are joined in front of a T die, and a T die that is connected to the feed block and the feed block to form a multilayer resin film.
- a method is disclosed in which the temperature of the heater provided in the feed block is controlled to reduce defects such as misalignment (flow marks) at the layer boundary where the layers join.
- Fig. 2 shows an outline of an example of the multilayer extrusion molding apparatus.
- the multi-layer extrusion molding equipment consists of a feed block 10 having a plurality of manifolds 14a-14 g, and a T-die 12 that is connected to the feed block 10 below the junction 16 of the resin from the manifolds 14a 14g. Has been.
- Each manifold 14a Around the junction of the resin passages from 14g, for example, heaters 20b, 22b, thermometers 28b, etc. on the resin passage on the outlet side of manifold 14b The temperature / viscosity of each molten resin material supplied from each manifold is controlled to equalize the temperature / viscosity, thereby reducing defects at the layered interface that joins the multilayer resin.
- the inside of the T die into which the resin flows after merging into multiple layers has a single-layer structure, and the merged and multilayered resin passes from the merging portion 16 to the outlet opening 34 of the die lip 32. Since the distance to reach a large distance and the molten resin moves over that distance, the T-die is only heated as a whole. It is impossible to maintain the temperature with a temperature difference, and since the heating temperature of each resin layer changes at the outlet opening 34, the melt viscosity of each resin layer cannot be kept the same. It is difficult to prevent the generation of flow marks.
- the method according to this publication can be applied only to a limited use such as using a resin in which the difference in melting point for obtaining the same melt viscosity is not so different. Also, in the methods disclosed in these publications, the film forming speed cannot be increased when the tension of the molten resin is small.
- Patent Document 1 Japanese Patent Laid-Open No. 08-290532
- Patent Document 2 Japanese Patent Laid-Open No. 11-309770
- the present invention relates to a multilayer film comprising a plurality of resin layers having different melt viscosities, a multilayer resin film having small surface irregularities, a resin-coated metal plate obtained by laminating a multilayer resin film on a metal plate, And a method for producing a multilayer resin film by laminating a plurality of molten resins having different melt viscosities at high speed without forming irregularities on the film surface, and laminating the multilayer resin film on a metal plate It aims at providing the manufacturing method of a resin coating metal plate.
- the multilayer resin film of the present invention is a multilayer resin film composed of two or more kinds of resin forces, and the melt tension at the extrusion temperature of at least one of the resins is lg or more. And a multilayer resin film characterized in that the thickness is at least one third of the total thickness (Claim 1),
- the resin-coated metal plate of the present invention is a resin-coated metal plate obtained by laminating the multilayer resin film of any one of the above (Claim 1 or 2) on a metal plate.
- two or more kinds of resins including at least one kind of resin having a melt tension of 1 g or more at an extrusion temperature are respectively obtained using a multi-manifold die. Controls the temperature of each extruder continuously installed in the manifold, each manifold, and the portion of the die adjacent to each manifold, and passes through the extruder, manifold, and manifold through which the resin with high melt viscosity passes. The temperature of the adjacent die part is kept higher than the temperature of the extruder, manifold, and die part adjacent to the manifold through which the low-viscosity resin passes.
- two or more types of resins including at least one type of resin having a melt tension of lg or more at the extrusion temperature are respectively obtained using a multi-manifold die.
- the extruder, the manifold, and the manifold through which the resin having a high melt viscosity passes are controlled by controlling the temperature of each of the extruders continuously provided in the manifold, each manifold, and the die portion adjacent to each manifold.
- a method for producing a resin-coated metal sheet is characterized in that each molten resin is laminated and multilayered and then extruded onto the metal sheet (Claim 5).
- FIG. 1 is a schematic diagram showing an example of a method for producing a multilayer film of the present invention.
- FIG. 2 is a schematic view showing an example of a conventional method for producing a multilayer film. Marks in the figure For No. 1, 1 is a multi-manifold die, 2a and 2b are manifolds, 3a, 3b, 4a and 4b are heaters, 5 is a lip land, 6a is an extruder, 6b is an extruder, and 7 is a discharge 8 is a multilayer resin film, 9 is a cooling roll, 10a, 10b, 11a and l ib is a heater, 12f is a winding means, 14a, 14b, 14c, 14d, 14e, 14f and 14gf
- Reference numeral 16 denotes a manifold, 16 denotes a junction, 20b and 22b denote heaters, 28 denotes a thermometer, 32 denotes a die lip, and 34 denotes an outlet opening.
- FIG. 1 is a schematic view showing an example of a method for producing a multilayer film of the present invention comprising a plurality of resin layers having different melt viscosities.
- the multi-manifold die 1 having two manifolds 2a and 2b includes an extruder 6a that melts and extrudes one resin with a high melt viscosity, and an extruder that extrudes a resin with a lower melt viscosity by heating and melting. 6b is provided so as to be connected to 2a and 2b through resin passages, respectively.
- Manifolds 2a and 2b are merged under the multi-manifold die 1 to form a rip land 5 and continue to a discharge port 7 provided in the lowermost die lip of the multi-manifold die 1.
- the multi-manifold die 1 includes a heater 11a for heating the side of the die body through which the higher melt viscosity passes and a heater for heating the side through which the lower melt viscosity passes.
- l ib heaters 3a and 3b provided adjacent to the manifolds 2a and 2b to heat the manifolds 2a and 2b, and heaters 4a and 4b force S are provided, as well as extruders 6a and 6b and multi-manifolds.
- Heaters 10a and 10b are provided for heating the resin passages connecting 2a and 2b, respectively.
- a temperature measuring means such as a thermocouple (not shown) is provided near the site where each of these heaters is provided, and the heating temperature is controlled to be constant while measuring the temperature of each site, so that the manifolds 2a and 2b The temperature of each heater is individually controlled so that the difference in viscosity of each heated molten resin is within a certain range.
- the two types of resins having a difference in melt viscosity heated and melted in the extruder 6a and the extruder 6b of 3000-20000 poise at a cutting speed of 20-500 seconds- 1 are respectively It passes through manifolds 2a and 2b provided in fold die 1 and is stacked at the inlet of lip land 5 combined below multi-manifold die 1 and is discharged from discharge port 7 provided in the lowermost die lip of die 1.
- a coiler that is discharged on a cooling roll 9 configured to circulate a coolant such as water inside the outlet 7 is cooled and solidified into a multilayer resin film 8 and is continuously wound in a coil shape. It is beaten by means of collecting 12 such as
- the multilayer resin film of the present invention can be formed as follows using the multilayer resin film production apparatus thus configured.
- the resin film that can be applied is not particularly limited, and for example, the following polyester resins can be applied.
- the acid component from which the polyester resin is derived includes terephthalic acid, isophthalic acid, orthophthalic acid, P- / 3-oxyethoxybenzoic acid, naphthalene-1,6-dicarboxylic acid, diphenoxetane-1,4'-dicarboxylic acid, 5_sodium sulfoisophthalic acid and other dibasic aromatic dicarboxylic acids, hexahydroterephthalic acid, cyclohexanediacetic acid and other alicyclic dicarboxylic acids, adipic acid, sebacic acid, dimer acid and other aliphatic dicarboxylic acids, trimer Oxalic acid, pyromellitic acid, hemellitic acid, 1,1,2,2-ethanete
- the alcohol component from which the polyester is derived include ethylene glycol, propylene glycol, 1,4 monobutanediol, neopentyl glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, and cyclohexane dimethanol.
- diazolinol pentaerythritol, glycerol, trimethylolpropane, 1,2,6-hexantriol, sorbitol, 1,1,4,4-tetrakis (hydroxymethyl) cyclohexane And monohydric alcohols.
- these can be used alone or in combination of two or more.
- the melt tension of the resin heated and melted by the extruder 6a shown in Fig. 1 is lg or more).
- Each pellet is heated and melted by the extruders 6a and 6b and guided to the manifolds 2a and 2b connected through the resin passages in the multi-manifold die 1 provided below the extruders. , Go towards the coalesced part.
- each heater is controlled to be 3,000 poises or less while being measured by a temperature measuring means such as a thermocouple provided near each heater.
- the molten resin having a difference in melt viscosity of not more than 3000 poise at a shear rate of 20 to 500 seconds 1 is combined with the lip land of the manifolds 2a and 2b. Laminated at the inlet of 5, and discharged from the discharge port 7 onto the cooling roll 9 and solidified to form a multilayer (two-layer) film 8. Especially when the molten resin is extruded at a high speed, the resin melts at the extrusion temperature. If the tension is less than lg, the extruded film-like molten resin will pulsate, causing the thickness in the longitudinal direction to become non-uniform or causing an ear in the width direction.
- Resin with a melt tension of lg or more is used for at least one kind of resin, and the thickness of resin with a melt tension of lg or more is 1/3 or more of the total thickness of the extruded multilayer film.
- the cooling roll 9 After adjusting the difference in melt viscosity and adjusting the discharge amount using a resin having a melt tension of lg or more for at least one of the resins, the cooling roll 9 The multilayer (two-layer) film 8 discharged and solidified is scraped off by the scraping means 12. In this way, the multilayer resin film of the present invention is produced.
- the multilayer resin film of the present invention obtained as described above preferably has an unevenness difference of 5 ⁇ m or less on the surface of the multilayer resin film.
- the unevenness difference exceeds 5 ⁇ m, the multilayer resin film, which is not only visually defective, is laminated on the metal plate to form a multilayer resin film-coated metal plate.
- drawing or ironing is performed, or when the neck-in processing of the opening at the top of the can is performed, the resin film peels off from the metal plate, and the degree of processing is locally different Therefore, it can be broken in drawing and ironing, or it can be broken in the neck ink. And can not be molded into cans.
- the multilayer resin film of the present invention is laminated and coated by discharging the multilayer resin heated and melted from the discharge part of the die lip directly into a metal plate in the form of a film using the above-described method for producing a multilayer resin film. It can be set as a multilayer resin film covering metal plate.
- a multilayer resin film prepared by using the above-described multilayer resin film manufacturing method may be laminated on a metal plate directly or via an adhesive to form a multilayer resin film-coated metal plate using a known lamination method. You can also.
- the difference in unevenness on the surface of the multilayer resin film after the layer coating is 5 ⁇ m or less for the same reason as above. Preferably there is.
- Permeation resistance to a polyester resin excellent A ethylene terephthalate / ethylene isophthalate sauce over preparative copolymer (ethylene isophthalate 5 mole 0/0), mp: 230 ° C, intrinsic viscosity: 0. 92, 27 0 ° C , Shear rate: 100 seconds—melt viscosity at 1 : 10000 poise, melt tension: 0.8 g (hereinafter simply referred to as Resin A.
- Melt tension is Kyapirograph 3A (trade name: manufactured by Toyo Seiki Co., Ltd.) Resin temperature: 260 ° C, extrusion speed: lOmmZ min., Take-up speed: 10mZ min., Nozzle diameter: lmm, nozole length: 10mm) and polyester resin B (ethylene) with excellent work adhesion terephthalate Z ethylene isophthalate copolymer as modified with (ethylene isophthalate sagging over preparative 15 mole 0/0) of trimellitic acid (0.3 mole 0/0), mp: 215 ° C, intrinsic viscosity: 0.9 Melting point: 215 ° C, temperature 270 ° C and shear rate: 100 seconds— 1 Melt viscosity: 800 poise, melt tension: 1.2 g) (hereinafter simply referred to as “resin B”), both of resin A and resin B were heated and melted at 270 ° C.
- the ratio of the thickness of resin A to resin B after forming the two-layer film on each manifold of the multi-manifold die provided with a heater for temperature control is 2: 1, and the two-layer resin film
- the molten resin A and the molten resin B were introduced by adjusting the discharge rate so that the thickness was 16 / m.
- the resin passage and manifold through which the molten resin A of the multi-manifold die passes and the resin A through which the molten resin A passes, and the resin passage and manifold through which the molten resin B passes through the multi-manifold die and the resin passage through which the molten resin B pass are respectively adjacent heaters. Both were preheated to 260 ° C., and molten resin A and molten resin B were passed through the respective manifolds. After the molten resin A and the molten resin B are heated in this way, the molten resin A and the molten resin B are combined and laminated at the merged portion of the manifold, and the speed of 150 mZ through the combined force of the manifold and the lip land.
- the ejected resin When ejected as a two-layer resin, the ejected resin did not pulsate and no ears were formed in the width direction of the film. After discharging, it was dropped on a cooling roll in which water was circulated inside the discharge port and solidified by cooling, and it was wound on a coiler as a two-layer resin film having a width of about 1 m.
- Resin A and resin B as in Example 1 were used, and the same extruder and multi-manifold die as in Example 1 were used. Resin A and Resin B were heated and melted under the same conditions as in Example 1 except that the discharge rate was adjusted so that the ratio was 2.5: 1, and the speed was 150 m / min via the lip land from the manifold merge point.
- the discharge rate was adjusted so that the ratio was 2.5: 1, and the speed was 150 m / min via the lip land from the manifold merge point.
- the discharged resin pulsated and an ear was formed in the width direction of the film. After discharging, it was dropped on a cooling roll in which water was circulated inside the discharge port and solidified by cooling, and was wound around a coiler as a two-layer resin film having a width of about lm.
- Resin A and resin B as in Example 1 were used, and the same extruder and multi-manifold die as in Example 1 were used. Resin A and Resin B were heated and melted under the same conditions as in Comparative Example 1 except that the discharge rate was adjusted so that the ratio was 2.5: 1. When the two-layer resin was discharged from the discharge port, the discharge resin did not pulsate, and no ears were generated in the width direction of the film. After discharging, on the cooling roll that circulates water inside the discharge port It was dropped and solidified by cooling, and it was wound on a coiler as a two-layer resin film having a width of about lm.
- Example 1 Polyester resin excellent in processability adhesiveness same resin A and C (ethylene terephthalate tallates / ethylene isophthalate copolymer (ethylene isophthalate 15 mole 0/0), mp: 215 ° C, intrinsic viscosity: 0 9. Melting point: 215 ° C, temperature: 270 ° C, shear rate: melt viscosity at 100 seconds 1 : 9000 poise, melt tension: 0.7 g) (hereinafter simply referred to as resin C) In the same manner as in Example 1, the discharge rate was adjusted so that the ratio of the thickness of Resin A to the thickness of Resin C after forming a two-layer film was 2: 1, and the resin A was subjected to the same conditions as in Example 1.
- resin C ethylene terephthalate tallates / ethylene isophthalate copolymer (ethylene isophthalate 15 mole 0/0), mp: 215 ° C, intrinsic viscosity: 0 9. Melting point: 215 ° C, temperature:
- Polyester resin D having excellent processability adhesiveness same resin A as in Example 1 (ethylene terephthalate tallates / ethylene isophthalate copolymer (ethylene isophthalate 15 mole 0/0) of trimellitic acid (0.2 mole%) in which denatured, mp: 215 ° C, intrinsic viscosity: 0.7, melting point: 215 ° C, the temperature 270 ° C a and a shear rate: 100 sec - melt viscosity at 1: 7500 poises, melt tension: 1. Og ) (Hereinafter simply referred to as Resin D), each was melted by using an extruder, Resin A at 280 ° C, and Resin D at 260 ° C.
- the resin passage and manifold through which the molten resin A of the multi-manifold die passes and the resin passage through which the molten resin A passes are at 280 ° C with the heater adjacent to it, and the resin passage through which the molten resin D of the multi-manifold die passes and the resin passage through which the molten resin D passes.
- Manifolds were preheated to 260 ° C with heaters adjacent to each, and molten resin A and molten resin D were passed through each manifold.
- the melt viscosity of Resin A at a temperature of 280 ° C and a shear rate of 100 seconds- 1 The temperature is 7500 poise, the temperature of Resin D is 260 ° C, and the melt viscosity at a shear rate of 100 seconds- 1 is 7000 poise.
- the molten resin A and the molten resin D are heated in this way, the molten resin A and the molten resin D are united and laminated at the united portion of the manifold, and then at a speed of 150 mZ through the lip land from the united point of the manifold.
- the discharge resin did not pulsate, and no ears were formed in the width direction of the film.
- Example 1 and Comparative Example 1-14 Continuing the thickness in the full width direction (approximately lm) every lm (16 locations) in the length of 15m in the longitudinal direction of the resin film 5 minutes after the start of film formation. Measured, and the difference between the maximum thickness and the minimum thickness of all measured values measured in the full width direction at 16 locations in the length direction was determined as a thickness irregularity.
- Table 1 shows the evaluation results.
- Example 1 1.6 1 5 (W minutes Comparative Example 1 6. 1 15 W minutes Comparative Example 2 1.9 80 m / min Comparative Example 3 5. 7 1 50 tn / min Example 2 2. 0 1 50 m / Min
- a resin-coated metal plate obtained by laminating the multilayer resin film of the present invention on a metal plate is a drawn can or It is suitable for molding into drawn iron cans, and the resin film does not peel off from the metal plate even after drawing, drawing ironing, or neck-in processing of the opening at the top of the can. Since there is no part with a different degree of processing, it can be stably molded into a can body without causing breakage in crushing and drawing and ironing or crashing in a neck-in carriage. Can do.
- At least one type of resin with a melt tension at the extrusion temperature of lg or more is included, and two or more types of resins with a difference in melt viscosity of 3000-20000 poise at a shear rate of 20 to 500 seconds 1 are added to the multi-manifold die.
- the extruders connected to each manifold, the respective manifolds, and the die parts adjacent to each manifold are controlled at their respective temperatures, through which high melt viscosity resin passes, The temperature of the die part adjacent to the manifold is kept higher than the temperature of the extruder through which the resin having a low melt viscosity passes, the manifold, and the die part adjacent to the manifold.
- the thickness of the resin melt tension is not less than lg the full
- Each melted resin was laminated to form a multilayer film so that it would be more than one third of the thickness, and it was obtained that pulsation and ear generation would not increase even if the film was formed at a high speed.
- the thickness unevenness of the resin film is extremely small.
- the multilayer film obtained in this way has a difference in unevenness on the surface of 5 ⁇ ⁇ ⁇ or less, it not only has excellent visual smoothness but also melts in the resin film as in a normal multilayer film.
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- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNA2004800437592A CN1997516A (zh) | 2004-08-06 | 2004-08-06 | 多层树脂膜、树脂被覆金属板、多层树脂膜的制造方法及树脂被覆金属板的制造方法 |
EP04771358.1A EP1780007B1 (en) | 2004-08-06 | 2004-08-06 | Multilayer resin film, resin-coated metal plate, multilayer resin film producing method, and resin-coated metal plate producing method |
KR1020077000688A KR101022266B1 (ko) | 2004-08-06 | 2004-08-06 | 다층수지필름, 수지피복 금속판, 다층수지필름의 제조방법,및 수지피복 금속판의 제조방법 |
PCT/JP2004/011359 WO2006013633A1 (ja) | 2004-08-06 | 2004-08-06 | 多層樹脂フィルム、樹脂被覆金属板、多層樹脂フィルムの製造方法、および樹脂被覆金属板の製造方法 |
US11/659,499 US20080075926A1 (en) | 2004-08-06 | 2004-08-06 | Description Multilayer Resin Films, Resin-Coated Metal Plates, a Method of Producing Multilayer Resin Films and a Method of Producing Resin-Coated Metal Plates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2004/011359 WO2006013633A1 (ja) | 2004-08-06 | 2004-08-06 | 多層樹脂フィルム、樹脂被覆金属板、多層樹脂フィルムの製造方法、および樹脂被覆金属板の製造方法 |
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WO2006013633A1 true WO2006013633A1 (ja) | 2006-02-09 |
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PCT/JP2004/011359 WO2006013633A1 (ja) | 2004-08-06 | 2004-08-06 | 多層樹脂フィルム、樹脂被覆金属板、多層樹脂フィルムの製造方法、および樹脂被覆金属板の製造方法 |
Country Status (5)
Country | Link |
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US (1) | US20080075926A1 (ja) |
EP (1) | EP1780007B1 (ja) |
KR (1) | KR101022266B1 (ja) |
CN (1) | CN1997516A (ja) |
WO (1) | WO2006013633A1 (ja) |
Families Citing this family (3)
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JP5755835B2 (ja) | 2009-09-29 | 2015-07-29 | 富士フイルム株式会社 | 内視鏡用可撓管及びその製造方法 |
US9586385B2 (en) * | 2014-08-27 | 2017-03-07 | 3M Innovative Properties Company | Inorganic multilayer lamination transfer films |
TW201618961A (zh) | 2014-08-27 | 2016-06-01 | 3M新設資產公司 | 電多層層壓轉印膜 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS63154322A (ja) * | 1986-12-19 | 1988-06-27 | Mitsubishi Kasei Corp | 金属被覆用複合フイルムまたはシ−トの製造法 |
JPH1086308A (ja) * | 1996-07-22 | 1998-04-07 | Kishimoto Akira | 積層体及びそれを用いた容器 |
JPH11240068A (ja) * | 1998-02-26 | 1999-09-07 | Mitsui Chem Inc | 多層インフレーションフィルムの製造方法、多層インフレーションフィルムおよび多層インフレーションフィルムからなる包装材 |
JP2000071388A (ja) * | 1998-09-01 | 2000-03-07 | Tsutsumi Yotaro | 製缶用積層体及びシームレス缶 |
JP2004299390A (ja) * | 2003-03-19 | 2004-10-28 | Toyo Seikan Kaisha Ltd | ラミネート用多層フィルム、ラミネート材、缶耐及び缶蓋 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005115744A1 (ja) * | 2004-05-31 | 2005-12-08 | Jfe Steel Corporation | 樹脂被覆金属板 |
-
2004
- 2004-08-06 KR KR1020077000688A patent/KR101022266B1/ko not_active IP Right Cessation
- 2004-08-06 CN CNA2004800437592A patent/CN1997516A/zh active Pending
- 2004-08-06 EP EP04771358.1A patent/EP1780007B1/en active Active
- 2004-08-06 WO PCT/JP2004/011359 patent/WO2006013633A1/ja active Application Filing
- 2004-08-06 US US11/659,499 patent/US20080075926A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS63154322A (ja) * | 1986-12-19 | 1988-06-27 | Mitsubishi Kasei Corp | 金属被覆用複合フイルムまたはシ−トの製造法 |
JPH1086308A (ja) * | 1996-07-22 | 1998-04-07 | Kishimoto Akira | 積層体及びそれを用いた容器 |
JPH11240068A (ja) * | 1998-02-26 | 1999-09-07 | Mitsui Chem Inc | 多層インフレーションフィルムの製造方法、多層インフレーションフィルムおよび多層インフレーションフィルムからなる包装材 |
JP2000071388A (ja) * | 1998-09-01 | 2000-03-07 | Tsutsumi Yotaro | 製缶用積層体及びシームレス缶 |
JP2004299390A (ja) * | 2003-03-19 | 2004-10-28 | Toyo Seikan Kaisha Ltd | ラミネート用多層フィルム、ラミネート材、缶耐及び缶蓋 |
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Title |
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SAWADA K.: "Plastic Oshidashi Seikei no Saishin Gijutsu.", 25 June 1993 (1993-06-25), pages 121 - 124, XP002996440 * |
See also references of EP1780007A4 * |
Also Published As
Publication number | Publication date |
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KR20070047281A (ko) | 2007-05-04 |
KR101022266B1 (ko) | 2011-03-21 |
EP1780007B1 (en) | 2018-10-17 |
US20080075926A1 (en) | 2008-03-27 |
EP1780007A4 (en) | 2010-10-27 |
EP1780007A1 (en) | 2007-05-02 |
CN1997516A (zh) | 2007-07-11 |
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