WO1995010117A1 - Cross-linked acrylate coating material useful for forming capacitor dielectrics and oxygen barriers - Google Patents
Cross-linked acrylate coating material useful for forming capacitor dielectrics and oxygen barriers Download PDFInfo
- Publication number
- WO1995010117A1 WO1995010117A1 PCT/US1994/011257 US9411257W WO9510117A1 WO 1995010117 A1 WO1995010117 A1 WO 1995010117A1 US 9411257 W US9411257 W US 9411257W WO 9510117 A1 WO9510117 A1 WO 9510117A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylate
- layer
- substrate
- monomer
- sheet
- Prior art date
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 227
- 239000003990 capacitor Substances 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000001301 oxygen Substances 0.000 title claims abstract description 64
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 64
- 230000004888 barrier function Effects 0.000 title claims abstract description 55
- 238000000576 coating method Methods 0.000 title description 44
- 239000011248 coating agent Substances 0.000 title description 38
- 239000003989 dielectric material Substances 0.000 title description 8
- 239000000758 substrate Substances 0.000 claims abstract description 106
- 239000000178 monomer Substances 0.000 claims abstract description 100
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 230000035699 permeability Effects 0.000 claims abstract description 27
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 24
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 24
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 230000008021 deposition Effects 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 4
- -1 polypropylene Polymers 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 26
- 239000004743 Polypropylene Substances 0.000 claims description 25
- 229920001155 polypropylene Polymers 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 10
- 239000004677 Nylon Substances 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- 229920001778 nylon Polymers 0.000 claims description 9
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002985 plastic film Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 4
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 4
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012815 thermoplastic material Substances 0.000 claims description 3
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 9
- 229920006255 plastic film Polymers 0.000 claims 4
- 230000001464 adherent effect Effects 0.000 claims 3
- 238000007599 discharging Methods 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract description 13
- 230000005494 condensation Effects 0.000 abstract description 13
- 238000004804 winding Methods 0.000 abstract description 9
- 238000009832 plasma treatment Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 155
- 239000010408 film Substances 0.000 description 31
- 230000008020 evaporation Effects 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 125000004386 diacrylate group Chemical group 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 4
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QTKIQLNGOKOPOE-UHFFFAOYSA-N 1,1'-biphenyl;propane Chemical compound CCC.C1=CC=CC=C1C1=CC=CC=C1 QTKIQLNGOKOPOE-UHFFFAOYSA-N 0.000 description 2
- GNPWYHFXSMINJQ-UHFFFAOYSA-N 1,2-dimethyl-3-(1-phenylethyl)benzene Chemical compound C=1C=CC(C)=C(C)C=1C(C)C1=CC=CC=C1 GNPWYHFXSMINJQ-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011140 metalized polyester Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- DMQYPVOQAARSNF-UHFFFAOYSA-N 3-[2,3-bis(3-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OCCCOCC(OCCCOC(=O)C=C)COCCCOC(=O)C=C DMQYPVOQAARSNF-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- XCHLRFRZJLYDOF-UHFFFAOYSA-N CCC.OC(=O)C=C.OC(=O)C=C Chemical compound CCC.OC(=O)C=C.OC(=O)C=C XCHLRFRZJLYDOF-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000069444 Tetrameres Species 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011104 metalized film Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
- H01G2/12—Protection against corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
- B05D3/144—Pretreatment of polymeric substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
- B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
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Definitions
- the thin films are desirably resistant to permeation by oxygen, water vapor and odorous gases.
- barrier films are commonly made of costly plastics because less costly films are too permeable to oxygen or water to give a long shelf life. Reduced cost barrier films are highly desirable. There are many products that are packaged in plastic bottles, tubes or vials which also need protection from oxidation or contamination by environmental gasses or which must be in impermeable containers so that components of the contents are not lost by diffusion through the containers.
- metallized sheet dielectrics are commonly used.
- Higher voltage capacitors are generally constructed of aluminum foil electrodes and sheet dielectric material such as a thermoplastic polypropylene and polyester film. Capacitors intended for service at more than about 600 volts are completely impregnated with a dielectric liquid with good gas absorbing properties. Typical dielectric liquids with good gas absorbing properties are PXE (phenyl xylyl ethane), MIPB (mono isopropyl biphenyl), DOP (dioctyl phthalate), castor oil, polypropylene glycol and mineral oil. High voltage capacitors have not been able to take advantage of the self healing properties of metallized electrodes.
- the dielectric liquid causes swelling of the thermoplastic sheets, which causes cracking of the thin film metal electrode and an open circuit quickly develops. It would be desirable to have wound capacitors made with metallized film for higher voltages where self healing can occur, and often where it is necessary that the capacitor be liquid filled.
- a barrier with low oxygen and water permeability having a thermoplastic substrate, a cross-linked acrylate layer on one face of the substrate and a layer of oxygen barrier material deposited on the same face of the substrate as the acrylate layer, preferably over the acrylate layer, or in some embodiments, under the acrylate layer.
- the acrylate layer is a polymerization product of an acrylate monomer having a molecular weight in the range of from 150 to 600.
- the acrylate layer may be formed from a photopolymerizable acrylate that is sufficiently low viscosity to be sprayed on the substrate or applied by dipping.
- there is another cross-linked acrylate layer over the oxygen barrier layer it is preferable to deposit a top acrylate layer over a metallized layer before the metallized layer contacts any surfaces.
- the surface of the thermoplastic substrate is prepared for deposition of the acrylate by either heating the surface of the substrate above its melting point without deforming the substrate or by plasma treating the surface for enhancing adhesion of the acrylate. Chilling the substrate enhances deposition efficiency.
- metallized capacitor electrodes may be protected from damage by corrosion or by dielectric liquids by applying coatings of resistant polymers on one or both faces of the dielectric.
- a sheet material suitable for winding a metallized sheet capacitor employing as a substrate a thermoplastic dielectric sheet.
- a conductive metal layer is deposited on at least one face of the dielectric sheet.
- One layer of polymerized acrylate is formed on the same face of the dielectric sheet as the conductive layer, and another layer of polymerized acrylate may be formed on the opposite face of the dielectric sheet.
- the acrylate layers are formed by evaporating an acrylate monomer having a molecular weight in the range of from 150 to 600, preferably in the range of from 200 to 400, and condensing the monomer on a face of the sheet substrate as a monomer film.
- the acrylate monomer is then polymerized for forming the acrylate layer. Modifying the surface of the dielectric sheet for increasing its surface energy, preferably by plasma treatment, enhances curing or polymerization of the film by an electron beam or ultraviolet radiation.
- FIG. 1 illustrates schematically a metallized sheet capacitor constructed according to principles of this invention.
- FIGs. 3, 4 and 5 illustrate, in fragmentary transverse cross section, other embodiments of material suitable for winding capacitors.
- FIG. 6 is a schematic illustration of coating apparatus for forming such a capacitor sheet material.
- FIG. 7 is a graph with the axes representing acrylate shrinkage and layer thickness, respectively.
- FIG. 8 is a graph illustrating condensation efficiency as a function of temperature.
- FIG. 9 is a fragmentary cross section of a capacitor made with metallized sheet coated with a polymerized acrylate.
- FIG. 10 illustrates in transverse cross section a coated polypropylene with low oxygen permeability.
- FIG. 11 illustrates in transverse cross section a coated thermoplastic substrate with low oxygen permeability.
- FIG. 12 illustrates an exemplary container constructed according to principles of this invention.
- FIG. 13 is a schematic illustration of apparatus for coating substrates by spraying.
- FIG. 14 is a schematic illustration of coating apparatus for forming a barrier sheet material.
- An exemplary capacitor 10 comprises a can 11, the end of which is cut away in FIG. 1 to show the roll of capacitor material 12 inside the can.
- the layers of material forming the capacitor are wound into a cylindrical roll.
- the roll of capacitor material comprises alternating layers of metal and dielectric coiled in a tight spiral.
- the metal layers form the electrodes of the capacitor and the dielectric material between the electrodes permits accumulation of charge in the capacitor.
- Such a capacitor, intended for use at higher voltages may be filled with a dielectric liquid such as those mentioned above.
- FIG. 2 illustrates in three fragmentary transverse cross sections exemplary materials for winding such a capacitor.
- a sheet suitable for winding a capacitor has a thermoplastic substrate 13 such as thin polypropylene or polyester sheet which has a stable dielectric constant and high dielectric strength.
- a layer of metal 14 which may be vacuum deposited or sputtered is formed on at least one face of the substrate.
- a layer of polymerized acrylate 16 is deposited either over or under the metal layer as described hereinafter. In the embodiment illustrated in FIG. 2a, another layer of polymerized acrylate 17 is formed on the opposite face of the substrate.
- each sheet has a portion of the metallized layer 14 exposed along an edge of the sheet. That is, a portion of the metallized layer is not covered by an insulating layer of acrylate in this embodiment. These exposed edges of the metal layer are at opposite edges of adjacent sheets in the capacitor and provide an area to which electrical contact can be made so that alternate sheets of the capacitor material form the opposite plates of the capacitor.
- FIG. 2b illustrates another embodiment of sheet for forming a rolled capacitor.
- a layer of metal 14 is deposited on the substrate 13 and a layer of polymerized acrylate 16 is formed over the metal layer.
- the entire metal layer is covered with acrylate. Only one face of the substrate has a coating of acrylate.
- FIG. 2c reverses the layers on the substrate.
- this embodiment there is a layer of polymerized acrylate 16 formed directly on the substrate 13.
- a deposited layer of metal 14 In direct contact with and over the acrylate layer is a deposited layer of metal 14. Again, there is no acrylate layer on the opposite face of the substrate.
- the metal may extend all the way to each edge of the sheet or may be spaced a short distance from the edge of the sheet along one edge.
- FIG. 3 illustrates a variation of the capacitor material having a layer of polymerized acrylate 18 on each face of a thermoplastic substrate 19. A layer of metal 21 is deposited on top of one of the acrylate layers.
- FIG. 4 illustrates another slight variation from an embodiment as illustrated in FIG.
- a capacitor may have one electrode formed on a thermoplastic substrate 27.
- a layer of polymerized acrylate 28 is formed on each face of the substrate.
- a layer of metal 29 is deposited for forming the one electrode.
- the other electrode in such a capacitor comprises a sheet of aluminum foil 31. That electrode may be separated from an adjacent layer of metal (not shown) on another substrate via a sheet 32 of dielectric materials such as poly ⁇ propylene.
- the polypropylene and polyester materials are desirable as dielectrics for capacitors since they have a stable dielectric constant and high dielectric strength. If a metallized polypropylene, for example, is tried in a liquid filled capacitor, the thermoplastic apparently swells and ruptures the thin metallized layer. By having a very thin layer of polymerized acrylate in direct contact with the metallized electrode, the damage caused by dielectric liquid can be avoided. It is believed that the thermoset acrylate supports or stabilizes the metal film and prevents cracking despite swelling of the film substrate.
- An exemplary barrier material as illustrated in FIG. 11 comprises a thermoplastic substrate 110 having a cross-linked acrylate layer 111 on one face.
- the acrylate layer is overlain by a layer 112 of oxygen barrier material.
- a final cross-linked acrylate layer 113 is optionally formed over the oxygen barrier layer.
- Typical sheets for packaging foodstuffs include metallized polypropylene, nylon or polyester sheet.
- Metallized nylon has an oxygen permeability of about 0.05 ml/ 100 in 2 /hour (ml/645 cm 2 /hour) as measured with a Mocon Oxtran System available from Modern Controls, Minneapolis, Minnesota.
- Metallized polyester has a typical oxygen permeability of about 0.08.
- Metallized polypropylene on the other hand, has an oxygen permeability of about 2.5 and is not usually suitable for packaging where low oxygen permeability is important.
- Sheet polypropylene without any coating may have an oxygen permeability of about 100. However, if a layer of aluminum is applied to a surface of a polypropylene sheet substrate, the oxygen permeability decreases to about 2.5. Surprisingly, when an acrylate layer only about one micrometer thick is formed on the polypropylene and then covered with a layer of metal, the oxygen permeability drops to about 0.05, a value lower than metallized polyester. It is hypothesized that the film of liquid acrylate monomer deposited on the surface of the polypropylene has a smooth, high temperature surface and the surface remains smooth when the acrylate is polymerized. The metallized layer can then form a good oxygen barrier.
- a layer of acrylate monomer is deposited on the substrate and crosslinked.
- the acrylate layer is then coated with an oxygen barrier layer of SiO x or Al 2 O 3 , both of which have good resistance to oxygen permeability.
- the high temperature resistance of the crosslinked acrylate layer permits the notably higher temperature deposition of silicon oxide or aluminum oxide on the thermoplastic substrate.
- Other deposited barrier films may be formed of nitrides or silicides that can be vacuum or vapor deposite. For example, silicon nitride, aluminum nitride, or titanium nitride may be used. The materials need not be stoichiometric compounds and often are substoichiometric with excess metal.
- a still greater surprise occurs when another polymerized acrylate layer is formed over the oxygen barrier layer.
- the permeability through a polypropylene barrier material drops to about 0.002 which is appreciably better than the oxygen permeability of metallized nylon.
- the second acrylate layer may protect the metallized layer and assure retention of the oxygen barrier properties of the metal.
- a preferred composite material with low oxygen permeability has a layer of polymerized acrylate, a layer of barrier material such as SiO x , Al 2 O 3 , silicon nitride, titanium nitride or aluminum nitride and another layer of polymerized acrylate on a thermoplastic substrate.
- the layers of acrylate reduce permeability dramatically and the layer overlying the barrier material protects the barrier material from mechanical damage and also provides a surface suitable for printing.
- the acrylate comprises hexane diol diacrylate (HDDA) with a molecular weight of 226 and/or tripropylene glycol diacrylate (TRPGDA) with a molecular weight of about 300.
- HDDA hexane diol diacrylate
- TRPGDA tripropylene glycol diacrylate
- Other acrylates may be used, sometimes in combination, such as monoacrylates 2- phenoxy ethyl acrylate (M.W. 192), isobornyl acrylate (M.W. 208) and lauryl acrylate
- Molten zinc or lead-tin solder is then sprayed onto the ends of the roll (a process called Schooping) to establish electrical contact with the metallized layer.
- a connecting lead is either welded or soldered to the relatively thick contact material.
- the zinc or solder Schooping apparently enters between the metallized plastic sheets and may melt a portion of the sheet to make mechanical and electrical contact to the thin metallized layer on the sheet.
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SK434-96A SK283289B6 (en) | 1993-10-04 | 1994-10-04 | Cross-linked acrylate coating material useful for forming capacitor dielectrics and oxygen barriers |
JP51099295A JP3101682B2 (en) | 1993-10-04 | 1994-10-04 | Crosslinked acrylate coating materials useful for forming dielectric and oxygen barriers in capacitors |
DE1994632229 DE69432229T2 (en) | 1993-10-04 | 1994-10-04 | CROSSLINKED ACRYLATE COATING MATERIAL FOR THE PRODUCTION OF CAPACITOR DIELECTRICS AND OXYGEN BARRIERS |
AT94930583T ATE233939T1 (en) | 1993-10-04 | 1994-10-04 | CROSS-LINKED ACRYLIC COATING MATERIAL FOR PRODUCING CAPACITOR DIELECTRICS AND OXYGEN BARRIERS |
BR9407741A BR9407741A (en) | 1993-10-04 | 1994-10-04 | Acrylate coating |
EP19940930583 EP0758482B1 (en) | 1993-10-04 | 1994-10-04 | Cross-linked acrylate coating material useful for forming capacitor dielectrics and oxygen barriers |
AU79655/94A AU694143B2 (en) | 1993-10-04 | 1994-10-04 | Cross-linked acrylate coating material useful for forming capacitor dielectrics and oxygen barriers |
KR1019960701781A KR100241470B1 (en) | 1993-10-04 | 1994-10-04 | Cross-linked acrylate coating material useful for forming capacitor dielectric |
FI961478A FI961478A0 (en) | 1993-10-04 | 1996-04-02 | Crosslinked acrylate coating for the formation of capacitors' insulations and the acid barrier |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/131,328 US5440446A (en) | 1993-10-04 | 1993-10-04 | Acrylate coating material |
US22857994A | 1994-04-15 | 1994-04-15 | |
US08/131,328 | 1994-04-15 | ||
US08/228,579 | 1994-04-15 |
Publications (1)
Publication Number | Publication Date |
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WO1995010117A1 true WO1995010117A1 (en) | 1995-04-13 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1994/011257 WO1995010117A1 (en) | 1993-10-04 | 1994-10-04 | Cross-linked acrylate coating material useful for forming capacitor dielectrics and oxygen barriers |
Country Status (11)
Country | Link |
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US (3) | US5725909A (en) |
EP (2) | EP0758482B1 (en) |
JP (2) | JP3101682B2 (en) |
KR (1) | KR100241470B1 (en) |
AT (2) | ATE233939T1 (en) |
AU (1) | AU694143B2 (en) |
BR (1) | BR9407741A (en) |
DE (2) | DE69432229T2 (en) |
FI (1) | FI961478A0 (en) |
SK (1) | SK283289B6 (en) |
WO (1) | WO1995010117A1 (en) |
Cited By (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996025243A1 (en) * | 1995-02-17 | 1996-08-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for producing a layer system on substrates and the layer system produced by the said method |
EP0787826A1 (en) * | 1996-01-30 | 1997-08-06 | Becton, Dickinson and Company | Blood collection tube assembly |
EP0787824A2 (en) * | 1996-01-30 | 1997-08-06 | Becton, Dickinson and Company | Non-Ideal Barrier coating sequence composition |
EP0787825A1 (en) * | 1996-01-30 | 1997-08-06 | Becton, Dickinson and Company | Blood collection tube assembly |
EP0789370A1 (en) * | 1996-02-07 | 1997-08-13 | Catalina Coatings, Inc. | Metallized film capacitor |
EP0789092A3 (en) * | 1996-01-30 | 1997-08-27 | Becton Dickinson Co | |
EP0799068A1 (en) * | 1994-12-23 | 1997-10-08 | University Of Florida Research Foundation, Inc. | Combined plasma and gamma radiation polymerization method for modifying surfaces |
EP0842046A1 (en) * | 1996-04-04 | 1998-05-20 | Sigma Laboratories of Arizona, Incorporated | Hybrid polymer film |
US5811183A (en) * | 1995-04-06 | 1998-09-22 | Shaw; David G. | Acrylate polymer release coated sheet materials and method of production thereof |
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Also Published As
Publication number | Publication date |
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SK43496A3 (en) | 2003-03-04 |
EP0722787A2 (en) | 1996-07-24 |
KR960705330A (en) | 1996-10-09 |
EP0758482A4 (en) | 1997-06-04 |
EP0758482B1 (en) | 2003-03-05 |
JP3101682B2 (en) | 2000-10-23 |
EP0758482A1 (en) | 1997-02-19 |
DE69430754D1 (en) | 2002-07-11 |
ATE218398T1 (en) | 2002-06-15 |
DE69432229D1 (en) | 2003-04-10 |
ATE233939T1 (en) | 2003-03-15 |
BR9407741A (en) | 1997-02-12 |
EP0722787B1 (en) | 2002-06-05 |
JP2000235930A (en) | 2000-08-29 |
AU7965594A (en) | 1995-05-01 |
US6231939B1 (en) | 2001-05-15 |
SK283289B6 (en) | 2003-05-02 |
FI961478A (en) | 1996-04-02 |
DE69432229T2 (en) | 2003-09-25 |
EP0722787A3 (en) | 1997-06-04 |
AU694143B2 (en) | 1998-07-16 |
KR100241470B1 (en) | 2000-02-01 |
US6420003B2 (en) | 2002-07-16 |
JPH08512256A (en) | 1996-12-24 |
US20010001284A1 (en) | 2001-05-17 |
US5725909A (en) | 1998-03-10 |
DE69430754T2 (en) | 2003-01-02 |
FI961478A0 (en) | 1996-04-02 |
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