CN100387633C - Film for laminate and laminate comprising the same - Google Patents
Film for laminate and laminate comprising the same Download PDFInfo
- Publication number
- CN100387633C CN100387633C CNB2004800137530A CN200480013753A CN100387633C CN 100387633 C CN100387633 C CN 100387633C CN B2004800137530 A CNB2004800137530 A CN B2004800137530A CN 200480013753 A CN200480013753 A CN 200480013753A CN 100387633 C CN100387633 C CN 100387633C
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- Prior art keywords
- vibrin
- film
- laminating
- composition
- metallic matrix
- Prior art date
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- Expired - Lifetime
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- 238000010030 laminating Methods 0.000 claims abstract description 76
- 229920001225 polyester resin Polymers 0.000 claims abstract description 30
- 239000004645 polyester resin Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims description 114
- 229920001577 copolymer Polymers 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 49
- 239000011159 matrix material Substances 0.000 claims description 48
- 230000004927 fusion Effects 0.000 claims description 40
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyethylene terephthalate unit Polymers 0.000 claims description 7
- 229920005989 resin Polymers 0.000 abstract description 48
- 239000011347 resin Substances 0.000 abstract description 48
- 238000000034 method Methods 0.000 abstract description 34
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- 238000001125 extrusion Methods 0.000 abstract description 6
- 239000000155 melt Substances 0.000 abstract description 2
- 239000000796 flavoring agent Substances 0.000 abstract 1
- 235000019634 flavors Nutrition 0.000 abstract 1
- 230000010349 pulsation Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 121
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 238000011156 evaluation Methods 0.000 description 23
- 238000000576 coating method Methods 0.000 description 20
- 229920000728 polyester Polymers 0.000 description 20
- 230000006978 adaptation Effects 0.000 description 19
- 238000003475 lamination Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 238000012545 processing Methods 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 229910000838 Al alloy Inorganic materials 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000012528 membrane Substances 0.000 description 8
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 7
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 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 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
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- 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
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- XDZMPRGFOOFSBL-UHFFFAOYSA-N 2-ethoxybenzoic acid Chemical compound CCOC1=CC=CC=C1C(O)=O XDZMPRGFOOFSBL-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FQORROGUIFBEFC-UHFFFAOYSA-N OC(=O)C1=CC([Na])=CC(C(O)=O)=C1S(O)(=O)=O Chemical compound OC(=O)C1=CC([Na])=CC(C(O)=O)=C1S(O)(=O)=O FQORROGUIFBEFC-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
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- 238000003556 assay Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 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
- 238000011049 filling Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 229940059574 pentaerithrityl Drugs 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
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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Images
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- Laminated Bodies (AREA)
Abstract
A film for a laminate which comprises a first polyester resin containing 0.01 to 0.50 mole % of a polyfunctional component and exhibits a melt tensile strength of 50 mN or more; the film wherein the first polyester resin contains 10 to 20 mole % of a coplymerization component; and a film for a laminate which comprises a layer comprising the first polyester resin and another layer comprising another polyester resin. The above film is free from the shaking or pulsation thereof and can cover a metallic plate in a uniform thickness with good adhesion, even when it is laminated on the metallic plate by the use of the high speed extrusion laminating method, and the film comprising a resin containing the above-specified amount of a coplymerization component exhibits further improved adhesion to a metal. The film comprising two layers can also have good flavor characteristics in addition to the above.
Description
Technical field
The present invention relates to contain the film of vibrin system of multifunctional composition and the laminating material that this film that is covered is made, more particularly, relate to film and metal sheet can high speed laminated, can be with the good laminating material of processibility that good thickness evenness and binding property are overlayed on the film on the metal sheet and this film that is covered is made.
Technical background
Past, extensively utilize resin layer coated metal surface as the method for giving the metallic substance erosion resistance, coating method as such technology use, the crowd knows that the thermosetting resin that has Resins, epoxy, resol, acrylic resin, vibrin system etc. is dispersed in the method for solution coat on the metallic surface in the solvent, perhaps, utilize the sizing agent of isocyanate-based, epoxy system, phenolic aldehyde system etc., make preformed film, for example, polyester system, ethylene series, polyamide-based film and the metallic matrix method of fitting.
The bonding heat fusing tackiness of thermoplastic resin of utilizing of metallic matrix and thermoplastic resin also is widely known by the people, and the fused films of thermoplastic polyester that the known preformed film adhered method or make on metal sheet of utilizing that heat bonding makes thermoplastic polyester etc. is extruded in this method etc. is fitted in the method on the metal sheet.
Adopt the latter's the extruding layer platen press and the applying method of metal sheet, can handle very at a high speed, can obtain simultaneously to reduce and make the operation that film accompanies and the advantage of running cost.
As extruding layer platen press, the general T pattern head method of using forcing machine and T pattern head that adopts, but this T pattern head method is because the instability of forcing machine and die head inside flows or all there is air gap in what between die head and metal sheet, so use the occasion of general polyester, film swing, fluctuation etc. take place, and difficult binding property forms on metal sheet well to be stablized and the coating of uniform thickness is arranged.When improving the input speed of resin, cause these phenomenons especially easily, make the high speed lamination of vibrin very difficult.
As solving as the method for above-mentioned this problem, all motions are arranged, for example the applicant opens melt viscosity under the temperature of having put down in writing in the flat 10-86308 communique when melt extruding than (the leading portion speed during the polyester extrusion temperature 12.2 seconds the spy
-1Following melt viscosity η
12.2Velocity of shear during/polyester extrusion temperature 1216 seconds
-1Under melt viscosity η
1216) at the scope and the η that equal greater than 2.0
1216Equaling greater than 500 pools, after resin layer is melted and extrudes, by chilling is the laminating method of feature, when having put down in writing the vibrin that uses above polyprotonic acid of the ethylene oxide adduct that contains bis-phenol or trifunctional and polyvalent alcohol, this laminating method can suppress to draw resonance effect, utilizes the high speed lamination can obtain homogeneity and the good lining of binding property.
Special in addition open to have put down in writing in the 2001-72747 communique based on what contain 0.1～2.0 mole of % have the fusing point of ethylene glycol terephthalate of compound that 3 or 4 ester bonds form functional groups greater than 220 ℃ polyester, it is good that the die swelling of measuring under the temperature of fusing point+40 of this polyester ℃ is that the polyester more than 1.3 is extruded processibility.
Summary of the invention
Yet above-mentioned film for laminating requires tunicle that better adaptation (adherence) is arranged still can not fully meeting the demands aspect the cementability of metallic substance.
The polyester that contains multifunctional composition in addition, because easy residual monomer or oligopolymer, so the smell that this constituents stripping causes becomes problem, in the above-mentioned back-polyester of the prior art, also must carry out certain processing to polyester in order to reduce such monomer or oligopolymer.
Therefore do not produce as above-mentioned film swing when extruding laminating and metal sheet lamination at a high speed yet or fluctuate even the purpose of this invention is to provide to adopt, and can be overlayed on film on the metal sheet well with uniform thickness and binding property.
Another object of the present invention provides the homogeneity and the good laminating material of adaptation of the low molecular weight compositions stripping, the smell that prevent in the polyester good (Off レ one バ one property), while coating.
The invention provides film for laminating, it is characterized in that it is 50mN or above vibrin that this film comprises the multifunctional composition, the fusion tension force that contain 0.01～0.50 mole of %.
Above-mentioned film for laminating is preferred
Vibrin be based on the polyethylene terephthalate unit of the copolymer composition that contains 10～20 moles of % copolymer polyester resin,
Copolymer composition be m-phthalic acid,
The fusing point of copolymer polyester resin be lower than 220 ℃,
With the layer that aforementioned vibrin is first vibrin, the second other vibrin of lamination constitutes on the layer that first vibrin constitutes make,
The fusion tension force of fusion warp tension ratio second vibrin of first vibrin big,
The ratio of first vibrin and the fusion tension force of second vibrin be 1: 1～5: 1,
8. first vibrin is 50: 1～1: 5 with the ratio of the thickness of second vibrin.
Also provide a kind of laminating material according to the present invention, it is characterized in that making this film contact and make with metallic matrix by laminated above-mentioned film for laminating and metallic matrix.
Because film for laminating of the present invention is that 50mN or the copolymer polyester resin more than the 50mN are made by containing 0.01～0.50 mole of multifunctional composition of %, fusion tension force, even therefore be laminated to the occasion on the metallic matrix at high speed, also can prevent film swing or fluctuation, membrane supplying with homogeneous film thickness to metallic matrix, special in simultaneously containing the copolymer composition of 10～20 moles of %, the good laminating material of adaptation of film and metallic matrix can be provided.
Promptly, general vibrin (polyethylene terephthalate) is because fusion tension force and melt viscosity are low, so extrude when being laminated on the metallic matrix phenomenon of the film swing that the transverse end of the effusive molten resin film of generation T pattern head is rocked or the wave phenomenon that the effusive molten resin film of T pattern head longitudinally produces membrane thickness unevenness at high speed.Therefore, can not obtain uniform thickness, cause also reducing simultaneously with the adaptation of metallic matrix.On the other hand since the fusion tensile increase and to cause viscosity obviously to rise, so extrude poor in processability during the common forcing machine of use, can not extrude at a high speed.
The present invention from the viewpoint, by making vibrin contain 0.01～0.50 mole of multifunctional composition of %, on polyester backbone, import multifunctional composition, form side chain or cross linked chain, not making melt viscosity exceedingly rise, make fusion tension force is 50mN or more than the 50mN, even also can prevent to produce film swing or fluctuation effectively to extrude lamination at a high speed.
Result by aftermentioned embodiment can illustrate this action effect of the present invention.Promptly do not contain multifunctional composition, and fusion tension force is less than the vibrin (comparative example 1) of 50mN, though or contain multifunctional composition with the amount of above-mentioned scope, but in the vibrin (comparative example 2) of fusion tension force less than 50mN, when extruding with the speed of 100m/min, the swing of generation film, on the contrary, contain multifunctional composition with above-mentioned amount, film swing or fluctuation do not take place in the vibrin (embodiment 1～4) that fusion tension force is equal to or greater than 50mN, think by making multifunctional composition and the fusion tension force that vibrin contains 0.01～0.50 mole of % be equal to or greater than 50mN, then present excellent high speed and extrude plyability.
In addition, such polyester film lamination material, expectation further improves the binding property of film, and especially contain the copolymer polyester resin of m-phthalic acid with the amount of 10～20 moles of % among the present invention as copolymer composition as vibrin, preferred use, therefore can significantly improve the adaptation of film and metallic matrix.Particularly improving and the adaptation of film improves aspects such as thermotolerance, processibility simultaneously and preferably regulates and be copolymerized into fusing point that component makes copolymer polyester resin and be lower than 220 ℃, especially become 200～219 ℃ scope among the present invention.
By the result of aftermentioned embodiment this action effect also of the present invention as can be seen.Promptly with the amount of above-mentioned scope contain m-phthalic acid copolymer polyester resin (embodiment 1～4), can obtain good result aspect the adaptation of film, mismatch on the contrary, fully in the vibrin (comparative example 3) of m-phthalic acid or the copolyester (comparative example 4) that the m-phthalic acid amount is lacked than above-mentioned scope, the adaptation of film is poorer at the copolymer polyester resin of above-mentioned scope than m-phthalic acid amount.In addition, in the copolymer polyester resin that the m-phthalic acid amount is Duoed than above-mentioned scope (comparative example 5), the thermotolerance variation, therefore think for have concurrently two kinds of performances of adaptation and thermotolerance importantly the m-phthalic acid amount in above-mentioned scope.
In addition, contain the vibrin (first vibrin) of this multifunctional composition because polymerization velocity is fast, easy residual monomer or oligopolymer, the smell that this low molecular weight compositions stripping causes becomes problem, but be laminated in multilayer film on first polyester resin layer by forming second vibrin not contain this low molecular weight compositions among the present invention, can prevent the smell reduction that the low molecular weight compositions stripping from first polyester resin layer causes.
Promptly, utilize first vibrin that the extrude plyability of multilayer film under high speed improved, the smell reduction by using second vibrin to prevent to use this first vibrin to cause, can provide the multilayer film that possess all characteristics as multilayer film integral body.
In the multilayer film of the present invention, the fusion tension force of fusion warp tension ratio second vibrin of preferred first vibrin is big.Promptly, first vibrin, owing to the existence of multifunctional composition can not make melt viscosity in the forcing machine rise to make fusion tension force reach 50mN or more than the 50mN, but in second vibrin, because there are correlationship in fusion tension force and melt viscosity, so melt viscosity became too high when fusion tension force was big, forcing machine is applied over-drastic load, the cause that might be able to not extrude.
In addition, among the present invention especially first vibrin with preferred 1.1: 1～5: 1 of the ratio of the fusion tension force of second vibrin, particularly preferably in 1.5: 1～3: 1 scopes.That is, the difference of the fusion tension force of first vibrin and second vibrin is big, and the fusion tensile is than greater than above-mentioned scope the time, might fluctuate when extruding lamination at a high speed.And in the above-mentioned scope of comparing of fusion tension force hour, it is too high that the melt viscosity of second vibrin becomes, and as mentioned above, forcing machine applied the over-drastic load, might be able to not extrude.
The thickness of described first vibrin and second vibrin than preferably 50: 1～1: 5, spy preferably 10: 1～1: 1 scope.By making thickness than in above-mentioned scope, but balance is extruded plyability and smell two specific characters under having concurrently at a high speed well.
The laminating material that the film for laminating of the present invention that is covered forms, because the homogeneity and the adaptation of tunicle are good, thus have can stretch-proof processing, the processing of stretching deep drawn, stretching attenuate stretch process, the excellent machining property of the processing of bending harshnesses such as stretching attenuate stretch process of stretching.
Description of drawings
Fig. 1 is the figure of one of the cross section structure of expression laminating material of the present invention example.
Fig. 2 is the figure of one of the cross section structure of expression laminating material of the present invention example.
Fig. 3 is the figure of one of the cross section structure of expression laminating material of the present invention example.
Fig. 4 is the figure of one of the cross section structure of expression laminating material of the present invention example.
Fig. 5 is the figure of one of the cross section structure of expression laminating material of the present invention example.
Fig. 6 is the figure of one of the device of expression manufacturing laminating material of the present invention example.
Embodiment
(first vibrin)
The vibrin that uses with first vibrin of film as individual layer film for laminating of the present invention and laminated multi-layer, be to contain 0.01～0.50 mole of % of multifunctional composition, particularly contain the vibrin of 0.05～0.40 mole of %, except fusion tension force is 50mN or the above this point of 50mN, can use the vibrin of known in the past dicarboxylic acid composition and glycol component system.
That is, by in polyester backbone, import 3 officials can or above multifunctional composition, form side chain or cross linked chain, can make fusion tension force reach 50mN or more than the 50mN.
As the dicarboxylic acid composition, consider that from the mechanical properties or the thermal property of coating more than 50% of preferred dicarboxylic composition, special preferred 80% is a terephthalic acid, can certainly contain terephthalic acid carboxylic acid composition in addition.As the carboxylic acid composition beyond the terephthalic acid that becomes copolymer composition, can enumerate naphthalic acid, right-beta-hydroxy (oxy) ethoxybenzoic acid, xenyl-4,4 '-dicarboxylic acid, biphenoxyl ethane-4,4 '-dicarboxylic acid, 5-sodiosulfoisophthalic acid, six hydrogen terephthalic acids, hexanodioic acid, sebacic acid etc.
As glycol component, consider from the mechanical properties or the thermal property of coating, preferred 50% or more of glycol component, the spy is preferred is ethylene glycol more than 80%, as the glycol component beyond the ethylene glycol, can enumerate 1,4-butyleneglycol, propylene glycol, neopentyl glycol, 1, the ethylene oxide adduct of 6-hexylene glycol, Diethylene Glycol, triethylene glycol, cyclohexanedimethanol, dihydroxyphenyl propane, glycerol, TriMethylolPropane(TMP) etc.
Multifunctional composition is trifunctional or above polyprotonic acid and polyvalent alcohol, can enumerate trimellitic acid, Pyromellitic Acid, benzene-1,2,3-tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,1,2-ethane tricarboxylic acid, 1,3,5-pentane tricarboxylic acid, 1,2,3,4-pentamethylene tetracarboxylic acid, biphenyl-3,4, polyprotonic acid such as 3 ', 4 '-tetracarboxylic acid or tetramethylolmethane, glycerol, TriMethylolPropane(TMP), 1,2,6-hexanetriol, Sorbitol Powder, 1,1,4, polyvalent alcohols such as 4-four (methylol) hexanaphthene, but most preferably use trimellitic acid.
The preferred per unit polyester of the content of multifunctional composition contains 0.01～0.50 mole of %, especially preferably contains 0.05～0.40 mole of %, when being lower than above-mentioned scope, difficulty makes fusion tension force reach 50mN or more than the 50mN, can not prevent to extrude at a high speed film swing or the fluctuation that lamination causes effectively, and during greater than above-mentioned scope, have melt extrude that characteristic reduces, tendency that the mechanical property of coating or thermotolerance reduce.
The vibrin of the multifunctional composition of the used cooperation of the present invention, both can be the homopolymerization polyester, also can be the copolyester or the blend of these polyester more than 2 kinds or 2 kinds, but the most suitable special use contains the m-phthalic acid as copolymer composition with 10～20 moles of %, best amount with 11～17 moles of %, more than 50% of its spent acid composition, particularly being terephthalic acid more than 80%, more than 50% of pure composition, particularly is that the ethylene glycol terephthalate unit of ethylene glycol is the copolyester of main body more than 80%.By using m-phthalic acid, can reduce fusing point or crystallinity, raising binding property, promptly with the adaptation of metallic matrix as the dicarboxylic acid composition.
Consider the preferred 0.5～2.0dL/g of limiting viscosity, special preferred scope that vibrin of the present invention uses phenol/tetrachloroethane mixed solvent to measure at 0.6～1.5dL/g with the viewpoint that melt extrudes characteristic from the rerum natura of coating.
In addition, when satisfying the adaptation with film, also satisfy thermotolerance, processibility, melt extrude characteristic, preferably have and be lower than 220 ℃, spy and preferably have 200～219 ℃ fusing point (Tm).Preferred glass transition temperature more than 30 ℃, special preferably 50～120 ℃ scope in addition.
The polyester resin layer that the present invention uses can be according to antiblocking agent, titanium dioxide pigment such as (titanium whites), oxidation inhibitor, stablizer, various static inhibitor, lubricants etc. such as the known resin of known prescription cooperation Synergist S-421 95 itself, for example amorphous silicas.
(second vibrin)
Multilayer film of the present invention are multilayer film that the laminated second other vibrin forms on first vibrin that above-mentioned vibrin constitutes, this second vibrin preferably use with the relation of first polyester resin layer in, its fusion warp tension ratio first vibrin ratio little, fusion tension force is 1.1: 1～5: 1 a vibrin.
Particularly, the known in the past vibrin that can use the dicarboxylic acid composition enumerated in first vibrin and glycol component to constitute, but because second polyester resin layer is the resin layer that keeps the smell of multilayer film, Gu Te preferably based on by the dicarboxylic acid composition 80% or above be terephthalic acid and glycol component 80% or above be the polyester of the ethylene glycol terephthalate that constitutes of ethylene glycol.
In addition, consider that second vibrin preferably uses the limiting viscosity of phenol/tetrachloroethane mixed solvent mensuration in 0.5～2.0dl/g, special preferred scope at 0.6～1.5dl/g from the object and the viewpoint that melt extrudes characteristic of coating.In addition, consider to preferably have 160～270 ℃, spy from thermotolerance, processibility and the viewpoint that melt extrudes characteristic and preferably have 200～260 ℃ fusing point (Tm).In addition, the preferred glass transition temperature is 30 ℃ or above, special preferred 50～120 ℃ scope.
Also similarly can cooperate above-mentioned known in the past resin Synergist S-421 95 in second polyester resin layer according to known prescription with first polyester resin layer.
(metallic matrix)
As the metallic matrix for the treatment of the above-mentioned film of lamination, use light metal plate or these paper tinsels such as various surface treated steel plates or aluminium among the present invention.
As surface treated steel plate, can use cold-rolled steel sheet annealing back temper rolling (Tone Quality calendering) or the steel plate that obtains of secondary cold-rolling, promptly carry out one or two or more kinds the steel plate in the surface treatments such as zinc-plated, zinc-plated, nickel plating, the processing of electrolysis chromic acid, chromic acid processing to SR material or DR material.One example of the surface treated steel plate that is fit to is that the electrolysis chromic acid is handled steel plate, particularly has 10～200mg/m
2Metallic chromium layer and 1～50mg/m
2The steel plate of the chromium oxide layer of (press chromium metal convert), this steel plate the combining of adaptation and erosion resistance of filming.Another example of surface treated steel plate is that 0.6～11.2g/m is arranged
2The hard tin (Block リ キ plate) of zinc-plated amount.This tin preferably carries out the chromic acid processing or chromic acid/phosphoric acid is handled, and makes it to convert by chromium metal, and the chromium amount is 1～30mg/m
2Can use the aluminium-coated steel plate of aluminizing, implement aluminium pressure welding etc. as an other example.
As the light metal plate, except so-called pure aluminum plate, can use aluminium alloy plate.At aluminium alloy plate good aspect erosion resistance and the processibility is that Mn:0.2～1.5 weight %, Mg:0.8～5 weight %, Zn:0.25～0.3 weight % and Cu:0.16～0.26 weight %, rest part are arranged is the aluminium alloy plate of A1 component.These light metal plates also preferably carry out the chromic acid processing or chromic acid/phosphoric acid processing makes it to convert by chromium metal, and the chromium amount is 20～300mg/m
2
The thickness of metal sheet is also because of the kind of metal, the purposes or the size difference of laminating material, but generally preferably have the thickness of 0.10～0.50mm, wherein surface treated steel plate preferably has the thickness of 0.10～0.30mm, and the light metal plate preferably has the thickness of 0.15～0.40mm.
When adopting the extruding layer platen press that film of the present invention and metallic matrix are carried out lamination, because the binding property of film of the present invention and metallic matrix is good, so do not need on metallic matrix, to set in advance especially adhesion primer coating (then プ ラ ィ マ one), adhesion primer coating can be set as required certainly yet.
Such bottom coating is that metallic matrix and vibrin are shown good fusible bottom coating, representative coatings as the bottom coating of binding property and good corrosion resistance, be that the phenolic aldehyde epoxy that solvable type phenolic resin type resol and bisphenol-type epoxy resin by all phenols and formaldehyde-derived constitute is a coating, particularly with 50: 50～5: 95, particularly contain the coating of resol and Resins, epoxy with 40: 60～10: 90 weight ratio.Adhesion primer generally can be set as the thickness of 0.3～5 μ m.
(laminating material)
Laminating material of the present invention, be that handle is at film of the present invention, promptly, the single thin film that first vibrin constitutes, and described single thin film on the multilayer film that form of laminated other vibrin (containing second vibrin) overlayed on the laminating material that forms on the metallic matrix, wherein the mode that contacts with metallic matrix of the layer that constitutes with first vibrin is covered.
Laminating material of the present invention is processed into jar or during cover etc., must be at least become jar or the face of the internal surface of cover on form film of the present invention, can certainly become laminated film 5 of the present invention on the face of outside surface.
The occasion of the multilayer film of the layer that the layer that other first vibrin forms and second vibrin form, aspect smell, importantly make first polyester resin layer be laminated in the metal matrix side, but be not used in the occasion of the internal surface of container etc., do not have this restriction, can make the laminated one-tenth of first polyester resin layer top layer yet.
Formed film on the film that first vibrin constitutes in addition, the film that preferably aforesaid second vibrin constitutes, but do not get rid of other the film that thermoplastic resin constituted.
Fig. 1 is one of the cross section structure of an expression laminating material of the present invention routine composition.In laminating material shown in Figure 11, on metallic matrix 2, form the film 3 that first vibrin becomes.
In the laminating material 1 shown in Figure 2, on a face of metallic matrix 2, on the film 3 that first vibrin constitutes, form the film 4 that second vibrin constitutes.
In the laminating material 1 that Fig. 3 represents, on a face of metallic matrix 2, on the film 3 that first vibrin constitutes, form the film 4 that second vibrin constitutes, on another side, form the film 5 that first vibrin constitutes.
In addition, in the laminating material 1 that Fig. 4 represents, on two faces of metallic matrix 2, form first polyester resin layer 3,5 and second polyester resin layer 4,6.
And Fig. 5 is except in the laminating material of representing at Fig. 2, is being provided with between first polyester resin layer 3 and the metallic matrix 2 beyond the sizing agent resin layer 7, and other are identical with Fig. 1.
(laminating method)
Film of the present invention can adopt extrusion moulding moulding such as T pattern head method or blowing system embrane method, and further form the film that constitutes by other vibrin occasion as the multilayer film on upper strata, except employing co-extrusion modling method, a plurality of forcing machines that use adaptation resin type requirements, use multilayer multimode head, other can be identical with common T pattern head method or blowing system embrane method, after using forcing machine with various resin melting mixings, by T pattern head or the first-class shape moulding of extruding multilayer film of circular die.The film that can certainly adopt the various resins of extrusion moulding systems such as T pattern head method or blowing system embrane method to constitute is undertaken laminated by bonding these films then.
The form of the non-stretched film that film also can obtain with the cast shaping process that carries out chilling by the film that will extrude is used, can also with by under draft temperature, this film carried out in succession or simultaneously two-way stretch, and will stretch after the form use of the biaxially oriented film made of film heat setting.
The laminating material that lamination film of the present invention is made on metallic matrix, the multilayer film that also can adopt known laminating of past such as dry lamination method to press on the metallic matrix upper strata to state the film that first vibrin constitutes or form the layer that second vibrin constitutes as required on this film carry out moulding, but film of the present invention as mentioned above, since at a high speed to extrude plyability good, Gu Te preferably adopts extruding layer platen press described later.Therefore can under very at a high speed, handle operation of following during system film such as can reduce that film curls simultaneously or the cost that reduces this operation.
Below, the example that is shaped to the laminating material that forms the layer that other vibrin constitutes on the layer that constitutes at copolymer polyester resin describes the extruding layer platen press applicable to laminating material of the present invention.
In Fig. 6 of the device configuration that expression extruding layer platen press is used, along path 12 configurations of metallic matrix 11: the heating region 13 of metallic matrix; An a pair of multilayer multimode 15a, 15b, forcing machine 14a, the 14b of first copolymer resins of the path 12 both sides face-off of the next comfortable metallic matrix of their supplies and the forcing machine 14c of second vibrin, the film of 14b; Pressure roll (prerol1) 16a, 16b, they are from receiving the film of extruding from die head 15a, 15b with the offside (the second vibrin side) of the bonding plane of metallic matrix 11 and at the whole width of film; A pair of laminating roll 18a, 18b, they receive film 17a, 17b from pressure roll 16a, 16b, and the first vibrin 14a, 14b and the second vibrin 14c, 14d are bonded on the two sides of metallic matrix 11; With, make the quenching apparatus 20 of formed laminating material 19 chillings.
In addition, in the device shown in Figure 6, form the lower floor of first vibrin formation and the upper strata that second vibrin constitutes respectively on the two sides of metallic matrix, can certainly be only form first polyester resin layer and form the layer that second vibrin constitutes as the upper strata of this layer in the one side of metallic matrix, this occasion can not used either party die head.
In the device that Fig. 6 represents, between a pair of laminating roll 18a, 18b and with respect to the line at the center of articulamentum pressure roller 18a, 18b, metallic matrix 11 is passed through, after utilizing the fused film 17 of pressure roll 16a, 16b reception from the vibrin of die head 15a and 15b, utilize corresponding laminating roll 18a, 18b to support transmission, supply to the position 21 of nipping between laminating roll, make the multilayer film 17 of the molten adhesive aggregation ester resin in two sides of metallic matrix 11 simultaneously.
Can prevent that thus metallic matrix and vibrin from reducing because of the performance that unnecessary heating causes, vibrin can side by side be covered on the two sides of metallic matrix, and utilize the pressure roll limit to guarantee bonding necessary resin temperature with metallic matrix, the cooling of resin molding is carried out on the limit, the swing of film in the time of can preventing to extrude lamination or the excessive width of cloth that contracts, the film that does not reduce flat is wide and improve the output of product.In addition, can make the vibrin lining at high speed and be film and have high-performance, be i.e. the laminating material of thickness evenness, high working property, high adaptation, high epithelium rerum natura etc.
When using device shown in Figure 6 to make laminating material in addition, be directed to the position of nipping of laminating roll 18a, 18b at heating region 13 heated metallic matrixes 11, but because path 2 and laminating roll 18a, the 18b of metallic matrix are set according to above-mentioned position relation, so till the position 21 of nipping of metallic matrix 11 arrival laminating roll 18a, 18b, can avoid and the contacting of miscellaneous part, the reduction of the surface temperature of metallic matrix 11 maintains the jogging speed that is equivalent to put in the air speed of cooling.
Therefore the temperature that has of metallic matrix 11 and thermal capacity can be effectively used in the hot melt adhesion with polyester resin film, can not need reheat and obtain high bond strength between polyester resin film 17 and metallic matrix 11.
Resin metallic laminating material from laminating roll is discharged carries out chilling by it being led quenching apparatus, can become resin-coatedly to be film like and to have high-performance, i.e. the laminating material of thickness evenness, high working property, high adaptation, high epithelium rerum natura etc.
(tank body and cover)
Laminating material of the present invention is owing to be covered homogeneity and adaptation, processibility are good, so be used for tank body and cover especially effectively, the film that preferred especially aforementioned vibrin constitutes is positioned at this moulding of the inner surface side at least of tank body and cover.
Tank body, the known method of forming of can adopting is over made jar with above-mentioned laminating material by 2 jars or 3 jars etc.
Special seamless jar of preferably not having side face seam can adopt methods such as stretch process, the processing of stretching deep drawn, stretching attenuate stretch process, the curved stretching attenuate stretch process that stretches to make.Jar sidewall sections preferred resin coated metal plate adopt to stretch-again the bend tension that forms of stretch process or adopt again attenuate stretch process thin-walled property make it to become the resin-coated metal sheet original thickness 20～95%, special 30～85% the thickness that preferably becomes.
Cover also can be adopted over known cover method for making above-mentioned laminating material is carried out machine-shaping in addition.
The shape of cover also can adopt to be provided with and form the known shapes of past such as easy open end that content is poured out indentation of using with opening and the wrench that breaks a seal usefulness in addition.
Embodiment
Adopt following example explanation the present invention.
Characteristic value of the present invention adopts following assay method to measure.
(1) fusing point (Tm)
With differential scanning calorimeter DSC7 (パ one キ Application ェ Le マ one corporate system), with the speed of 10 ℃/min will about 5mg under nitrogen gas stream the resin heating, will be based on the temperature of the maximum height of the endotherm(ic)peak of crystallization fusion this moment as Tm.
(2) limiting viscosity (IV)
In the weight ratio of phenol, tetrachloroethane is 1: 1 mixing solutions, use resin dissolves Ubbelohde viscometers (ゥ ベ ロ one デ type viscosity Meter) to measure at 30 ℃.
(3) fusion tension force
Do to supply with resin in two spiral shell forcing machine (セ グ メ Application ト two Shaft give as security out Machine) the 2D25W types of made inlaid type to the smart mechanism of Japan, under 240 ℃ of output 1.5kg/hr, resin temperature, melt extrude, speed by 100m/min is drawn the molten resin of extruding from the wire rod die head of L/D=15mm/3mm under 25 ℃ of ambiances, measure fusion tension force in the position of distance die head exit 450mm with load transducer.
(4) high speed plyability
Use as the T pattern head twin screw extruder of Fig. 4, to aluminium alloy plate, carry out lamination 260 ℃ of following fused are resin extruded, confirm film swing, the generation state that fluctuates with the speed of 100m/min.Judgement criteria is as follows.
[film swing (film shakes れ)]
Amplitude with the film swing is estimated with the ratio of the width of gained resin coating.
Be lower than 2% ... zero
2% or more than ... *
[fluctuation (Veins Move)]
Measure the thickness of the resin coating length direction 500mm of gained laminating material, estimate with the ratio of resin coating mean thickness by the amplitude of fluctuation (the れ width of cloth shakes) of measuring thickness.
Be lower than 10% ... zero
10% or more than ... *
(5) system jar suitable property
Use extruding layer suppress resin-coated aluminum alloy sheet, carry out the DI moulding, make the 350ml jar of internal diameter 66mm, high 122mm, by following standard evaluation processibility, adaptation.The DI moulding is after the resin-coated aluminum alloy sheet that will be coated with lubricant carries out stretch process, carries out stretch process, 3 sections attenuates processing and system jar under drying regime again.
[processibility]
Whether cylindrical shell destruction and press-bending Qu Jinhang evaluation take place during by the system jar.
Cylindrical shell destruction and press-bending do not take place, and can make jar ... zero
Cylindrical shell destruction and press-bending take place ... *
[adaptation]
Film during visual assessment system jar is peeled off, is floated.
Film not occurring peels off, floats (floating I) ... zero
Film occurring peels off, floats ... *
(6) smell
Filling ultrapure water in the good jar of system jar suitable property distills processings (125 ℃-30 minutes) Kaifeng, back, and taste, the turbidity of front and back, the difference of fragrance are handled in sense evaluation distillation.
There is not difference ... zero
Variant ... *
(embodiment 1)
After in having the 65mm φ forcing machine of extruding laminating apparatus, supplying with the ethylene glycol terephthalate that contains multifunctional composition and copolymer composition by the composition shown in the table 1 respectively and being the vibrin of main body, under than the high 30 ℃ temperature of the fusing point of resin, the thick layer that melt extrudes with 16 μ m on the aluminium alloy plate that is heated to 250 ℃ thickness of slab 0.280mm (A3004H 19 materials) is pressed on the face of aluminium alloy plate both sides.
The characteristic value of resin and evaluation result are shown in table 1 and table 2.Film swing, fluctuation do not take place and lamination well in speed that can 100m/min.System jar suitable property is also good.
(embodiment 2～4)
Except making multifunctional composition and copolymer composition is the composition shown in the table 1, and other are identical with embodiment 1.The characteristic value of resin and evaluation result are shown in table 1 and table 2.
Film swing, fluctuation do not take place and lamination well in speed that can 100m/min.System jar suitable property is also good.
(comparative example 1)
Except making multifunctional composition and copolymer composition is the composition shown in the table 1, and other are identical with embodiment 1.The characteristic value of resin and evaluation result are shown in table 1 and table 2.
Owing to do not contain multifunctional composition in the vibrin so fusion tension force is low, fierce swing take place under the speed of 100m/min.Therefore, laminating material is produced membrane thickness unevenness by film resin, generation cylindrical shell destruction during the system jar.
(comparative example 2)
Except making multifunctional composition and copolymer composition is the composition shown in the table 1, and other are identical with embodiment 1.The characteristic value of resin and evaluation result are shown in table 1 and table 2.
Though contain multifunctional composition in the vibrin, fusion tension force is low, and the film swing takes place under the speed of 100m/min.Therefore, the coated with resin of laminating material produces membrane thickness unevenness, during the system jar cylindrical shell takes place and destroys.
(comparative example 3)
Except making multifunctional composition and copolymer composition is the composition shown in the table 1, and other are identical with embodiment 1.The characteristic value of resin and evaluation result are shown in table 1 and table 2.
High-speed coating is good, but owing to do not contain copolymer composition in the vibrin, thus occur during system jar film peel off, unsteady.
(comparative example 4)
Except making multifunctional composition and copolymer composition is the composition shown in the table 1, and other are identical with embodiment 1.The characteristic value of resin and evaluation result are shown in table 1 and table 2.
High-speed coating is good, but since in the vibrin concentration of the copolymer composition that contains low, so occur during system jar film peel off, unsteady.
(comparative example 5)
Except making multifunctional composition and copolymer composition is the composition shown in the table 1, and other are identical with embodiment 1.The characteristic value of resin and evaluation result are shown in table 1 and table 2.
Though high-speed coating is good because the copolymer composition concentration height that contains in the vibrin, so fusing point obviously reduce, poor heat resistance, withdrawing from property of formpiston is poor during the system jar, bends.
(embodiment 5)
In having the forcing machine of extruding laminating apparatus 65mm φ, supply with respectively by forming the trimellitic acid that contains as multifunctional composition shown in the table 3, first vibrin as the m-phthalic acid of copolymer composition based on the polyester of ethylene glycol terephthalate unit, after containing ethylene glycol terephthalate unit as the m-phthalic acid composition of copolymer composition according to the composition shown in the table 3 and being second vibrin of main body, under than the high 30 ℃ temperature of the fusing point of resin, the thick layer that melt extrudes with 16 μ m on the aluminium alloy plate that is heated to 250 ℃ thickness of slab 0.280mm (A3004H 19 materials) is pressed on the face of aluminium alloy plate both sides.
Evaluation result is shown in table 4.Film swing, fluctuation, lamination well do not take place under the speed of 100m/min.A system jar suitable property, smell are also good.
(embodiment 6)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Film swing, fluctuation, lamination well do not take place under the speed of 100m/min.A system jar suitable property, smell are also good.
(embodiment 7)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Film swing, fluctuation do not take place under the speed of 100m/min, lamination well, a system jar suitable property, smell are also good.
(embodiment 8)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Film swing, fluctuation do not take place under the speed of 100m/min, lamination well, a system jar suitable property, smell are also good.
(comparative example 6)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Owing to do not contain multifunctional composition in first vibrin so fusion tension force is low, fierce film swing take place when 100m/min.When therefore producing membrane thickness unevenness, system jar on the coated with resin of laminating material cylindrical shell taking place destroys.
(comparative example 7)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Though contain multifunctional composition in first vibrin but fusion tension force is low, fierce film swing take place when 100m/min.When therefore the coated with resin of laminating material produces membrane thickness unevenness, system jar cylindrical shell taking place destroys.
(comparative example 8)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Because the multifunctional constituent concentration that contains in first vibrin is high so fusion tension force becomes very high, the fusion warp tension ratio of first vibrin and second vibrin becomes very big.Fierce fluctuation takes place when 100m/min.When therefore, the coated with resin of laminating material produces membrane thickness unevenness, system jar cylindrical shell taking place destroys.
(comparative example 9)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Though owing to contain multifunctional composition but fusion tension force is very low in first vibrin, the film swing takes place when 100m/min.When therefore, the coated with resin of laminating material produces membrane thickness unevenness, system jar cylindrical shell taking place destroys.
(comparative example 10)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Though the high speed plyability is good owing to do not contain copolymer composition in first vibrin, so occur during system jar film peel off, unsteady.
(comparative example 11)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Though the high speed plyability is good because the copolymer composition concentration that contains is low in first vibrin, so occur during system jar film peel off, unsteady.
(comparative example 12)
The amount of copolymer composition is that other are identical with embodiment 5 content of table 3 expression in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin.
Evaluation result is shown in table 4.Though the high speed plyability is good because the copolymer composition concentration height that contains in first vibrin, so fusing point obviously reduces poor heat resistance, thus when making jar the withdrawing from property of formpiston poor, bend.
(comparative example 13)
The amount of copolymer composition is the content shown in the table 3 in the amount of multifunctional composition and copolymer composition and second vibrin in making employed first vibrin, and other are identical with embodiment 5.
Evaluation result is shown in table 4.Though high speed plyability, system jar suitable property are good, produce muddy in the distillation of smell evaluation is handled in the ultrapure water.Estimate that this is that smell is poor from the result of the stripping composition of second vibrin that contains the high density copolymer composition.
Table 2
Table 4
Claims (8)
1. film for laminating, it is characterized in that comprising vibrin, this vibrin contains the multifunctional composition of 0.01～0.50 mole of %, and fusion tension force is 50mN or more than the 50mN, this film be by with aforementioned vibrin as first vibrin, the layer that the laminated second other vibrin constitutes on the layer that first vibrin constitutes forms, and the fusion tension force of fusion warp tension ratio second vibrin of aforementioned first vibrin is big.
2. the described film for laminating of claim 1, wherein, aforementioned first vibrin is 1.1: 1～5 with the ratio of the fusion tension force of second vibrin: 1.
3. the described film for laminating of claim 1, wherein, aforementioned first vibrin is 50: 1～1 with the ratio of the thickness of second vibrin: 5.
4. the described film for laminating of claim 1, wherein, aforementioned vibrin is the copolymer polyester resin based on the polyethylene terephthalate unit that contains 10～20 moles of % copolymer compositions.
5. the described film for laminating of claim 4, wherein, aforementioned copolymer composition is a m-phthalic acid.
6. the described film for laminating of claim 5, wherein, the fusing point of aforementioned copolymer polyester resin is lower than 220 ℃.
7. laminating material by the described film for laminating of lining claim 1 on metallic matrix, makes it to contact with metallic matrix and forms.
8. laminating material by the described film for laminating of lining claim 1 on metallic matrix, makes the layer that is made of first vibrin contact with metallic matrix and forms.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003076195 | 2003-03-19 | ||
| JP076195/2003 | 2003-03-19 | ||
| JP361803/2003 | 2003-10-22 |
Publications (2)
| Publication Number | Publication Date |
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| CN1791627A CN1791627A (en) | 2006-06-21 |
| CN100387633C true CN100387633C (en) | 2008-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800137530A Expired - Lifetime CN100387633C (en) | 2003-03-19 | 2004-03-12 | Film for laminate and laminate comprising the same |
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| Country | Link |
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| CN (1) | CN100387633C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070882B (en) * | 2009-11-24 | 2014-04-09 | 奥瑞金包装股份有限公司 | Polyester film for being adhered to surface of metal thin plate and manufacture method thereof |
| JP6037777B2 (en) * | 2012-10-31 | 2016-12-07 | 東洋鋼鈑株式会社 | Resin-coated metal plate for squeezed iron can, squeezed iron can and method for producing squeezed iron can |
| JP5741878B2 (en) * | 2013-04-18 | 2015-07-01 | 住友ベークライト株式会社 | Steel sheet coating film |
| JP6244729B2 (en) * | 2013-08-07 | 2017-12-13 | 東洋製罐株式会社 | Resin-coated seamless aluminum can |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4957820A (en) * | 1987-10-15 | 1990-09-18 | Cmb Foodcan Plc | Laminated metal sheet |
| US6013360A (en) * | 1996-07-15 | 2000-01-11 | Sinco Engineering, S.P.A. | Blown polyester film |
| EP1055697A1 (en) * | 1999-05-24 | 2000-11-29 | SINCO RICERCHE S.p.A. | Mono- or biaxially-stretched polyester resin foamed sheets |
| JP2001200038A (en) * | 2000-01-14 | 2001-07-24 | Mitsubishi Rayon Co Ltd | Polyester resin, polyester resin composition and extrusion molding |
| US20010020046A1 (en) * | 2000-03-02 | 2001-09-06 | Sinco Ricerche S.P.A. | Blow-molded foamed films of polyester resin |
| CN1395599A (en) * | 2000-05-30 | 2003-02-05 | 尤尼吉可株式会社 | Polyester film for metal sheet laminating, metal sheet laminated with this film, and metal vessel formed from this metal sheet |
-
2004
- 2004-03-12 CN CNB2004800137530A patent/CN100387633C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4957820A (en) * | 1987-10-15 | 1990-09-18 | Cmb Foodcan Plc | Laminated metal sheet |
| US6013360A (en) * | 1996-07-15 | 2000-01-11 | Sinco Engineering, S.P.A. | Blown polyester film |
| EP1055697A1 (en) * | 1999-05-24 | 2000-11-29 | SINCO RICERCHE S.p.A. | Mono- or biaxially-stretched polyester resin foamed sheets |
| JP2001200038A (en) * | 2000-01-14 | 2001-07-24 | Mitsubishi Rayon Co Ltd | Polyester resin, polyester resin composition and extrusion molding |
| US20010020046A1 (en) * | 2000-03-02 | 2001-09-06 | Sinco Ricerche S.P.A. | Blow-molded foamed films of polyester resin |
| CN1395599A (en) * | 2000-05-30 | 2003-02-05 | 尤尼吉可株式会社 | Polyester film for metal sheet laminating, metal sheet laminated with this film, and metal vessel formed from this metal sheet |
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| CN1791627A (en) | 2006-06-21 |
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