CN105658839A - 柔性复合材料、其制造方法及其用途 - Google Patents
柔性复合材料、其制造方法及其用途 Download PDFInfo
- Publication number
- CN105658839A CN105658839A CN201480043126.5A CN201480043126A CN105658839A CN 105658839 A CN105658839 A CN 105658839A CN 201480043126 A CN201480043126 A CN 201480043126A CN 105658839 A CN105658839 A CN 105658839A
- Authority
- CN
- China
- Prior art keywords
- flexible
- matrix material
- paper tinsel
- plastic foil
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 230000008021 deposition Effects 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000011888 foil Substances 0.000 claims description 69
- 229920003023 plastic Polymers 0.000 claims description 63
- 239000004033 plastic Substances 0.000 claims description 62
- 238000000151 deposition Methods 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 49
- 239000011159 matrix material Substances 0.000 claims description 32
- 230000002708 enhancing effect Effects 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- -1 vinyl halides Chemical class 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000007740 vapor deposition Methods 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229960001866 silicon dioxide Drugs 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 230000005670 electromagnetic radiation Effects 0.000 claims description 6
- 230000005662 electromechanics Effects 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 230000005622 photoelectricity Effects 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000005388 borosilicate glass Substances 0.000 claims description 5
- 230000035699 permeability Effects 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229920002313 fluoropolymer Polymers 0.000 claims description 3
- 239000004811 fluoropolymer Substances 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims description 2
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920006216 polyvinyl aromatic Polymers 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- 239000005368 silicate glass Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229920001707 polybutylene terephthalate Polymers 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 239000002985 plastic film Substances 0.000 abstract 1
- 229920006255 plastic film Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 79
- 239000000126 substance Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 238000009834 vaporization Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000008016 vaporization Effects 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000005566 electron beam evaporation Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 229920001940 conductive polymer Polymers 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 239000004697 Polyetherimide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 230000003678 scratch resistant effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920005570 flexible polymer Polymers 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000574 NaK Inorganic materials 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NSIKFNOYIGGILA-UHFFFAOYSA-N [Na].[Na].[K] Chemical compound [Na].[Na].[K] NSIKFNOYIGGILA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- QZFJRYUBWMFRFJ-UHFFFAOYSA-N cadmium copper Chemical compound [Cu][Cd][Cd] QZFJRYUBWMFRFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000012780 transparent material 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
本发明涉及柔性复合材料，其包含给定上表面和下表面的塑料箔，以及通过等离子体增强热气相沉积直接施加到至少一个所述表面上并包含无机层气相沉积材料的至少一个针对气体和液体的介电阻隔层。该柔性复合材料可用于制造柔性电路或显示器，并对氧和/或水蒸气具有高阻隔效果。
Description
本发明涉及可用于柔性电子器件领域的柔性复合材料，尤其可用于制造柔性电子电路、柔性印刷电路板、柔性显示器（例如柔性LCD显示器或柔性OLED显示器）、柔性发光元件（例如柔性LED或柔性OLED）、柔性发电机或蓄能器（如柔性太阳能电池或柔性蓄电池）或柔性扁平电缆。
柔性电子器件，也称为柔性电路，是通过在柔性聚合物基板上安装电子器件来组装电子电路的技术。在此，例如使用耐高温聚合物的箔或透明聚合物的箔。此外，柔性电路可以是已经通过成像工艺，例如通过丝网印刷或通过喷墨印刷向其施加印刷电路，如银-、铜-、铝-或铂-迹线的箔。柔性电子电路可以使用与用于刚性印刷电路板相同的结构元件来制造，并可以在生产过程中调节为所需形状或可以在使用过程中弯曲。这些柔性印刷电路（FPC）可以使用光刻技术来制造。在柔性箔上制造电路或制造柔性扁平电缆（FFC）的一种替代途径是在两层塑料箔如聚对苯二甲酸乙二醇酯（PET）之间层压非常薄的金属条。为此，这些PET层涂有在层压过程中活化的热固性粘合剂。FPC和FFC对于许多应用表现出一系列优点：
·可制造固定安装的电子组件，其中需要三维（inAchsen）电连接，例如在照像机中
·可产生电连接，其中该组件必须在预期使用过程中表现出柔性，例如在移动电话中
·可在组件之间构造电连接，以取代更重和更庞大的电缆线束，例如在汽车、轮船、飞机、火箭或卫星中，以及
·可在其中板厚度或空间原因（Platzgründe）是决定因素的环境中产生电连接。
柔性电路容易受到来自环境的化学侵袭。例如，氧或水蒸气会对微电子电路的寿命产生不利影响。这尤其是在这些电路用在化学腐蚀性环境中时成立。始终尝试将电子电路与环境隔离，以确保它们的稳定性和更长的功能性。对此的一个实例是将集成电路封装在树脂中。在柔性电路的情况下，这样的方法将对产品的柔性产生不利影响。已经尝试使用薄玻璃箔来包封柔性电路。这里的缺点在于，在许多情况中这些玻璃箔的柔性不足。在弯曲层压材料时，尤其在不同曲率下，这些产品常常失效，玻璃箔开裂并丧失其原始的功能。
具有潜在的巨大用户利益的其它领域是柔性透明显示器、柔性透明发光元件或柔性光伏元件。可以赋予这些元件应用所需的任何形状，并允许设计师开辟全新的应用领域。因此，可以以这种方式打破通信设备如智能电话迄今为止所采用的条形形状。此外，还有可能以完全新的形状制造需要阻隔和/或耐候性涂层的部件。包含塑料的部件通常可比玻璃部件更简单地成型。可以以全新的形状制造玻璃-塑料复合材料部件。特别在汽车制造中，柔性显示器或发光元件可以无缝整合在内部空间设计的形式语言中。这样的柔性显示器和发光元件或光伏元件可以以节约空间的方式使用和运输，例如以卷曲形式。这些元件中使用的电子器件对水和氧气敏感，因此必须被保护。这可以通过用塑料箔封装来实现。但是，迄今尚未已知对氧和水蒸气具有足够高的阻隔功能同时又是极其柔性的并能够在使用中任意折叠或塑形而不因此丧失其功能的塑料箔。
令人惊讶地，现在已经发现具有塑料箔的配备有阻隔层的复合材料不具有已知解决方案的缺点，并且非常适合作为用于柔性电子器件的阻隔箔。
这种复合材料是热稳定的，显示出对氧和水蒸气的极高的阻隔效果，耐受湿气，可以均匀地施加或层压，具有光滑表面，表现出优异的层间粘附性，是柔性和防刮的，并且可以是透明的。
本发明涉及柔性复合材料，其包含给定上表面和下表面的塑料箔，以及对气体和液体，特别是对氧和水蒸气的至少一个介电阻隔层，其通过等离子体增强热气相沉积直接施加到至少一个表面上并包含无机层气相沉积材料。
介电层在不同基板表面上的等离子体增强热气相沉积原则上是已知的。这种工艺的实例描述在WO2011/009444A1、WO2010/009719A1和WO2011/035783A1中。在这些文献中并未描述塑料箔与介电层的组合。特别令人惊讶的是，柔性塑料箔与气相沉积的介电层形成了极其牢固附着的组合，这种组合既没有削弱初始箔的柔性，也没有削弱其在柔性电子器件的生产与使用中的应用。就氧和水蒸气而言，用本发明的复合材料能够实现对封闭的产品，尤其是柔性电子产品如柔性电子电路、柔性印刷电路板、柔性显示器、柔性发光元件、柔性发电机或蓄能器或柔性扁平电缆的非常好的保护。
根据本发明的一个方面，提供了在塑料箔上制造涂层的方法，其中所述方法包括以下步骤：提供具有至少一个待涂覆的表面的塑料箔，并借助热汽化至少一种无机层气相沉积材料在待涂覆的塑料箔表面上沉积至少一种无机层气相沉积材料，由此在待涂覆的塑料箔表面上制造涂层。该涂层可完全或仅部分借助等离子体增强热电子束汽化来制造。这种施加方法是特别温和的。许多塑料仅具有有限的热稳定性。这种方法的优点在于可在低于100℃的温度下施加。
本发明的另一方面涉及涂覆的塑料箔，尤其根据前述方法制备，其中在至少一个表面上形成至少部分由至少一种无机层气相沉积材料构成的涂层。由此可以施加厚度范围在几纳米至数微米的透明玻璃层，其与塑料箔结合一起形成柔性和同时透明的复合材料。
作为无机层气相沉积材料原则上可以使用能够在等离子体增强热电子束汽化条件下汽化的任何无机材料，尤其是基于金属、半导体、金属氧化物、金属碳化物或金属氮化物的材料。金属的优选实例是铝、金、银、铬、镍或铜；半导体的优选实例是硅、镓、碲化镉或铜-铟-镓-硒-硫-化合物；如铜-铟-镓二硒化物或铜-铟二硫化物；金属氧化物的优选实例是氧化铝、二氧化硅、氮化硅、碳化硅、二氧化钛、氧化锆、铟-锡氧化物、氟掺杂的氧化锡、铟-镓-锡氧化物或尤其是气相沉积玻璃材料。优选使用硅酸盐玻璃，特别优选使用硼硅酸盐玻璃。
借助本发明可实现这样的可能性，通过沉积至少一种无机层气相沉积材料以有效的方式为各种应用目的在塑料箔上生成单独设计的全面积或结构化涂层。这种材料能够提供用于各种应用的塑料箔的构型化的涂层。
与不同的无机层气相沉积材料结合可得到单独或结合的优点，由此根据应用情况和所用无机层气相沉积材料可以进行不同的优化。因此，与类似厚度的获自气相沉积玻璃材料的层相比，由单组分体系二氧化硅获得的气相沉积层通常具有更高的光透射，尤其在紫外波长范围内。二氧化硅的击穿电压也更高。氧化铝的特点是高耐刮性和高光学折射率。二氧化钛具有非常高的光学折射率。与气相沉积玻璃相比，氮化硅具有高击穿电压，此外还具有高光学折射率。相反，气相沉积玻璃非常适合生产具有高的氧和水蒸气阻隔功能的表面层。
用无机层气相沉积材料能够借助等离子体增强热电子束汽化比较温和地涂覆塑料箔。
例如可用作气相沉积玻璃材料的硼硅酸盐玻璃的熔融温度为大约1300℃。对于二氧化硅而言，相应的温度为大约1713℃，对于氧化铝而言为大约2050℃，对于二氧化钛而言为大约1843℃，对于氮化硅而言为大约1900℃，对于碳化硅而言为超过2300℃。
使用无机层气相沉积材料的等离子体增强热电子束汽化可以实现优化的层沉积。等离子体增强的热汽化可以按照所需应用情况单独改变，以在制造塑料箔的涂层时形成所需层性质。借助等离子体增强例如还能够控制和优化层的粘附性和在层中的固有压缩-或拉伸应力。此外可影响该气相沉积层的化学计量。
在本发明的各种实施方案中，该塑料箔的涂层可以制成单层或多层的。在多层结构的情况中，该塑料箔的两个表面可能均被涂覆和/或在一个表面上沉积多个层。在这种情况中，可由第一气相沉积材料沉积成至少一个子层，并且由另一气相沉积材料沉积成至少一个另外的子层。例如可提供，第一子层由二氧化硅形成，随后在其上形成氧化铝或硼硅酸盐玻璃的层。
在一个实施方案中，除了借助等离子体增强热电子束汽化沉积的涂层的一个或多个子层而外可以借助其它制备方法形成一个或多个另外的子层，例如借助溅射或借助CVD方法（“ChemicalVaporDeposition”，化学气相沉积）。该涂层的一个或多个另外的子层可以在沉积该一个或多个子层之前和/或之后处理。
等离子体增强促进了气相沉积层的高品质。因此可实现好的密实度并由此实现好的密封性质。由于改善的层的生长，很少产生缺陷。待涂覆的基板无需预热。这样的涂覆也称为IAD-冷涂覆法。该方法的一个特殊的优点是高沉积速率，可以实现该高沉积速率，由此在总体上可优化生产时的处理时间。
在传统的气相沉积法中，为获得高的层品质必须对基板进行强预热。这导致冷凝粒子增多的解吸并因此降低了可达到的气相沉积速率。等离子体增强此外导致，可以使用等离子体束调整蒸汽叶（Dampfkeule），以实现汽化粒子在待涂覆的塑料表面上的各向异性到达。结果是可以在没有所谓的链接的情况下实现层沉积。在此，链接是在待涂覆的塑料箔表面上的不同区域之间的不合意的连接。
在优选的工艺设计中可具有一个或多个以下工艺特征。在一个实施方案中，该等离子体增强热电子束汽化法可以以大约20纳米/分钟至大约2微米/分钟的气相沉积速率进行。可以计划使用氧、氮和/或氩等离子体。替代或补充，在热汽化的工艺步骤之前可以进行预处理以活化和/或清洁待涂覆的塑料表面。该预处理可以使用等离子体进行，尤其是氧、氮和/或氩等离子体。优选地，该预处理原位进行，即在热汽化之前直接在涂覆装置中进行。
在本发明的一种适宜的实施方案中可提供，热汽化至少一种无机层气相沉积材料的步骤包括由至少两个汽化源构成的共同汽化的步骤。借助由至少两个汽化源构成的共同汽化可以沉积相同或不同的材料。
优选地，本发明的一个扩展提供，所述在待涂覆的塑料箔表面上制造涂层的步骤多次进行。
在本发明的另一有利实施方案中可提供，在该塑料箔的至少两个位置上制造该涂层。例如，可以在塑料箔的顶部和底部制造该涂层。可以以在时间上平行或相继的沉积工艺进行在顶部和底部的层沉积。
在本发明的优选的进一步扩展中，将结构化涂层施加到该塑料箔的至少一个表面上，并且该结构化涂层的结构是至少部分填充的。导电和/或透明材料可用于至少部分填充该结构化涂层。
在本发明的一种适宜的实施方案中，在该塑料箔的至少一个表面上制造至少一个导电区域。借助该至少一个导电区域可以例如制造一个或多个导轨。它们可以位于背离该涂层的塑料箔的表面上或直接位于被该涂层覆盖的塑料箔的表面上，或位于该塑料箔的两面上。
本发明的另一有利的实施方式提供，在结构化涂层上形成粘结层（Bond-Schicht）。该粘结层包含例如用于后续的金属化的晶种层和/或粘合剂层。
优选地，本发明的一种扩展提供，该塑料箔的至少一个表面的涂层形成为多层涂层。在一个实施方式中，用气相沉积玻璃材料的层，尤其是硼硅酸盐玻璃的层，或用二氧化硅和气相沉积玻璃材料，或用二氧化硅和氧化铝来形成该多层涂层，在这种情况下，气相沉积玻璃材料或氧化铝的子层构成二氧化硅上的覆盖层。这方面可提供，使用不同于热汽化的沉积技术，例如溅射来制造一个或多个子层。
在本发明的一种有利的实施方案中可提供，以0.05微米至100微米的层厚度，优选以0.1微米至50微米的层厚度和更优选以大约0.1微米至1微米的层厚度形成该涂层。对本发明的目的而言，使用轮廓仪（例如来自VeecoMetrologyGroup）测定层厚度。
在本发明的进一步扩展中提供，该塑料箔的表面在沉积至少一种无机层气相沉积材料的过程中具有最高大约120℃，优选最高大约100℃的温度。这种低基板温度在涂覆热敏材料时是特别有利的。在一个实施方案中使用等离子体增强热电子束汽化能使制得的层足够致密化，而无需为此进行任何后退火。
根据本发明，使用塑料箔作为基板。原则上可以涉及任意塑料，如热固性塑料，或特别是热塑性塑料。
该塑料通常是合成的有机聚合物。除了均聚物而外也可以使用共聚物。也可使用由有机聚合物的混合物制成的箔或由塑料复合材料制成的箔。
所用塑料箔可以由部分结晶和/或非晶的有机聚合物构成。优选使用由有机聚合物制成的透明箔。这在本说明书中应理解为是指在380纳米至780纳米的波长范围内，该箔对入射在箔表面上的电磁辐射具有至少80%、优选至少90%和最优选95%至100%的电磁辐射透射率。
特别优选使用由非晶有机聚合物制成的箔。
根据本发明使用的塑料箔的厚度可以在宽范围内变化。应如此选择箔厚度以确保预期用途所需的柔性。该塑料箔的典型厚度在0.5微米至5毫米，尤其在1微米至1毫米，最特别优选在5微米至500微米的范围内波动。
根据本发明使用的聚合物可以是以任意制得的产品，例如是通过自由基聚合、通过缩聚或通过加聚制得的产品。
优选使用的聚合物类型的实例是聚烯烃，如聚乙烯、聚丙烯、衍生自多环烯烃的聚合物，例如环烯烃共聚物，例如衍生自降冰片烯和乙烯。
优选使用的聚合物类型的另外的实例是聚卤乙烯或聚偏二卤乙烯（Polyvinylidenhalogenide），如聚氯乙烯、聚偏二氯乙烯或聚偏二氟乙烯。
优选使用的聚合物类型的另外的实例是聚乙烯基芳烃，如聚苯乙烯或苯乙烯与其它烯属不饱和单体的共聚物。
优选使用的聚合物类型的另外的实例是聚丙烯酸酯或聚甲基丙烯酸酯（“聚(甲基)丙烯酸酯”）、聚乙烯基醚、聚乙烯基羧酸酯、聚四卤代乙烯，如聚四氟乙烯，或丙烯腈均聚物或-共聚物。
优选使用的聚合物类型的另外的实例是聚甲醛均聚物或共聚物。
优选使用的聚合物类型的另外的实例是聚酰胺，如衍生自脂族或芳族二羧酸和衍生自芳族或脂族二胺以及衍生自芳族或脂族氨基羧酸的聚酰胺。其实例是衍生自己二酸和1,6-己二胺、衍生自癸二酸和1,6-己二胺、衍生自己内酰胺、或衍生自对苯二甲酸和衍生自1,4-二氨基苯的脂族聚酰胺。
优选使用的聚合物类型的另外的实例是包括聚碳酸酯的聚酯，如衍生自脂族或芳族二羧酸和衍生自芳族或脂族二醇以及衍生自芳族或脂族羟基羧酸或衍生自脂族或芳族二醇和衍生自光气的聚酯。其实例是衍生自对苯二甲酸和乙二醇、衍生自邻苯二甲酸和乙二醇、衍生自对苯二甲酸和1,4-丁二醇、衍生自羟基苯甲酸或衍生自双酚A和光气的聚酯。
特别优选涂覆有防刮气相沉积玻璃材料的聚碳酸酯。这些可特别好地用作例如汽车制造中的防刮部件。
优选使用的聚合物类型的另外的实例是聚氨酯，如衍生自脂族或芳族二异氰酸酯和衍生自芳族或脂族二醇的聚氨酯。其实例是衍生自苯基二异氰酸酯和衍生自聚烷撑二醇的聚氨酯。
优选使用的聚合物类型的另外的实例是聚烷撑二醇，如聚乙二醇、聚丙二醇或聚丁二醇，或聚乙烯基醇。这些聚合物当然必须在分子量和/或粘度方面加以选择以便由此能形成箔。
优选使用的聚合物类型的另外的实例是聚(有机)硅氧烷，如聚(二甲基)硅氧烷。这些聚合物当然也必须在分子量和/或粘度方面加以选择以便能由此形成箔。
非常特别优选使用由耐高温聚合物制成的箔作为基板。这在本说明书中应理解为是指该聚合物能用于150至250℃的持续使用温度。最高至400℃的短时温度峰值是可能的，例如在用于CVD或PACVD方法时。
特别优选使用的耐高温聚合物类别是：
·含氟聚合物如聚四氟乙烯或全氟烷氧基烷烃
·聚亚苯基类
·聚芳基类，其中芳环经由氧-或硫原子或经由CO或SO2基团连接；其实例是聚苯硫醚、聚醚砜或聚醚酮
·芳族聚酯（聚丙烯酸酯）或芳族聚酰胺（聚芳酰胺）；其实例是聚间苯二甲酰间苯二胺、聚对苯二甲酰对苯二胺和聚羟基苯甲酸酯及其共聚物
·杂环聚合物如聚酰亚胺、聚苯并咪唑类或聚醚酰亚胺。
另外可用作基板的箔是由导电聚合物制成的箔。这在本说明书中应理解为是指具有金属导电性的箔。
优选使用的导电聚合物类别是通过掺杂被赋予导电性的上述聚合物。
该聚合物首先是绝缘体或半导体。然后，在氧化或还原掺杂该聚合物时，才开始具有可与金属导体相比较的导电性。
导电聚合物的实例是聚苯胺或聚乙炔，例如可以通过掺杂五氟化砷或碘来显著提高其导电性。导电聚合物的另外的实例是掺杂的聚吡咯、聚苯硫醚、聚噻吩以及具有大环配体如酞菁的金属有机配合物。氧化性掺杂可以用五氟化砷、四氯化钛、溴或碘来实现；相反，还原性掺杂可以用钠-钾合金或二苯甲酮二锂（Dilithiumbenzophenonat）来实现。
涂覆的塑料箔的优选实施方案提供了以下特征的一个或多个：
借助等离子体增强热电子束汽化沉积的一个或多个层优选是根据DIN12116的至少2级的耐酸的。参考DIN12116以类似的方式进行。待测试的表面因此在盐酸（c=5.6摩尔/升）中煮沸六小时。随后，测定以毫克/100平方厘米为单位的重量损失。当六小时后表面重量损失的一半高于0.7毫克/100平方厘米且最高1.5毫克/100平方厘米时给予2级。更优选地，当六小时后表面重量损失的一半为最高0.7毫克/100平方厘米时给予1级。
替代或补充，提供根据DIN52322（ISO695）2级，更优选1级的耐碱性。这里也也以类似的方式参考进行。为了测定耐碱性，将表面暴露于沸腾的水溶液三小时。该溶液由等份数的氢氧化钠（c=1摩尔/升）和碳酸钠（c=0.5摩尔/升）组成。测定重量损失。当三小时后表面重量损失高于75毫克/100平方厘米且最高175毫克/100平方厘米时给予2级。根据1级，三小时后表面重量损失为最高75毫克/100平方厘米。
在一个实施方案中提供，借助等离子体增强热电子束汽化沉积的一个或多个层具有根据DIN12111（ISO719）的至少2级，优选1级的耐水解性。
替代或补充，还可以形成耐溶剂性。
在一个优选实施方式中，借助等离子体增强热电子束汽化沉积的层具有小于+500MPa的层内应力，其中正号表示在该层中的压应力。优选地，制得+200MPa至+250MPa以及–20MPa至+50MPa的层内应力，其中负号表示在该层中的拉应力。
在另一优选的实施方式中，该由借助等离子体增强热电子束汽化沉积的载体层和塑料箔组成的复合材料具有低于100(g/m2*24h*bar)、优选低于10-2(g/m2*24h*bar)、特别优选低于10-5(g/m2*24h*bar)和最特别优选10-6至10-10(g/m2*24h*bar)的氧渗透性。
在另一优选的实施方式中，该由借助等离子体增强热电子束汽化沉积的载体层和塑料箔组成的复合材料具有低于100(g/m2*24h*bar)、优选低于10-2(g/m2*24h*bar)、特别优选低于10-5(g/m2*24h*bar)和最特别优选10-6至10-10(g/m2*24h*bar)的水蒸气渗透性。
可以用来自Mocon（www.mocon.com）的仪器测定氧-和/或水蒸气渗透性。按照ASTMF1249进行该测定。
在一个特别优选的实施方式中，该由借助等离子体增强热电子束汽化沉积的载体层和塑料箔组成的复合材料是透明的。这在本说明书中应理解为是指在380纳米至780纳米的波长范围内，其对入射在涂有所述阻隔层的复合材料表面上的电磁辐射具有至少80%、优选至少90%和最特别优选95%至100%的电磁辐射透射率。
补充或替代，可以将借助等离子体增强热电子束汽化沉积的层制成耐刮的，具有按照ISO9385至少HK0.1120=400的Knoop硬度。
在本发明的一种实施方案中提供，借助等离子体增强热电子束汽化沉积的层在采用50纳米尖端的纳米压痕试验中以大于100mN的侧向力非常牢固地粘附在该塑料表面上。或者，该气相沉积层的粘附性可以通过胶带剥除试验或通过划格/胶带胶带剥除试验（DINENISO2409）来测定。
制造该涂层的方法可以调整，以形成一种或多种上述层性质。
在本发明的进一步扩展中提供，按照本发明涂覆的塑料箔与一个或多个基板结合。该基板又可以是箔或复合箔，例如是塑料箔和/或金属箔，或是电气、电子、光电、机电或微机械部件。按照本发明涂覆的箔与另外的箔或部件的结合例如可以通过粘合、层压或焊接来实现。按照本发明涂覆的塑料箔可以覆盖所述另外的箔或所述另外的复合箔的一个表面或其两个表面。按照本发明涂覆的塑料箔可以覆盖该部件的表面的一部分，或包封该部件的整个表面。根据本发明，该无机层气相沉积材料还可以施加到目前还不能配备成耐刮形式的特别形成的表面上。这将例如能够在汽车工程中提供全新的部件。
所述另外的基板可以是已经与按照本发明涂覆的塑料箔结合的任意产品。下文中用柔性电子器件作为例子来描述此类复合材料的一些优选实施方案。但是，其它产品也可以与按照本发明涂覆的塑料箔结合。
优选地，按照本发明涂覆的塑料箔与选自半导体器件、光电器件、机电器件和/或微机械器件的器件结合，或与构成柔性扁平电缆或柔性印刷电路的组成部分的复合箔结合。
本发明优选涉及包含柔性塑料箔（基箔）的柔性复合材料，其在一侧上施加有由导电材料，尤其是金属、导电聚合物和/或填充有金属的聚合物构成的图案，所述图案与施加到该侧的电子器件结合，例如与集成电路、晶体管、电容器、电阻和/或电感结合，并且其给定了电子电路，并且在该侧上和任选在远离其的一侧上涂有本发明的复合箔，以使得涂有该无机气相沉积材料的一侧朝外。具有这种电路类型的元件仅可以从一侧进入。但是，可以在基箔中提供孔洞以便提供用于与电子元件连接的导线。此外，这样的柔性电路配备有双通道。在这样的柔性电路中同样使用单一导电层。但是，有可能从两侧接近该导体图案的所选特征。
本发明优选在另一实施方案中涉及包含柔性塑料箔（基箔）的柔性复合材料，其在两侧上施加有由导电材料，尤其是金属、导电聚合物和/或填充有金属的聚合物构成的图案，所述图案与施加到一侧或两侧的电子器件结合，例如与集成电路、晶体管、电容器、电阻和/或电感结合，并且其给定了电子电路，并且在一侧上，任选在两侧上涂有本发明的复合箔，以使得涂有该无机气相沉积材料的一侧朝外。在这些双侧柔性电路中使用两个导体层。这些双侧柔性电路可以在采用或不采用通孔制造。通过通孔提供基箔两侧上的元件的连接，因此元件可以安置在两侧上。
本发明优选在另一实施方案中涉及包含至少两个柔性塑料箔（基箔）的柔性复合材料，所述柔性塑料箔在一侧或两侧上施加有由导电材料，尤其是金属、导电聚合物和/或填充有金属的聚合物构成的图案，所述图案与电子器件结合，例如与集成电路、晶体管、电容器、电阻和/或电感结合，所述电子器件位于一个基箔的一侧上或位于一个基箔的两侧上或位于多个基箔的一个或多个侧面上并且给定了电子电路，并且其在该复合材料的一侧上，任选在两侧上，涂有本发明复合箔，以使得涂有所述无机气相沉积材料的一侧朝外。在这些多层柔性电路中使用两个或多个导体层。通常用导电材料的各个图案之间的通孔来提供这些多层柔性电路，尽管这并非绝对必要的。该多层柔性电路的各个层可以以连续或不连续方式通过层压来构造。在需要最大程度的柔性的情况下，不连续层压的运用是惯用的。
本发明优选在另一实施方案中涉及由柔性电路和由刚性电路构成的复合材料（混合型结构），其在该复合材料的一侧上和任选在两侧上涂有本发明的复合箔，以使得涂有所述无机气相沉积材料的一侧朝外。这样的柔性电路是由刚性和柔性基板组成的柔性电路在单一结构中彼此层压的混合型结构。刚性柔性电路不应与硬化的柔性结构（其是简单的柔性电路，其中已经固定刚性元件以便可以就地支撑该电子器件的重量）混淆。在刚性柔性电路中的层通常也通过通孔彼此电连接。
用于制造柔性电路的基箔是柔性聚合物箔。其提供了用于层压件的基础层。在正常情况下，该柔性电路的基箔提供该柔性电路的大部分基本物理性能和电性能的载体。在柔性电路的无粘合构造中，该基底材料提供了所有特性性质。虽然多种厚度是可能的，但大部分柔性箔通常在5微米至500微米的相对薄的范围内使用。但是更薄或更厚的材料也是可能的。有许多可优选作为基箔用于制造柔性电路的不同的材料。其实例是聚酯（PET）、聚酰亚胺（PI）、聚萘二甲酸乙二醇酯（PEN）、聚醚酰亚胺（PEI）或各种含氟聚合物（FEP）。
可以以多层产品形式获得柔性电路。这通常通过层压来完成。粘合剂可以用作产生层压件的接合介质。可用粘合剂包括熔融粘合剂或热固性材料，其中通过固化进行粘合。
金属箔通常在柔性层压件中用作导电元件。金属箔是通常蚀刻成导线的材料。厚度不同的多种金属箔可以用于制造柔性电路。优选使用铜箔。
在另一优选的实施方式中，本发明的涂覆的塑料箔在由至少一层导电材料与至少一个塑料箔构成的层压件的外侧的一侧或两侧上使用，使得涂有该无机气相沉积材料的一侧朝外。导电材料层优选以图案形式，尤其以相互平行延伸的导轨形式形成，并任选安装在两片塑料箔之间。这样的层压件可以用作扁平电缆。
本发明还提供了用于制造上述涂覆的塑料箔的方法。
本发明的方法包括以下措施：
i）将给定上表面和下表面的塑料箔预先放置在气相沉积设备中，和
ii）通过无机层气相沉积材料的等离子体增强热气相沉积向至少一个所述表面上沉积至少一个针对气体和液体，尤其针对氧和水蒸气的介电阻隔层。
通过沉积一个或多个阻隔层可以提供机械稳定和耐刮的器件。
用本发明的方法可以提供涂有无机层气相沉积材料，尤其涂有玻璃的箔，其是耐刮的，并且其可以形成迄今为止用玻璃无法实现的各种形状。该表面具有玻璃的性质，但是形状与玻璃中通常固有的正常限制无关。由此，例如对于汽车工程以及对于火车和对于建筑施工而言，可以制造目前因材料限制而不可能实现的器件。
本发明的箔复合材料特别可用于制造电气、电子、光电、机电和微机械器件，并还用于制造柔性电连接。
电气器件的实例是柔性发电机或电能蓄能器，尤其是柔性太阳能电池（柔性光伏电池）或柔性蓄电池。
电子器件的实例是柔性电子电路或柔性印刷电路板。
光电器件的实例是柔性显示器，尤其是柔性LCD显示器或柔性OLED显示器；或柔性发光元件，尤其是柔性LED、柔性OLED或柔性激光二极管；或柔性光电晶体管。
机电器件的实例是继电器、麦克风或扬声器。
微机械部件的实例是传感器或动作器（例如继电器、开关、阀、泵）和微系统（例如微型马达或按钮）。
这些部件可以用于工业和家庭的许多领域，例如用于计算机、外围设备（如打印机或键盘）、移动电话、照相机、个人娱乐设备、饰品、功能性服装、监视器、汽车、船舶、飞机、火箭或卫星。
许多电路包括用于被动布线的结构，其用于连接电子元件如集成电路、电阻、电容等等，或用于在不同的电子器件之间建立连接（直接或借助插塞接头）。本发明还涉及上述涂覆的复合材料在用于连接电气、电子、光电、机电或微机械部件的电缆中的用途。
Claims (26)
1.柔性复合材料，其包含给定了上表面和下表面的塑料箔，和至少一个直接施加在至少一个表面上的等离子体增强热气相沉积的针对气体和液体的介电阻隔层，所述介电阻隔层包含无机层气相沉积材料。
2.根据权利要求1所述的复合材料，其特征在于所述塑料箔在两个表面上各具有至少一个等离子体增强热气相沉积的针对气体和液体的介电阻隔层。
3.根据权利要求1所述的复合材料，其特征在于所述介电阻隔层的无机层气相沉积材料选自铝、金、银、铬、镍、铜、硅、镓、氧化铝、二氧化硅、氮化硅、碳化硅、二氧化钛、氧化锆、铟-锡-氧化物、氟掺杂的氧化锡、铟-镓-锡氧化物、碲化镉、铜-铟-镓-硒-硫-化合物或气相沉积玻璃材料，优选硅酸盐玻璃，尤其是硼硅酸盐玻璃。
4.根据权利要求1所述的复合材料，其特征在于所述介电阻隔层的厚度为50纳米至100微米，优选为100纳米至50微米，特别优选为100纳米至1微米。
5.根据权利要求1所述的复合材料，其特征在于所述塑料箔选自热塑性塑料或热固性塑料，尤其选自透明塑料。
6.根据权利要求5所述的复合材料，其特征在于所述热塑性塑料选自聚烯烃、聚卤乙烯、聚偏二卤乙烯、聚乙烯基芳烃、聚丙烯酸酯、聚甲基丙烯酸酯、聚乙烯基醚、聚乙烯基羧酸酯、聚四卤代乙烯、丙烯腈均聚物或-共聚物、聚甲醛均聚物或-共聚物、聚酰胺、包括聚碳酸酯的聚酯、聚氨酯、聚亚烷基二醇和/或聚(有机)硅氧烷。
7.根据权利要求5所述的复合材料，其特征在于所述热塑性塑料是耐高温和优选透明的塑料，其选自含氟聚合物、聚亚苯基类、其中芳环经由氧-或硫原子或经由CO或SO2基团连接的聚/多芳基类、芳族聚酯、芳族聚酰胺和/或杂环聚合物，尤其是聚酰亚胺、聚苯并咪唑类或聚醚酰亚胺类。
8.根据权利要求5所述的复合材料，其特征在于所述热塑性塑料选自聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯，聚对苯二甲酸丁二醇酯、聚碳酸酯、聚丙烯腈和/或聚酰亚胺。
9.根据权利要求1所述的复合材料，其特征在于其具有低于100(g/m2*24h*bar)的氧渗透性和/或其具有低于100(g/m2*24h*bar)的水蒸气渗透性。
10.根据权利要求1所述的复合材料，其特征在于在380纳米至780纳米的波长范围内，其对入射在具有所述阻隔层的复合材料表面上的电磁辐射具有至少80%、优选至少90%和最特别优选95%至100%的电磁辐射透射率。
11.根据权利要求1所述的复合材料，其特征在于其与一个或多个基板结合，尤其与箔或复合箔和/或与电气、电子、光电、机电和/或微机械器件结合。
12.根据权利要求1所述的复合材料，其特征在于其与选自以下的器件结合：半导体器件、光电器件、机电器件和/或微机械器件，或与构成柔性扁平电缆或柔性印刷电路的组成部分的复合箔结合。
13.根据权利要求1所述的复合材料，其特征在于其是柔性复合材料，其包含在一侧上施加有由导电材料构成的图案的柔性塑料箔，所述图案与施加到该侧的电子器件结合并且给定了电子电路，并且在该侧上和任选在远离其的一侧上涂有根据权利要求1所述的复合箔，以使得涂有该无机气相沉积材料的一侧朝外。
14.根据权利要求1所述的复合材料，其特征在于其是柔性复合材料，其包含在两侧上施加有由导电材料构成的图案的柔性塑料箔，所述图案与施加到一侧或两侧的电子器件结合并且给定了电子电路，并且在一侧和任选两侧上涂有根据权利要求1所述的复合箔，以使得涂有该无机气相沉积材料的一侧朝外。
15.根据权利要求1所述的复合材料，其特征在于其是柔性复合材料，其包含在一侧上或在两侧上施加有由导电材料构成的图案的至少两个柔性塑料箔，所述图案与位于一个柔性塑料箔的一侧上或位于一个柔性塑料箔的两侧上或位于多个柔性塑料箔的一个或多个侧面上的电子器件结合并且给定了电子电路，并且其在该复合材料的一侧上和任选在两侧上涂有根据权利要求1所述的复合箔，以使得涂有所述无机气相沉积材料的一侧朝外。
16.根据权利要求1所述的复合材料，其特征在于其是由柔性电路和由刚性电路构成的复合材料，其在所述复合材料的一侧上和任选在两侧上涂有根据权利要求1所述的复合箔，以使得涂有所述无机气相沉积材料的一侧朝外。
17.根据权利要求1所述的柔性复合材料，其特征在于在由至少一个导电材料层和至少一个塑料箔构成的层压件的一个或两个外侧上使用根据权利要求1所述的涂覆的塑料箔，以使得涂有所述无机气相沉积材料的一侧朝外。
18.制造根据权利要求1所述的柔性复合材料的方法，包括至少以下措施：
i）将给定上表面和下表面的塑料箔预先放置在气相沉积设备中，和
ii）通过无机层气相沉积材料的等离子体增强热气相沉积在至少一个所述表面上沉积至少一个针对气体和液体的介电阻隔层。
19.根据权利要求1所述的柔性复合材料在制造电气、电子、光电、机电或微机械器件中以及在制造柔性电连接中的用途。
20.根据权利要求19所述的用途，其特征在于所述电气器件是柔性发电机或电能蓄能器，尤其是柔性太阳能电池或柔性蓄电池。
21.根据权利要求19所述的用途，其特征在于所述电子器件是柔性电子电路或柔性印刷电路板。
22.根据权利要求19所述的用途，其特征在于所述光电器件是柔性显示器，尤其是柔性LCD显示器或柔性OLED显示器；或柔性发光元件，尤其是柔性LED、柔性OLED或柔性激光二极管；或柔性光电晶体管。
23.根据权利要求19所述的用途，其特征在于所述机电器件是继电器、麦克风或扬声器。
24.根据权利要求19所述的用途，其特征在于所述微机械器件是传感器或动作器，尤其是继电器、开关、阀或泵，或微系统，尤其是微型马达或按钮。
25.根据权利要求19所述的用途，其特征在于所述器件和/或所述连接用于计算机、外围设备、移动电话、照相机、个人娱乐设备、饰品、功能性服装、监视器、汽车、船舶、飞机、火箭或卫星。
26.根据权利要求19所述的用途，其特征在于根据权利要求1所述的涂覆的复合材料在用于连接电气、电子、光电、机电或微机械器件的电缆中使用。
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| US201361859584P | 2013-07-29 | 2013-07-29 | |
| US61/859584 | 2013-07-29 | ||
| US14/328,887 US20150029681A1 (en) | 2013-07-29 | 2014-07-11 | Flexible composite, production thereof and use thereof |
| US14/328887 | 2014-07-11 | ||
| PCT/EP2014/066141 WO2015014775A2 (de) | 2013-07-29 | 2014-07-28 | Flexibler verbund, verfahren zu dessen herstellung und dessen verwendung |
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| CN105658839A true CN105658839A (zh) | 2016-06-08 |
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| US (1) | US20150029681A1 (zh) |
| EP (1) | EP3027785A2 (zh) |
| JP (1) | JP2016532577A (zh) |
| KR (1) | KR20160037197A (zh) |
| CN (1) | CN105658839A (zh) |
| TW (1) | TWI546406B (zh) |
| WO (1) | WO2015014775A2 (zh) |
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| CN110004423A (zh) * | 2019-05-14 | 2019-07-12 | 南京汇金锦元光电材料有限公司 | Cigs制备用强化隔离膜及制备方法 |
| CN110474570A (zh) * | 2019-09-16 | 2019-11-19 | 桂林电子科技大学 | 一种具有柔性可延展结构的温差发电器及其制作方法 |
| CN115613004A (zh) * | 2021-07-12 | 2023-01-17 | 北京印刷学院 | 内壁镀膜的塑料管及制备方法 |
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| CN106558279B (zh) * | 2017-01-13 | 2019-05-14 | 京东方科技集团股份有限公司 | 柔性显示装置及其制备方法 |
| DE102019133315A1 (de) * | 2019-12-06 | 2021-06-10 | Bayerische Motoren Werke Aktiengesellschaft | Lautsprechersystem |
| DE102020200053A1 (de) * | 2020-01-06 | 2021-07-08 | Heliatek Gmbh | Verkapselungssystem für ein optoelektronisches Bauelement mit mindestens einer ersten Verkapselung und einer zweiten Verkapselung, optoelektronisches Bauelement mit einem solchen Verkapselungssystem |
| WO2024084681A1 (ja) * | 2022-10-21 | 2024-04-25 | 株式会社アドバンテスト | 光導波路、および、光導波路の製造方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2016532577A (ja) | 2016-10-20 |
| WO2015014775A2 (de) | 2015-02-05 |
| KR20160037197A (ko) | 2016-04-05 |
| US20150029681A1 (en) | 2015-01-29 |
| WO2015014775A3 (de) | 2015-04-02 |
| EP3027785A2 (de) | 2016-06-08 |
| TWI546406B (zh) | 2016-08-21 |
| TW201522694A (zh) | 2015-06-16 |
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