WO2008075839A1 - Electromagnetic wave shield with vacuum deposited metal using water dispersed polyurethane - Google Patents
Electromagnetic wave shield with vacuum deposited metal using water dispersed polyurethane Download PDFInfo
- Publication number
- WO2008075839A1 WO2008075839A1 PCT/KR2007/006080 KR2007006080W WO2008075839A1 WO 2008075839 A1 WO2008075839 A1 WO 2008075839A1 KR 2007006080 W KR2007006080 W KR 2007006080W WO 2008075839 A1 WO2008075839 A1 WO 2008075839A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- polyol
- electromagnetic wave
- dispersed polyurethane
- polyurethane
- Prior art date
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 28
- 229920003023 plastic Polymers 0.000 claims abstract description 25
- 239000004033 plastic Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims description 35
- -1 caprolactone polyol Chemical class 0.000 claims description 33
- 229920005862 polyol Polymers 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 239000007921 spray Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000013530 defoamer Substances 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- 229920005906 polyester polyol Polymers 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 239000003960 organic solvent Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000003973 paint Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 150000002500 ions Chemical group 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000007772 electroless plating Methods 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 230000007928 solubilization Effects 0.000 description 5
- 238000005063 solubilization Methods 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000000722 Celosia argentea Nutrition 0.000 description 3
- 240000008365 Celosia argentea Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
-
- 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31605—Next to free metal
Definitions
- the present invention relates to a novel electromagnetic wave shield, and more particularly, to an electromagnetic wave shield for vacuum deposition employing water- dispersed polyurethane, in which a water-dispersed polyurethane composition is coated as a primer on a surface of a device, and a metal deposited layer is formed thereon for shielding an electromagnetic wave.
- Such conductive paint coating method comprises preparing a paint by employing a metal having a small diameter, and coating the paint to form a coat, as disclosed in Korean Patent Application No. 10-2000-0083111 and US Patent No. 4,518,524.
- Such conductive paint coating method has a shortcoming in that the coat has a large surface resistance of 25 micron to 30 Ohm since metal particle is dispersed in a polymer for a paint, and thus a coat therefrom is not dense on a surface.
- an expensive metal such as silver is required in excessive amounts for increasing an effect of shielding an electromagnetic wave in a conductive paint.
- Korean Patent No. 0387663 granted to Kyeong-Hee Lee discloses a method of enhancing the property of shielding electromagnetic waves by plating a metal on an engineering plastic not easy to perform electroless plating thereon.
- an ABS resin and/or a UV curable paint were spray coated on the surface of an engineering plastic, not easy to perform electroless plating thereon, such as polybutylene terephthalate (PBT), polypropylene (PP), polyester (PE), polyamide (PA), acryl or a mixture of two or more thereof, thereby forming a primer layer, and then a dry plating such as electroless plating, vacuum deposition, sputtering and ion plating was performed.
- a substrate includes a polycarbonate (PC) resin or an engineering plastic not containing an ABS resin, and not easy to perform electroless plating thereon.
- a conductive laminate includes copper, nickel, chrome, gold and silver, etc.
- a primer material to improve binding force between a substrate and a conductive laminate is an applicable primer comprising an ABS resin and/or a UV (ultraviolet) curable paint.
- ABS resin or UV curable paint has a shortcoming in that it is difficult to evenly coating on a plastic metal surface, and it is not easily adhered to the engineering plastic in solid state, and accordingly the adhesiveness of the metal layer formed thereon also becomes low.
- Korean Patent No. 0613140 granted to Polyscientech Inc. discloses a product that a composition for a primer layer comprising at least one polymer selected from a vinyl chloride based copolymer, polyester and polyurethane, polyisocyanate and an organic solvent is coated on a plastic substrate, and an organic silver composition is coated thereon.
- a composition for a primer layer comprising at least one polymer selected from a vinyl chloride based copolymer, polyester and polyurethane, polyisocyanate and an organic solvent is coated on a plastic substrate, and an organic silver composition is coated thereon.
- such method has a shortcoming in that much volatile organic solvent is exited during work since a strong organic solvent capable of swelling a primer layer is used in the organic silver composition and much organic solvent is also used in the primer layer.
- an electromagnetic wave shield comprising a plastic layer; a water- dispersed polyurethane primer layer formed on the plastic layer; and a metal deposited layer formed on the water-dispersed polyurethane primer layer.
- the plastic layer constitutes an interior or exterior material of an electronic device, and can be preferably used irrespective of solvent resistance.
- the plastic layer is a product that a metal film layer is not formed without a primer layer, or the adhesiveness and peeling resistance of a formed film layer are weak, and a plastic product of which improvement in peeling resistance is required.
- the plastic is polycarbonate, polymethyl methacrylate or a glass fiber used as material for a mobile phone case.
- the water-dispersed polyurethane primer layer is manufactured by spray coating a water-dispersed polyurethane spray composition prepared by dispersing water-dispersed polyurethane in water so that a metal deposited layer may be uniformly coated on an upper surface, and the appearance characteristic of a coated surface may be improved.
- spray coating method usual spray coating method can be used without any specific limitation.
- the water-dispersed polyurethane spray composition comprises 20 to 80% by weight of water-dispersed polyurethane, 19.97 to 79.97% by weight of a water-dispersed medium, 0.01 to 5% by weight of a leveling agent, 0.01 to 5% by weight of a flow modifier and 0.01 to 5% by weight of a defoamer so that it may be suitable for spray coating method through which a metal deposited layer can be uniformly formed.
- the leveling agent improves the leveling property of a surface to be sprayed, and various leveling agent can be used.
- the leveling agent is commercially available, and Flow-425 available at Tego Company can be used.
- the flow modifier is introduced in order to improve the flow of water-dispersed polyurethane thereby reforming a surface
- various commercially available flow modifiers can be used.
- Glide #100 available at Tego Company can be used as the flow modifier.
- the defoamer is used in order to suppress foaming in a water-dispersing agent to be sprayed, and Foamex #810 available at Tego Company can be preferably used.
- the water-dispersed polyurethane spray composition can comprise a small amount of an alcoholic organic solvent for diluting the leveling agent, the defoamer and the flow modifier, and increasing the dis- persibility with the water-dispersed polyurethane and the water-dispersed medium.
- a lower alcohol such as IPA, methanol and ethanol can be used in an amount of less than 5% by weight as the alcoholic organic solvent.
- a caprolactone polyol, an ester polyol, an acryl polyol and a mixture thereof can be preferably employed for providing a metal layer to be deposited with improved peeling resistance as the water-dispersed polyurethane used in the water-dispersed polyurethane composition.
- a caprolactone polyol containing carboxyl group can be more preferably employed for providing a metal layer to be deposited with improved peeling resistance as the caprolactone polyol.
- a caprolactone polyol containing carboxyl group is a polycaprolactone diol containing carboxyl group represented by Formula I below:
- n and m are an intiger of 1 to 10, preferably 1 to 5, and R is a linear or branched C2-C10 alkyl containing -COOH group.
- a mixture in which usual polyether polyols are mixed while controlling water dispersibility and adhesiveness can be used as a caprolactone polyol containing the carboxyl group.
- the polyester polyol prepared by reacting a polyol with an acid can be used.
- the polyester polyol can be prepared by employing an ester polyol prepared by reacting a polyol such as ethylene glycol, neophentyl glycol and hexane diol with an acid such as isophthalic acid, adipic acid and azellic acid for providing a metal deposited layer with improved peeling resistance.
- the acryl polyol is a polyol prepared by employing a compound selected from monomers having a hydroxyl group in vinyl form, e.g., 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyl acrylate and hydroxy propyl methacrylate, etc.
- a method of preparing the acryl polyol is disclosed in Korean Patent Application No. 10-1999-18863, and is also commercially available.
- an acryl polyol available at Japan Soko Chemistry having a molecular weight of 800 to 6000, more preferably 1000 to 3000 can be used.
- the water-dispersed polyurethane can be prepared by employing a method in which a prepolymer formed by reaction of the polyol with polyisocyanate is neutralized, thereby extending chains.
- the polyurethane prepolymer is prepared by mixing a caprolactone polyol having a carboxyl group and a poly- isocyanate with an organic solvent, and reacting in the presence of a catalyst, for example, a tin catalyst, e.g., dibutyltin dilauriate.
- organic solvent used in preparing the polyurethane prepolymer a usual organic solvent known to the art, for example, benzene, toluene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, acetic methyl, acetonitrile, chloroform, methylene chloride, carbone tetrachloride, 1,2-dichloroethane, 1,2,2-trichloroethane, tetrachloroethylene, and N- methyl pyrollidone, etc., can be used alone or a mixture thereof.
- the polyurethane prepolymer can be obtained by mixing polyester polyol, acryl polyol or a mixture thereof, and a compound having a carboxyl group, such as dimethyl propionic acid, with a polyisocyanate and an organic solvent, and reacting in the presence of a catalyst, for example, a tin catalyst.
- a catalyst for example, a tin catalyst.
- the water-dispersed polyurethane prepolymer is obtained by dispersing a polyurethane prepolymer in water according to a conventional method.
- the polyurethane prepolymer is reacted with triethylamine to be water soluble, and is chain-extended with a chain extender such as ethylenediamine, and thus is dispersed in water.
- the metal deposited layer is prepared by using a conventional metal deposition method.
- the metal deposited layer can be prepared by employing the method in which a metal is melted and deposited in vacuum, and the metal includes, but is not limited to, various forms such as silver, gold and aluminum.
- an electromagnetic shield comprising spray coating a water-dispersed polyurethane composition on a plastic substrate to form a primer; and depositing a metal on the spray coated layer.
- an electromagnetic shield in which a water-dispersed polyurethane primer layer is formed between a metal film layer and a base plastic for preventing a peeling phenomenon.
- the electromagnetic shield according to the present invention is eco-friendly and is capable of preventing crack in a plastic product due to the use of an organic solvent since it uses water-dispersed type polyurethane capable of minimizing the use of an organic solvent by a polyurethane primer solution, and employs a non-solvent type metal deposited layer.
- the polyurethane primer according to the present invention can prevent a formed film from being peeled due to good adhesiveness with a metal film formed on its upper part. Best Mode for Carrying Out the Invention
- a cooling apparatus, a thermometer, a stirrer and a mantle were prepared in IL cleaned 4-neck flask, and 406g of polytetramethylether glycol (PTMEG)(MW:2000), 105g of Placcel 205BA (MW:500), 0.5g of dibutyltin dilauriate (DBTDL), 130g of n- methyl pyrollidone (NMP) and 153g of 4,4'-dicyclohexylmethane diisocyanate were poured into the flask, and reacted for 4 hours to provide a polyurethane prepolymer.
- PTMEG polytetramethylether glycol
- DBTDL dibutyltin dilauriate
- NMP n- methyl pyrollidone
- NMP 4,4'-dicyclohexylmethane diisocyanate
- the solvent type polyurethane was prepared as below. [65] Cleaned 4L flask, a stirrer, a mantle, a cooling tube and moisture separator were equipped, 229g of ethylene glycol, 136g of neopentyl glycol, 365g of 1,6-hexanediol, 413g of isophthalic acid, 363g of adipic acid and 234g of azellic acid were poured and 0.3g of TBT (tributyltin) were poured, and when the temperature was elevated to around 130 0 C, melting and dehydration are slowly initiated.
- TBT tributyltin
- Example 7 [70] Cleaned 4L flask, a stirrer, a mantle, a cooling tube and moisture separator were equipped, 229g of ethylene glycol, 136g of neopentyl glycol, 365g of 1,6-hexanediol, 413g of isophthalic acid, 363g of adipic acid and 234g of azellic acid were poured and 0.3g of TBT (tributyltin) were poured, and when the temperature was elevated to around 130 0 C, melting and dehydration are slowly initiated.
- TBT tributyltin
- a stirrer, a mantle and a cooling tube were equipped in separate IL flask, 350g of diol (molecular weight of 3600) prepared as above, 249g of normal methyl pyrollidone and 39g of dimethylol propionic acid were poured and stirred, and 208g of isophorone diisocyanate and again O.lg of dibutyltin dilauriate were poured and reacted at 85 0 C for 4 hours to provide a terminal NCO prepolymer having a solid content of 70.5%.
- a stirrer, a mantle and a cooling tube were equipped in separate IL flask, 11Og of diol (molecular weight of 1950) prepared as above, 42g of acrylpolyol (molecular weight of 1000) UMM-1001 (Japan Soko Chemistry), 37g of dimethyl propionic acid and 21Og of normal methyl pyrollidone were poured and stirred, and 208g of isophorone diisocyanate and again 0. Ig of dibutyltin dilauriate were poured and reacted at 85 0 C for 4 hours to provide a terminal NCO prepolymer having a solid content of 65.4%.
- a stirrer, a mantle and a cooling tube were equipped in a cleaned IL flask, 384g of acrylpolyol (molecular weight of 1000, Japan Soko Chemistry), 45g of dimethyl propionic acid and 142g of normal methyl pyrollidone were poured and stirred, and 196g of isophorone diisocyanate and again O.lg of dibutyltin dilauriate were poured and reacted at 85 0 C for 4 hours to provide a terminal NCO prepolymer having a solid content of 81.4%.
- Deposition test Water-dispersed polyurethane prepared as above, a leveling agent, a flow modifier, a defoamer, an organic solvent and water were poured at ratios described in Table 6 below to provide a spray composition.
- Flow-425 Tego leveling additive. IPA.MeOH are diluted at 1:1 ratio to prepare in 20% concentration. [87] * Glide#100: Tego flow modifier additive. IPA.MeOH are diluted at 1:1 ratio to prepare in 30% concentration.
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Abstract
There is provided an electromagnetic wave shield employing water-dispersed polyurethane. The electromagnetic wave shield comprises a plastic layer; a water-dispersed polyurethane primer layer formed on the plastic layer; and a metal deposited layer formed on the water- dispersed polyurethane primer layer. The electromagnetic wave shield has excellent surface property of a deposited metal and good durability through providing peeling resistance for a metal deposited layer by water-dispersed polyurethane.
Description
Description
ELECTROMAGNETIC WAVE SHIELD WITH VACUUM DEPOSITED METAL USING WATER DISPERSED
POLYURETHANE
Technical Field
[1] The present invention relates to a novel electromagnetic wave shield, and more particularly, to an electromagnetic wave shield for vacuum deposition employing water- dispersed polyurethane, in which a water-dispersed polyurethane composition is coated as a primer on a surface of a device, and a metal deposited layer is formed thereon for shielding an electromagnetic wave. Background Art
[2] Presently, electronic devices such as an electronic range, TV, a radio, a computer and a mobile phone emit much electromagnetic wave.
[3] The emission of an electromagnetic wave occurs as a phenomenon such a noise or a communication error, and affects a human body. Concern about the electromagnetic wave shielding is growing and the need thereabout is increasing as the electromagnetic wave is more seriously recognized in the present day. Further, conventionally, a metal has been used as a device case; however, plastic is now used according to miniaturization of a device and increase in productivity. However, since plastic is electronically transparent, and thus electromagnetic waves are massively emitted therefrom, a measure therefor is urgently needed.
[4] As ways for shielding an electromagnetic wave, metal spraying, vacuum deposition, plating and a conductive paint are employed, and recently, material such as conductive plastic is also actively developed.
[5] A way employing a conductive paint has been widely employed since it is easy to handle and produce massively. Such conductive paint coating method comprises preparing a paint by employing a metal having a small diameter, and coating the paint to form a coat, as disclosed in Korean Patent Application No. 10-2000-0083111 and US Patent No. 4,518,524. However, such conductive paint coating method has a shortcoming in that the coat has a large surface resistance of 25 micron to 30 Ohm since metal particle is dispersed in a polymer for a paint, and thus a coat therefrom is not dense on a surface. Further, there has been a problem that an expensive metal such as silver is required in excessive amounts for increasing an effect of shielding an electromagnetic wave in a conductive paint.
[6] Meanwhile, a method of shielding an electromagnetic wave by film coating a metal having excellent electric conductivity on a structure of an electronic device generating
an electromagnetic wave (e.g., injection formed plastic mobile phone case) by vacuum deposition is introduced. However, there has been a problem that interface adhesiveness between a polymer resin, which is an injected material, and a metal layer coated thereon, which is a conductive film for shielding an electromagnetic wave, is weak. In order to solve the problem that the adhesiveness between a metal layer and an injected material is weak, a way of coating an acrylic resin or ABS resin, or UV curable paint as a primer, and then depositing a metal thereon has been developed.
[7] Korean Patent No. 0387663 granted to Kyeong-Hee Lee discloses a method of enhancing the property of shielding electromagnetic waves by plating a metal on an engineering plastic not easy to perform electroless plating thereon. In more particular, an ABS resin and/or a UV curable paint were spray coated on the surface of an engineering plastic, not easy to perform electroless plating thereon, such as polybutylene terephthalate (PBT), polypropylene (PP), polyester (PE), polyamide (PA), acryl or a mixture of two or more thereof, thereby forming a primer layer, and then a dry plating such as electroless plating, vacuum deposition, sputtering and ion plating was performed. A substrate includes a polycarbonate (PC) resin or an engineering plastic not containing an ABS resin, and not easy to perform electroless plating thereon. A conductive laminate includes copper, nickel, chrome, gold and silver, etc. A primer material to improve binding force between a substrate and a conductive laminate is an applicable primer comprising an ABS resin and/or a UV (ultraviolet) curable paint. Thus, the patent discloses a method of providing the property of shielding harmful electromagnetic waves by coating a primer on a substrate, and then electroless plating. However, such ABS resin or UV curable paint has a shortcoming in that it is difficult to evenly coating on a plastic metal surface, and it is not easily adhered to the engineering plastic in solid state, and accordingly the adhesiveness of the metal layer formed thereon also becomes low.
[8] Accordingly, a method of providing good adhesiveness and forming uniform film between a deposited metal layer and a lower resin layer is being developed. Korean Patent No. 0613140 granted to Polyscientech Inc. discloses a product that a composition for a primer layer comprising at least one polymer selected from a vinyl chloride based copolymer, polyester and polyurethane, polyisocyanate and an organic solvent is coated on a plastic substrate, and an organic silver composition is coated thereon. However, such method has a shortcoming in that much volatile organic solvent is exited during work since a strong organic solvent capable of swelling a primer layer is used in the organic silver composition and much organic solvent is also used in the primer layer.
[9] Further, such method has a shortcoming in that the solvent contacts with a plastic case on coating the primer or the organic silver composition. If the plastic product
contacts with the organic solvent, minute crack is generated in the plastic product, ESCR (Environment Stress Crack Resistance) is decreased, and thus crack is generated in the plastic during use.
[10] Accordingly, a method of solving the problem of environmental pollution or inner environmental crack due to the use of an organic solvent is continuously needed. Disclosure of Invention Technical Problem
[11] It is an object of the invention to provide an electromagnetic wave shield employing water-dispersed polyurethane.
[12] It is another object of the invention to provide a method of manufacturing an electromagnetic wave shield employing water-dispersed polyurethane.
[13] It is still another object of the invention to provide a composition for spraying water-dispersed polyurethane used in manufacturing an electromagnetic wave shield.
[14] It is still yet another object of the invention to provide water-dispersed polyurethane used in manufacturing an electromagnetic wave shield. Technical Solution
[15] In order to accomplish the above objects, according to one aspect of the invention, there is provided an electromagnetic wave shield comprising a plastic layer; a water- dispersed polyurethane primer layer formed on the plastic layer; and a metal deposited layer formed on the water-dispersed polyurethane primer layer.
[16] In the above aspect of the present invention, the plastic layer constitutes an interior or exterior material of an electronic device, and can be preferably used irrespective of solvent resistance. In an embodiment of the present invention, the plastic layer is a product that a metal film layer is not formed without a primer layer, or the adhesiveness and peeling resistance of a formed film layer are weak, and a plastic product of which improvement in peeling resistance is required. In a preferable embodiment of the present invention, the plastic is polycarbonate, polymethyl methacrylate or a glass fiber used as material for a mobile phone case.
[17] In the above aspect of the present invention, the water-dispersed polyurethane primer layer is manufactured by spray coating a water-dispersed polyurethane spray composition prepared by dispersing water-dispersed polyurethane in water so that a metal deposited layer may be uniformly coated on an upper surface, and the appearance characteristic of a coated surface may be improved. As the spray coating method, usual spray coating method can be used without any specific limitation.
[18] In the above aspect of the present invention, the water-dispersed polyurethane spray composition comprises 20 to 80% by weight of water-dispersed polyurethane, 19.97 to 79.97% by weight of a water-dispersed medium, 0.01 to 5% by weight of a leveling
agent, 0.01 to 5% by weight of a flow modifier and 0.01 to 5% by weight of a defoamer so that it may be suitable for spray coating method through which a metal deposited layer can be uniformly formed.
[19] In the above aspect of the present invention, the leveling agent improves the leveling property of a surface to be sprayed, and various leveling agent can be used. In an embodiment of the present invention, the leveling agent is commercially available, and Flow-425 available at Tego Company can be used.
[20] In the above aspect of the present invention, the flow modifier is introduced in order to improve the flow of water-dispersed polyurethane thereby reforming a surface, and various commercially available flow modifiers can be used. In an embodiment of the present invention, Glide #100 available at Tego Company can be used as the flow modifier.
[21] In the above aspect of the present invention, the defoamer is used in order to suppress foaming in a water-dispersing agent to be sprayed, and Foamex #810 available at Tego Company can be preferably used.
[22] In an embodiment of the present invention, the water-dispersed polyurethane spray composition can comprise a small amount of an alcoholic organic solvent for diluting the leveling agent, the defoamer and the flow modifier, and increasing the dis- persibility with the water-dispersed polyurethane and the water-dispersed medium. In an embodiment of the present invention, a lower alcohol such as IPA, methanol and ethanol can be used in an amount of less than 5% by weight as the alcoholic organic solvent.
[23] In the above aspect of the present invention, a caprolactone polyol, an ester polyol, an acryl polyol and a mixture thereof can be preferably employed for providing a metal layer to be deposited with improved peeling resistance as the water-dispersed polyurethane used in the water-dispersed polyurethane composition.
[24] In an embodiment of the present invention, a caprolactone polyol containing carboxyl group can be more preferably employed for providing a metal layer to be deposited with improved peeling resistance as the caprolactone polyol.
[25] In a preferable embodiment of the present invention, a caprolactone polyol containing carboxyl group is a polycaprolactone diol containing carboxyl group represented by Formula I below:
[26]
-CO(CH2LO l- H
Im
(I)
[27] wherein n and m are an intiger of 1 to 10, preferably 1 to 5, and R is a linear or branched C2-C10 alkyl containing -COOH group. In the present invention, a caprolactone polyol containing the carboxyl group is commercially available, and preferably n=2, and m=l, and R is Placcel 205BA available at Daicel Chemical Industries represented by formula below:
[28]
C2H5
-CH2-C-CH2-
COOH
[29] In a preferable embodiment of the present invention, a mixture in which usual polyether polyols are mixed while controlling water dispersibility and adhesiveness can be used as a caprolactone polyol containing the carboxyl group.
[30] In the present invention, the polyester polyol prepared by reacting a polyol with an acid can be used. In a preferable embodiment of the present invention, the polyester polyol can be prepared by employing an ester polyol prepared by reacting a polyol such as ethylene glycol, neophentyl glycol and hexane diol with an acid such as isophthalic acid, adipic acid and azellic acid for providing a metal deposited layer with improved peeling resistance.
[31] In another embodiment of the present invention, the acryl polyol is a polyol prepared by employing a compound selected from monomers having a hydroxyl group in vinyl form, e.g., 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyl acrylate and hydroxy propyl methacrylate, etc. A method of preparing the acryl polyol is disclosed in Korean Patent Application No. 10-1999-18863, and is also commercially available. Preferably, an acryl polyol available at Japan Soko Chemistry, having a molecular weight of 800 to 6000, more preferably 1000 to 3000 can be used.
[32] In the present invention, the water-dispersed polyurethane can be prepared by employing a method in which a prepolymer formed by reaction of the polyol with polyisocyanate is neutralized, thereby extending chains.
[33] In a preferable embodiment of the present invention, the polyurethane prepolymer is prepared by mixing a caprolactone polyol having a carboxyl group and a poly- isocyanate with an organic solvent, and reacting in the presence of a catalyst, for example, a tin catalyst, e.g., dibutyltin dilauriate. As the organic solvent used in preparing the polyurethane prepolymer, a usual organic solvent known to the art, for example, benzene, toluene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, acetic methyl, acetonitrile, chloroform, methylene chloride, carbone tetrachloride, 1,2-dichloroethane, 1,2,2-trichloroethane, tetrachloroethylene, and N- methyl pyrollidone, etc., can be used alone or a mixture thereof.
[34] In another preferable embodiment of the present invention, the polyurethane prepolymer can be obtained by mixing polyester polyol, acryl polyol or a mixture thereof, and a compound having a carboxyl group, such as dimethyl propionic acid, with a polyisocyanate and an organic solvent, and reacting in the presence of a catalyst, for example, a tin catalyst.
[35] In the present invention, the water-dispersed polyurethane prepolymer is obtained by dispersing a polyurethane prepolymer in water according to a conventional method. In a preferable embodiment of the present invention, the polyurethane prepolymer is reacted with triethylamine to be water soluble, and is chain-extended with a chain extender such as ethylenediamine, and thus is dispersed in water.
[36] In the present invention, the metal deposited layer is prepared by using a conventional metal deposition method. In a preferable embodiment of the present invention, the metal deposited layer can be prepared by employing the method in which a metal is melted and deposited in vacuum, and the metal includes, but is not limited to, various forms such as silver, gold and aluminum.
[37] According to another aspect of the invention, there is provided a product in which the water-dispersed polyurethane is used as a primer.
[38] According to still another aspect of the invention, there is provided a method of manufacturing an electromagnetic shield comprising spray coating a water-dispersed polyurethane composition on a plastic substrate to form a primer; and depositing a metal on the spray coated layer.
Advantageous Effects
[39] According to the present invention, there is provided an electromagnetic shield in which a water-dispersed polyurethane primer layer is formed between a metal film layer and a base plastic for preventing a peeling phenomenon.
[40] The electromagnetic shield according to the present invention is eco-friendly and is capable of preventing crack in a plastic product due to the use of an organic solvent since it uses water-dispersed type polyurethane capable of minimizing the use of an
organic solvent by a polyurethane primer solution, and employs a non-solvent type metal deposited layer. The polyurethane primer according to the present invention can prevent a formed film from being peeled due to good adhesiveness with a metal film formed on its upper part. Best Mode for Carrying Out the Invention
[41] The present invention will be described in greater detail with reference to the following examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.
[42] Examples 1 to 6
[43] Preparation of a polyurethane prepolymer
[44] A cooling apparatus, a thermometer, a stirrer and a mantle were prepared in IL cleaned 4-neck flask, and 406g of polytetramethylether glycol (PTMEG)(MW:2000), 105g of Placcel 205BA (MW:500), 0.5g of dibutyltin dilauriate (DBTDL), 130g of n- methyl pyrollidone (NMP) and 153g of 4,4'-dicyclohexylmethane diisocyanate were poured into the flask, and reacted for 4 hours to provide a polyurethane prepolymer.
[45] While 42Og of ion exchanged water, 12.3g of triethylamine and 50g of isopropyl alcohol were mixed in a separate 2L beaker and agitated vigorously, 350g of the polyurethane prepolymer prepared as above were poured slowly to solubilize in water. After vigorous agitation and solubilization in water for about 30 minutes, 80g of ion exchanged water and 1.7g of ethylene diamine were mixed and poured slowly, and after pouring and then vigorous agitation for about 20 minutes, the temperature was elevated to 7O0C, and slow agitation was performed for 1 hour. After agitation, a water- soluble polyurethane resin with 32% solid content, pH 8.7 was obtained.
[46] Deposition test
[47] Water-dispersed polyurethane prepared as above, a leveling agent, a flow modifier, a defoamer, an organic solvent and water were poured at ratios described in Table 1 below to provide a spray composition.
[48] Table 1
[49] * Flow-425: Tego leveling additive. IPA.MeOH are diluted at 1:1 ratio to prepare in 20% concentration.
[50] * Glide#100: Tego flow modifier additive. IPA.MeOH are diluted at 1:1 ratio to prepare in 30% concentration.
[51] * Foamex#810: Tego defoamer [52] * IPA: isopropyl alcohol [53] The spray composition prepared as above was spray coated on the plastic side of polycarbonate material, and then the coated product was dried at 750C for 1 hour. After drying, the spray coated polycarbonate was put into a vacuum chamber, and then subjected to aluminum deposition at 7O0C for 1 hour.
[54] Spray suitability, adhesiveness, gloss, leveling property, electric resistance, salt water resistance and crack resistance for the product prepared as above were tested.
[55] The test results are summarized in Table 2 below. [56] Table 2
[57] ©: very good, O: good Δ: somewhat insufficient
[58] Comparative example 1 [59] A spray composition was prepared by employing the PUD prepared the same as in Example 1 with ingredients at ratios described in Table 3 below, and the respective properties are summarized in Table 4.
[60] Table 3
[61]
[62] ©: very good, O: good, Δ: somewhat insufficient. [63] Vacuum depositing property for the spray composition prepared in Examples 1 to 6 and solvent type polyurethane was observed. Vacuum depositing property is totally observed for color reproduction, surface uniformity and gloss uniformity with naked eyes after forming a primer layer on a glass substrate and depositing silver thereon. The results are summarized in Table 5 below.
[64] The solvent type polyurethane was prepared as below. [65] Cleaned 4L flask, a stirrer, a mantle, a cooling tube and moisture separator were equipped, 229g of ethylene glycol, 136g of neopentyl glycol, 365g of 1,6-hexanediol, 413g of isophthalic acid, 363g of adipic acid and 234g of azellic acid were poured and 0.3g of TBT (tributyltin) were poured, and when the temperature was elevated to
around 1300C, melting and dehydration are slowly initiated. Then nitrogen is slowly added, and the temperature is continuously elevated to 2500C, and while maintaining 2500C, reaction is performed until acid value reaches below 0.1. After reaction is completed, a transparent polyester diol having average molecular weight of 3600 and acid value below 0.1 was prepared. 175Og of polyesterdiol prepared as above, 593g of ethyl acetate, 593g of methylethyl ketone and 0.3g of dibutyltin dilauriate were poured and stirred, and then 29.2g of toluene diisocyanate were poured and reacted at 900C for 5 hours to provide a polyurethane resin having a solid content of 60% and a viscosity of 1500 cps.
[66] 30 parts by weight of the polyurethane resin prepared as above, 20 parts by weight of toluene, 15 parts by weight of ethyl acetate, 20 parts by weight of methylethyl ketone, 5 parts by weight of xylene and a polyisocyanate trimer having a solid content of 30% were poured as curing agents to prepare a polyurethane solvent type spray composition.
[67] Table 5
[68] ©: very good, O: good, Δ: somewhat insufficient, X: bad. [69] Example 7 [70] Cleaned 4L flask, a stirrer, a mantle, a cooling tube and moisture separator were equipped, 229g of ethylene glycol, 136g of neopentyl glycol, 365g of 1,6-hexanediol, 413g of isophthalic acid, 363g of adipic acid and 234g of azellic acid were poured and 0.3g of TBT (tributyltin) were poured, and when the temperature was elevated to around 1300C, melting and dehydration are slowly initiated. Then nitrogen is slowly
added, and the temperature is continuously elevated to 25O0C, and while maintaining 25O0C, reaction is performed until acid value reaches below 0.1. After reaction is completed, a transparent polyester diol having average molecular weight of 3600 and acid value below 0.1 was prepared.
[71] A stirrer, a mantle and a cooling tube were equipped in separate IL flask, 350g of diol (molecular weight of 3600) prepared as above, 249g of normal methyl pyrollidone and 39g of dimethylol propionic acid were poured and stirred, and 208g of isophorone diisocyanate and again O.lg of dibutyltin dilauriate were poured and reacted at 850C for 4 hours to provide a terminal NCO prepolymer having a solid content of 70.5%.
[72] Then, 350g of prepolymer were poured into a separate flask in the presence of 41Og of ion exchanged water and 8.9g of triethylamine, and subjected to vigorous agitation and solubilization in water. Then, 63g of ethylene diamine aqueous solution (5% in water) were poured, and chain extension was performed with vigorous agitating to prepare water-dispersed polyurethane.
[73] Example 8
[74] 17Og of ethylene glycol, 57Og of neopentyl glycol, 208g of terephthalic acid, 138g of isophthalic acid and 61 Ig of adipic acid were poured and 0.3g of TBT (tributyltin) were poured, and when the temperature was elevated to around 13O0C, melting and dehydration are slowly initiated. Then nitrogen is slowly added, and the temperature is continuously elevated to 25O0C, and while maintaining 25O0C, reaction is performed until acid value reaches below 0.1. After reaction is completed, a transparent polyester diol having average molecular weight of 1950 and acid value below 0.1 was prepared.
[75] A stirrer, a mantle and a cooling tube were equipped in separate IL flask, 11Og of diol (molecular weight of 1950) prepared as above, 42g of acrylpolyol (molecular weight of 1000) UMM-1001 (Japan Soko Chemistry), 37g of dimethyl propionic acid and 21Og of normal methyl pyrollidone were poured and stirred, and 208g of isophorone diisocyanate and again 0. Ig of dibutyltin dilauriate were poured and reacted at 850C for 4 hours to provide a terminal NCO prepolymer having a solid content of 65.4%.
[76] Then, 350g of prepolymer were poured into a separate flask while stirring in the presence of 352g of ion exchanged water and 8.3g of triethylamine, and subjected to vigorous agitation and solubilization in water. Then, 63g of ethylene diamine aqueous solution (5% in water) were poured, and chain extension was performed with vigorous agitating to prepare water-dispersed polyurethane.
[77] Example 9
[78] A stirrer, a mantle and a cooling tube were equipped in a cleaned IL flask, 384g of acrylpolyol (molecular weight of 1000, Japan Soko Chemistry), 45g of dimethyl propionic acid and 142g of normal methyl pyrollidone were poured and stirred, and
196g of isophorone diisocyanate and again O.lg of dibutyltin dilauriate were poured and reacted at 850C for 4 hours to provide a terminal NCO prepolymer having a solid content of 81.4%.
[79] Then, 35Og of prepolymer were poured into a separate flask while stirring in the presence of 552g of ion exchanged water and 8.3g of triethylamine, and subjected to vigorous agitation and solubilization in water. Then, 63g of ethylene diamine aqueous solution (5% in water) were poured, and chain extension was performed with vigorous agitating to prepare water-dispersed polyurethane.
[80] Comparative example 3 [81] A stirrer, a mantle and a cooling tube were equipped in a cleaned IL flask, 384g of polypropylene glycol (molecular weight of 1000), 45g of dimethyl propionic acid and 142g of normal methyl pyrollidone were poured and stirred, and 196g of isophorone diisocyanate and again O.lg of dibutyltin dilauriate were poured and reacted at 850C for 4 hours to provide a terminal NCO prepolymer having a solid content of 81.4%.
[82] Then, 35Og of prepolymer were poured into a separate flask while stirring in the presence of 552g of ion exchanged water and 8.3g of triethylamine, and subjected to vigorous agitation and solubilization in water. Then, 63g of ethylene diamine aqueous solution (5% in water) were poured, and chain extension was performed with vigorous agitating to prepare water-dispersed polyurethane.
[83] Deposition test [84] Water-dispersed polyurethane prepared as above, a leveling agent, a flow modifier, a defoamer, an organic solvent and water were poured at ratios described in Table 6 below to provide a spray composition.
[85] Table 6
[86] * Flow-425: Tego leveling additive. IPA.MeOH are diluted at 1:1 ratio to prepare in 20% concentration.
[87] * Glide#100: Tego flow modifier additive. IPA.MeOH are diluted at 1:1 ratio to prepare in 30% concentration.
[88] * Foamex#810: Tego defoamer [89] * IPA: isopropyl alcohol [90] The spray composition prepared as above was spray coated on the plastic side of polycarbonate material, and then the coated product was dried at 750C for 1 hour. After drying, the spray coated polycarbonate was put into a vacuum chamber, and then subjected to aluminum deposition at 7O0C for 1 hour.
[91] Spray suitability, adhesiveness, gloss, leveling property, electric resistance, salt water resistance and crack resistance for the product prepared as above were tested.
[92] The test results are summarized in Table 7 below. [93] Table 7
[94] ©: very good, O: good, Δ: somewhat insufficient, X: bad. [95] Although the present invention has been described with reference to several embodiments of the invention, the description is illustrative of the invention and is not to be construed as limiting the invention. Various modifications and variations may occur to those skilled in the art, without departing from the spirit and scope of the invention as defined by the appended claims.
Claims
[1] An electromagnetic wave shield comprising a plastic layer; a water-dispersed polyurethane primer layer formed on the plastic layer; and a metal deposited layer formed on the water-dispersed polyurethane primer layer.
[2] The electromagnetic wave shield according to claim 1, wherein the water- dispersed polyurethane primer layer is formed by spray drying a spray composition comprising water-dispersed polyurethane.
[3] The electromagnetic wave shield according to claim 2, wherein the spray composition comprises water-dispersed polyurethane, a leveling agent, a flow modifier and a defoamer.
[4] The electromagnetic wave shield according to claim 1, wherein the water- dispersed polyurethane is prepared by employing a polyol including a caprolactone polyol, a polyester polyol, an acryl polyol and a mixture thereof.
[5] The electromagnetic wave shield according to claim 4, wherein the caprolactone polyol is a caprolactone polyol containing a carboxyl group.
[6] The electromagnetic wave shield according to claim 4, wherein the polyester polyol is an ester polyol prepared by reacting a polyol selected from ethylene glycol, neophentyl glycol, hexane diol and a mixture thereof with an acid selected from isophthalic acid, adipic acid, azelic acid and a mixture thereof.
[7] A polyurethane composition for spraying a metal deposited primer comprising
20 to 80% by weight of water-dispersed polyurethane, 19.97 to 79.97% by weight of water, 0.01 to 5% by weight of a leveling agent, 0.01 to 5% by weight of a flow modifier and 0.01 to 5% by weight of a defoamer.
[8] The polyurethane composition for spraying a metal deposited primer according to claim 7, wherein the water-dispersed polyurethane is prepared by employing a polyol including a caprolactone polyol, a polyester polyol, an acryl polyol and a mixture thereof.
[9] The polyurethane composition for spraying a metal deposited primer according to claim 8, wherein the caprolactone polyol is a caprolactone polyol containing a carboxyl group.
[10] The polyurethane composition for spraying a metal deposited primer according to claim 8, wherein the polyester polyol is an ester polyol prepared by reacting a polyol selected from ethylene glycol, neophentyl glycol, hexane diol and a mixture thereof with an acid selected from isophthalic acid, adipic acid, azelic acid and a mixture thereof.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/516,225 US20100068531A1 (en) | 2006-12-19 | 2007-11-29 | Electromagnetic wave shield with vacuum deposited metal using water dispersed polyurethane |
| EP07834370A EP2119333A1 (en) | 2006-12-19 | 2007-11-29 | Electromagnetic wave shield with vacuum deposited metal using water dispersed polyurethane |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060129821A KR100761435B1 (en) | 2006-12-19 | 2006-12-19 | Electromagnetic wave shield with vacuum deposited metal using water dispersed polyurethane |
| KR10-2006-0129821 | 2006-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2008075839A1 true WO2008075839A1 (en) | 2008-06-26 |
Family
ID=38738627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2007/006080 WO2008075839A1 (en) | 2006-12-19 | 2007-11-29 | Electromagnetic wave shield with vacuum deposited metal using water dispersed polyurethane |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20100068531A1 (en) |
| EP (1) | EP2119333A1 (en) |
| KR (1) | KR100761435B1 (en) |
| CN (1) | CN101569250A (en) |
| WO (1) | WO2008075839A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9109138B2 (en) | 2011-08-02 | 2015-08-18 | Toray Plastics (America), Inc. | Optically clear biaxially oriented polyester film with anti-iridescent primer layer |
| US20130089721A1 (en) | 2011-08-02 | 2013-04-11 | Tracy Paolilli | Non-iridescent film with polymeric particles in primer layer |
| JP5712095B2 (en) * | 2011-09-16 | 2015-05-07 | 藤森工業株式会社 | Electromagnetic wave shielding material for FPC |
| US10224445B2 (en) * | 2015-11-02 | 2019-03-05 | S-Energy Co., Ltd. | Back sheet, method of manufacturing the same, solar cell module using the same and method of manufacturing solar cell |
| CN114719683A (en) * | 2022-04-01 | 2022-07-08 | 江苏铁锚玻璃股份有限公司 | Silver-based electromagnetic shielding and electromagnetic stealth film system structure |
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| US5945213A (en) * | 1995-09-04 | 1999-08-31 | Yoshino Denka Kogyo, Inc. | EMI shield and a method of forming the same |
| KR20020042121A (en) * | 2000-11-30 | 2002-06-05 | 이경희 | The coating method on the engineering plastics |
| KR20050050720A (en) * | 2003-11-26 | 2005-06-01 | 주식회사 코오롱 | Paint composition of composite materials for emi shielding |
| KR20060075234A (en) * | 2004-12-28 | 2006-07-04 | 제일모직주식회사 | Composition for electromagnetic interference shielding using carbon nanotube |
| US20060145302A1 (en) * | 2004-12-30 | 2006-07-06 | Kim Sang J | Coating composition for electronic devices |
| KR100613140B1 (en) * | 2006-05-24 | 2006-08-17 | 주식회사 폴리사이언텍 | Electromagnetic wave shielding plastic molded product by using conductive silver ink |
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| US4518524A (en) * | 1983-06-27 | 1985-05-21 | Acheson Industries, Inc. | Silver coating composition for use in electronic applications and the like |
| DE69317035T2 (en) * | 1992-11-09 | 1998-06-10 | Chugai Ings Co | Manufacturing process of a molded plastic body with electromagnetic shielding |
| JPH1126977A (en) * | 1997-07-02 | 1999-01-29 | Daido Steel Co Ltd | Sheet for absorbing electromagnetic wave |
| DE69803022T2 (en) * | 1997-09-25 | 2002-08-01 | Mitsubishi Chemical Corp., Tokio/Tokyo | Secluded plastic film |
| KR100444332B1 (en) * | 1999-12-20 | 2004-08-16 | 도요 보세키 가부시키가이샤 | Infrared absorption filter |
| KR100431248B1 (en) * | 2000-01-14 | 2004-05-12 | 써모트론 주식회사 | Plating Method on A Nonconductor Using Conductive Polymer Composition |
| US6875810B2 (en) * | 2000-10-25 | 2005-04-05 | Dainippon Ink And Chemicals, Inc. | Aqueous dispersions of polyurethane resins and aqueous adhesives |
| US6900383B2 (en) * | 2001-03-19 | 2005-05-31 | Hewlett-Packard Development Company, L.P. | Board-level EMI shield that adheres to and conforms with printed circuit board component and board surfaces |
| US7271216B2 (en) * | 2003-02-25 | 2007-09-18 | Sanyo Chemical Industries, Ltd. | Polyurethane resin aqueous dispersion and sheet material obtained from the same |
| KR100585944B1 (en) * | 2003-05-20 | 2006-06-01 | 제일모직주식회사 | Conductive silicone resin composition and the electromagnetic wave shielding gasket prepared thereby |
| JP5095909B2 (en) * | 2003-06-24 | 2012-12-12 | ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． | Catalyst composition and deposition method |
| KR101081524B1 (en) * | 2004-04-07 | 2011-11-08 | 나노캠텍주식회사 | Conductive Film and Sheet, and Method for preparing the same |
-
2006
- 2006-12-19 KR KR1020060129821A patent/KR100761435B1/en not_active IP Right Cessation
-
2007
- 2007-11-29 CN CNA2007800473272A patent/CN101569250A/en active Pending
- 2007-11-29 US US12/516,225 patent/US20100068531A1/en not_active Abandoned
- 2007-11-29 EP EP07834370A patent/EP2119333A1/en not_active Withdrawn
- 2007-11-29 WO PCT/KR2007/006080 patent/WO2008075839A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5945213A (en) * | 1995-09-04 | 1999-08-31 | Yoshino Denka Kogyo, Inc. | EMI shield and a method of forming the same |
| KR20020042121A (en) * | 2000-11-30 | 2002-06-05 | 이경희 | The coating method on the engineering plastics |
| KR20050050720A (en) * | 2003-11-26 | 2005-06-01 | 주식회사 코오롱 | Paint composition of composite materials for emi shielding |
| KR20060075234A (en) * | 2004-12-28 | 2006-07-04 | 제일모직주식회사 | Composition for electromagnetic interference shielding using carbon nanotube |
| US20060145302A1 (en) * | 2004-12-30 | 2006-07-06 | Kim Sang J | Coating composition for electronic devices |
| KR100613140B1 (en) * | 2006-05-24 | 2006-08-17 | 주식회사 폴리사이언텍 | Electromagnetic wave shielding plastic molded product by using conductive silver ink |
Also Published As
| Publication number | Publication date |
|---|---|
| US20100068531A1 (en) | 2010-03-18 |
| CN101569250A (en) | 2009-10-28 |
| EP2119333A1 (en) | 2009-11-18 |
| KR100761435B1 (en) | 2007-09-27 |
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