JP6293599B2 - Manufacturing method of electronic devices - Google Patents
Manufacturing method of electronic devices Download PDFInfo
- Publication number
- JP6293599B2 JP6293599B2 JP2014142168A JP2014142168A JP6293599B2 JP 6293599 B2 JP6293599 B2 JP 6293599B2 JP 2014142168 A JP2014142168 A JP 2014142168A JP 2014142168 A JP2014142168 A JP 2014142168A JP 6293599 B2 JP6293599 B2 JP 6293599B2
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- JP
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- Prior art keywords
- functional film
- film
- cellulose
- inorganic
- forming
- 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.)
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- 238000004519 manufacturing process Methods 0.000 title claims description 49
- 239000000203 mixture Substances 0.000 claims description 90
- 239000010954 inorganic particle Substances 0.000 claims description 86
- 229920003043 Cellulose fiber Polymers 0.000 claims description 73
- 229920002678 cellulose Polymers 0.000 claims description 68
- 239000001913 cellulose Substances 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 63
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 41
- 239000000835 fiber Substances 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 37
- 239000004065 semiconductor Substances 0.000 claims description 36
- 125000003172 aldehyde group Chemical group 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 125000000468 ketone group Chemical group 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 239000007921 spray Substances 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 239000002798 polar solvent Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 150000007529 inorganic bases Chemical class 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052714 tellurium Inorganic materials 0.000 claims description 7
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000010248 power generation Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 description 51
- 239000010410 layer Substances 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000011889 copper foil Substances 0.000 description 16
- 238000005259 measurement Methods 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 15
- 238000003860 storage Methods 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 238000005507 spraying Methods 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 10
- 230000017525 heat dissipation Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002612 dispersion medium Substances 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 239000011863 silicon-based powder Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920002201 Oxidized cellulose Polymers 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- -1 bromide metals Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
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- 238000007665 sagging Methods 0.000 description 3
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- 239000011122 softwood Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
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- 235000010493 xanthan gum Nutrition 0.000 description 3
- 229940082509 xanthan gum Drugs 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 241000196324 Embryophyta Species 0.000 description 2
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
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- 238000010009 beating Methods 0.000 description 2
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- 239000011362 coarse particle Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
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- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 2
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- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- UXBLSWOMIHTQPH-UHFFFAOYSA-N 4-acetamido-TEMPO Chemical compound CC(=O)NC1CC(C)(C)N([O])C(C)(C)C1 UXBLSWOMIHTQPH-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
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- 241000894006 Bacteria Species 0.000 description 1
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Description
本発明は、電気絶縁膜、半導体膜、誘電体膜といった機能膜の形成材料として用いられる、無機粒子含有機能膜形成用組成物を用いた電子デバイスの製法に関するものである。 The present invention is an electrically insulating film, a semiconductor film, used as the material for the formation of a functional film such as a dielectric film, it relates to preparation of an electronic device using the inorganic particles-containing functional film-forming composition.
各種の電子デバイスを構成する、電気絶縁膜、半導体膜、誘電体膜といった機能膜は、例えば、その形成材料である無機粒子が分散された塗布液をコーティングした後、その塗膜を加熱により焼結させることにより、形成することが可能である。上記塗布液においては、無機粒子や溶媒の他、塗布液の安定性、塗布環境の制御等の観点から、通常、バインダーが添加される。 Functional films, such as electrical insulating films, semiconductor films, and dielectric films, that make up various electronic devices, for example, are coated with a coating solution in which inorganic particles that form the material are dispersed, and then the coating film is baked by heating. It can be formed by bonding. In the coating solution, in addition to inorganic particles and a solvent, a binder is usually added from the viewpoints of stability of the coating solution and control of the coating environment.
しかしながら、無機粒子を含有する塗布液中にバインダーを添加すると、無機粒子が凝集しやすくなる。このような無機粒子の凝集は、塗膜の均一性の悪化を引き起し、それに起因し、強度、絶縁性、導電性、熱伝導性等といった皮膜性能の悪化を生じる。したがって、上記塗布液には、液中の無機粒子が充分な分散性（均一分散性）を示すことが求められている。また、長期にわたって安定に保存できるように、その均一分散性を長期間維持することも求められている。 However, when a binder is added to the coating liquid containing inorganic particles, the inorganic particles are likely to aggregate. Such agglomeration of the inorganic particles causes deterioration of the uniformity of the coating film, resulting in deterioration of film performance such as strength, insulation, conductivity, thermal conductivity and the like. Therefore, the coating liquid is required to exhibit sufficient dispersibility (uniform dispersibility) of the inorganic particles in the liquid. In addition, it is also required to maintain the uniform dispersibility for a long period of time so that it can be stably stored for a long period of time.
これらの課題を解決する手段として、従来では、例えば、無機粒子に表面処理を施す方法（特許文献１参照）や、分散剤を添加する方法（特許文献２，３参照）等が提案されている。 As means for solving these problems, conventionally, for example, a method of performing surface treatment on inorganic particles (see Patent Document 1), a method of adding a dispersant (see Patent Documents 2 and 3), and the like have been proposed. .
しかしながら、上記無機粒子に表面処理を施す方法では、求められる性能を保持したまま、無機粒子の凝集が完全に抑制されるレベルまで表面処理を行なうことは非常に困難である。また、上記分散剤を添加する方法では、無機粒子が小さいほどその表面積が増大するため、無機粒子を充分に安定化させるためには大量の分散剤が必要になる。しかし、塗布液に大量の分散剤を配合すると、形成した皮膜にも分散剤が残存するため、強度、絶縁性、導電性、熱伝導性等の皮膜性能の悪化が生じるといった問題がある。 However, in the method of performing surface treatment on the inorganic particles, it is very difficult to perform the surface treatment to a level at which aggregation of the inorganic particles is completely suppressed while maintaining the required performance. In the method of adding the dispersant, the smaller the inorganic particles, the larger the surface area. Therefore, a large amount of dispersant is required to sufficiently stabilize the inorganic particles. However, when a large amount of dispersant is added to the coating solution, the dispersant remains in the formed film, and there is a problem that film performance such as strength, insulation, conductivity, and thermal conductivity is deteriorated.
また、前記機能膜形成用の塗布液を、例えばスプレー法によってコーティングする場合において、大量に吹き付けた際、液だれが生じやすく塗膜厚が不均一になるといった問題もある。これを解決するため、従来では少量ずつ吹き付ける方法がとられていたが、この方法では生産性の点で劣る。また、単に塗布液の粘度を高めて液だれを防止するといった手法では、スプレー性に支障をきたすおそれもある。 Further, when the coating liquid for forming the functional film is coated by, for example, a spray method, there is also a problem that when a large amount is sprayed, dripping easily occurs and the coating thickness becomes non-uniform. In order to solve this, conventionally, a method of spraying a small amount at a time has been taken, but this method is inferior in productivity. Further, the technique of simply increasing the viscosity of the coating solution to prevent dripping may cause a problem in sprayability.
本発明は、このような事情に鑑みなされたもので、無機粒子の均一分散性に優れ、保存安定性に優れるとともに、スプレー性、液だれ防止性に優れる、無機粒子含有機能膜形成用組成物を用いた電子デバイスの製法の提供をその目的とする。 The present invention has been made in view of such circumstances, and is a composition for forming an inorganic particle-containing functional film that is excellent in uniform dispersibility of inorganic particles, excellent in storage stability, and excellent in sprayability and dripping prevention . It is an object of the present invention to provide a method for manufacturing an electronic device using the above.
上記の目的を達成するため、本発明は、無機基材上に、電気絶縁膜，半導体膜または誘電体膜である無機粒子含有機能膜と、電極層とが形成されてなる電子デバイスの製法であって、上記無機基材上の一部もしくは全面に、下記の（α）に示す無機粒子含有機能膜形成用組成物を塗布する工程と、その塗膜を加熱により焼結させ、上記無機粒子含有機能膜を形成する工程と、その機能膜上及び／又は前記無機基材上に上記電極層を形成する工程と、を備えた電子デバイスの製法を第１の要旨とする。
（α）下記の（Ａ）〜（Ｃ）成分を含有する無機粒子含有機能膜形成用組成物。
（Ａ）ホウ素、リチウム、ナトリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、ジルコニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、鉄、コバルト、ニッケル、テルル、銅、亜鉛、アルミニウム、ケイ素、リン、ガリウム、インジウム、スズ、鉛およびビスマスからなる群から選ばれた少なくとも一つの元素を含む無機粒子であって、その平均粒径が１００ｎｍ〜３０μｍである無機粒子。
（Ｂ）数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的にカルボキシル基、アルデヒド基，およびケトン基のいずれかに酸化変性されており、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇ、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であるとともに、そのセルロースの非晶領域量が１０〜２５％である、セルロース繊維。
（Ｃ）極性溶媒。
In order to achieve the above object , the present invention provides a method for producing an electronic device in which an inorganic insulating material , a semiconductor film or a dielectric film, which is a dielectric film, and an electrode layer are formed on an inorganic substrate. there, a portion or the entire surface of the above inorganic substrate, the steps of applying the inorganic particles-containing functional film forming composition shown in the following (alpha), is sintered by heating the coated film, the inorganic particles forming a containing functional film, and the step of forming the electrode layer on the functional film and / or on the inorganic substrate, the preparation of an electronic device provided with a first aspect.
(Α) A composition for forming an inorganic particle-containing functional film containing the following components (A) to (C).
(A) Boron, lithium, sodium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, tellurium, copper, zinc, aluminum, silicon Inorganic particles containing at least one element selected from the group consisting of phosphorous, gallium, indium, tin, lead and bismuth, and having an average particle size of 100 nm to 30 μm.
(B) Cellulose fibers having a number average fiber diameter of 2 to 150 nm, wherein the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively oxidized and modified to any of a carboxyl group, an aldehyde group, and a ketone group. The content of carboxyl groups is 1.2 to 2.5 mmol / g, the total content of aldehyde groups and ketone groups as measured by the semicarbazide method is less than 0.3 mmol / g, and the amorphous region of the cellulose Cellulose fiber, the amount of which is 10-25%.
(C) Polar solvent.
また、本発明は、アルミニウム箔からなる基材上に半導体膜と電極層とが形成されてなる、太陽光発電機能を有する電子デバイスの製法であって、上記基材の少なくとも一方の面に、下記の（α）に示す無機粒子含有機能膜形成用組成物であって、その無機粒子の主成分をケイ素とするものを塗布する工程と、その塗膜を加熱により焼結させ、半導体膜を形成する工程と、その半導体膜に不純物をドープさせてＰ型及びＮ型の半導体部分を形成する工程と、上記Ｐ型及びＮ型の半導体部分が形成された半導体膜上に上記電極層を形成する工程と、を備えた電子デバイスの製法を第２の要旨とする。
（α）下記の（Ａ）〜（Ｃ）成分を含有する無機粒子含有機能膜形成用組成物。
（Ａ）ホウ素、リチウム、ナトリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、ジルコニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、鉄、コバルト、ニッケル、テルル、銅、亜鉛、アルミニウム、ケイ素、リン、ガリウム、インジウム、スズ、鉛およびビスマスからなる群から選ばれた少なくとも一つの元素を含む無機粒子であって、その平均粒径が１００ｎｍ〜３０μｍである無機粒子。
（Ｂ）数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的にカルボキシル基、アルデヒド基，およびケトン基のいずれかに酸化変性されており、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇ、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であるとともに、そのセルロースの非晶領域量が１０〜２５％である、セルロース繊維。
（Ｃ）極性溶媒。
Further, the present invention is a method for producing an electronic device having a solar power generation function, in which a semiconductor film and an electrode layer are formed on a base material made of an aluminum foil, on at least one surface of the base material, The composition for forming an inorganic particle-containing functional film shown in (α) below, a step of applying a silicon-based inorganic particle as a main component, and sintering the coating film by heating, forming a step, a step of forming a semiconductor portion of the impurities by doping P-type and N-type to the semiconductor film, the electrode layer on the P-type and N-type semiconductor film semiconductor portion is formed in the formation a step of the manufacturing method of the electronic device with the second aspect.
(Α) A composition for forming an inorganic particle-containing functional film containing the following components (A) to (C).
(A) Boron, lithium, sodium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, tellurium, copper, zinc, aluminum, silicon Inorganic particles containing at least one element selected from the group consisting of phosphorous, gallium, indium, tin, lead and bismuth, and having an average particle size of 100 nm to 30 μm.
(B) Cellulose fibers having a number average fiber diameter of 2 to 150 nm, wherein the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively oxidized and modified to any of a carboxyl group, an aldehyde group, and a ketone group. The content of carboxyl groups is 1.2 to 2.5 mmol / g, the total content of aldehyde groups and ketone groups as measured by the semicarbazide method is less than 0.3 mmol / g, and the amorphous region of the cellulose Cellulose fiber, the amount of which is 10-25%.
(C) Polar solvent.
すなわち、本発明者らは、無機粒子の均一分散性に優れ、保存安定性に優れるとともに、スプレー性、液だれ防止性に優れる塗布液を得るため、鋭意研究を重ねた。その研究の過程で、数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的にカルボキシル基、アルデヒド基，およびケトン基のいずれかに酸化変性されており、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇ、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であるとともに、そのセルロースの非晶領域量が１０〜２５％である、微細なセルロース繊維（Ｂ）に着目した。そして、要求する皮膜性能に応じ、特定元素を含む、特定粒径の無機粒子（Ａ）を用い、その無機粒子（Ａ）と、上記特殊なセルロース繊維（Ｂ）とを組み合わせて、極性溶媒（Ｃ）に希釈し、機能膜形成用組成物（塗布液）を調製したところ、上記特殊なセルロース繊維（Ｂ）がバインダーとして機能するとともに、無機粒子（Ａ）の凝集が抑制されて均一に分散するようになり、コーティングした際の塗膜の均一性に優れるようになることから、無機粒子（Ａ）の特性に従い、強度、絶縁性、導電性、熱伝導性等といった皮膜性能が良好に得られるようになることを突き止めた。また、上記組成物は、長期保存しても粘度低下が殆どなく、保存安定性に優れるようになり、しかも、静置状態では高い粘性を示すが、せん断力を加えると粘性が低下するようになることから、スプレー性と液だれ防止性との双方が両立するようになり、所期の目的が達成できることを見いだし、本発明に到達した。なお、上記特殊なセルロース繊維（Ｂ）は、特に、非晶領域を特定量有するとともに、アルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であり、この点が、本出願人が予てから使用してきたセルロース繊維（例えば、特願２０１２−１２７２９３号参照）と異なるのであるが、本発明者らは、今回の研究の結果、上記のように非晶領域を特定量有するセルロース繊維（Ｂ）を用いることにより、従来では得ることのできなかった、極性溶媒（Ｃ）に対する優れた分散性を持ち、無機粒子（Ａ）の高い分散安定性が顕著に得られるようになることを突き止めたことから、本発明の電子デバイスの製法に用いられる機能膜形成用組成物では、特願２０１２−１２７２９３号に記載の発明に対して、主に、この点における改良が見込まれるものとなる。 That is, the present inventors have intensively studied in order to obtain a coating solution having excellent uniform dispersibility of inorganic particles, excellent storage stability, and excellent sprayability and dripping prevention. In the course of the research, it is a cellulose fiber having a number average fiber diameter of 2 to 150 nm, and the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively a carboxyl group, an aldehyde group, or a ketone group. The content of carboxyl groups is 1.2 to 2.5 mmol / g, the total content of aldehyde groups and ketone groups is less than 0.3 mmol / g as measured by the semicarbazide method, Attention was paid to fine cellulose fibers (B) having an amorphous region amount of 10 to 25%. And according to the membrane | film | coat performance to request | require, the inorganic particle (A) containing a specific element is used, the inorganic particle (A) and the said special cellulose fiber (B) are combined, and a polar solvent ( When the composition for forming a functional film (coating solution) was prepared by diluting to C), the special cellulose fiber (B) functions as a binder, and the aggregation of inorganic particles (A) is suppressed and uniformly dispersed. Since the coating film has excellent uniformity when coated, good film performance such as strength, insulation, conductivity, thermal conductivity, etc. can be obtained according to the characteristics of the inorganic particles (A). I found out that I could be. In addition, the composition has little decrease in viscosity even after long-term storage and becomes excellent in storage stability. Moreover, it exhibits high viscosity in a stationary state, but the viscosity decreases when shearing force is applied. Thus, both the sprayability and the dripping prevention property are compatible, and it has been found that the intended purpose can be achieved, and the present invention has been achieved. In addition, the special cellulose fiber (B) has a specific amount of an amorphous region, and the total content of aldehyde groups and ketone groups is less than 0.3 mmol / g. Although it is different from the cellulose fiber which has been used (for example, refer to Japanese Patent Application No. 2012-127293), as a result of this research, the present inventors have found that the cellulose fiber (B) has a specific amount of an amorphous region as described above. It has been found that the use of this material has an excellent dispersibility with respect to the polar solvent (C), which could not be obtained in the past, and the high dispersion stability of the inorganic particles (A) can be obtained remarkably. from the functional film forming composition used in the preparation of the electronic device of the present invention, with respect to the invention described in Japanese Patent Application No. 2012-127293, mainly, it is expected improvements in this respect It becomes shall.
このように、本発明の電子デバイスの製法に用いられる無機粒子含有機能膜形成用組成物は、数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的にカルボキシル基、アルデヒド基，およびケトン基のいずれかに酸化変性されており、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇ、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であるとともに、そのセルロースの非晶領域量が１０〜２５％である、微細なセルロース繊維（Ｂ）を、要求する皮膜性能に応じて選定された特定元素を含む特定粒径の無機粒子（Ａ）とともに含有し、これらが極性溶媒（Ｃ）に希釈されてなるものである。本発明の電子デバイスの製法に用いられる無機粒子含有機能膜形成用組成物においては、上記セルロース繊維が無機粒子を安定に担持するため、界面活性剤等の分散剤を使用することなく、上記無機粒子の凝集を抑制することができ、上記無機粒子が均一に分散するようになる。また、本発明の電子デバイスの製法に用いられる無機粒子含有機能膜形成用組成物は、コーティングした際の塗膜の均一性が高いことから、無機粒子の特性に従って、強度、絶縁性、導電性、熱伝導性等といった皮膜性能を良好に得ることができる。よって、上記組成物からなる皮膜は、電気絶縁膜、半導体膜、誘電体膜といった機能膜として優れた性能を発揮することができる。さらに、本発明の電子デバイスの製法に用いられる無機粒子含有機能膜形成用組成物は、上記無機粒子の均一分散状態を長期間保持することができ、長期保存しても粘度低下が殆どないことから、保存安定性に優れ、しかも、スプレー性と液だれ防止性との双方が良好であることから、スプレー法によって大量に吹き付けても液だれが少なく、優れた作業性が得られるようになる。 Thus, the composition for forming an inorganic particle-containing functional film used in the method for producing an electronic device of the present invention is a cellulose fiber having a number average fiber diameter of 2 to 150 nm, and C6 of each glucose unit in the cellulose molecule. The hydroxyl group at the position is selectively oxidized and modified to any of a carboxyl group, an aldehyde group, and a ketone group, the carboxyl group content is 1.2 to 2.5 mmol / g, and the aldehyde group as measured by the semicarbazide method A fine cellulose fiber (B) having a total content of ketone groups of less than 0.3 mmol / g and an amorphous region amount of cellulose of 10 to 25% was selected according to the required film performance. It is contained together with inorganic particles (A) having a specific particle size containing a specific element, and these are diluted with a polar solvent (C). In the composition for forming an inorganic particle-containing functional film used in the method for producing an electronic device of the present invention, since the cellulose fiber stably supports inorganic particles, the inorganic fiber can be used without using a dispersant such as a surfactant. Aggregation of particles can be suppressed, and the inorganic particles are uniformly dispersed. In addition, the composition for forming an inorganic particle-containing functional film used in the method for producing an electronic device of the present invention has high uniformity of the coating film when coated, and therefore, according to the characteristics of the inorganic particles, strength, insulation, conductivity The film performance such as thermal conductivity can be obtained satisfactorily. Therefore, a film made of the above composition can exhibit excellent performance as a functional film such as an electrical insulating film, a semiconductor film, and a dielectric film. Furthermore, the inorganic particle-containing functional film-forming composition used in the method for producing an electronic device of the present invention can maintain a uniform dispersion state of the inorganic particles for a long period of time, and there is almost no decrease in viscosity even after long-term storage. Therefore, it has excellent storage stability, and both sprayability and dripping prevention are good, so that even when sprayed in large quantities by the spray method, there is little dripping and excellent workability can be obtained. .
したがって、無機基材上に、電気絶縁膜，半導体膜または誘電体膜である無機粒子含有機能膜と、電極層とが形成されてなる電子デバイスの製法や、アルミニウム箔からなる基材上に半導体膜と電極層とが形成されてなる、太陽光発電機能を有する電子デバイスの製法において、その無機粒子含有機能膜や半導体膜を、上記特定の無機粒子含有機能膜形成用組成物を塗布して焼結させることにより形成すると、優れた作業性で、均一な無機粒子含有機能膜や半導体膜を形成することができ、それによって優れた電子デバイスを製造することができる。 Therefore, an electronic device manufacturing method in which an inorganic particle-containing functional film, which is an electrical insulating film, a semiconductor film or a dielectric film, and an electrode layer are formed on an inorganic substrate, or a semiconductor on a substrate made of aluminum foil In a method for producing an electronic device having a photovoltaic power generation function, in which a film and an electrode layer are formed, the inorganic particle-containing functional film or the semiconductor film is coated with the specific inorganic particle-containing functional film-forming composition. When formed by sintering, a uniform inorganic particle-containing functional film or semiconductor film can be formed with excellent workability, whereby an excellent electronic device can be manufactured.
つぎに、本発明の実施の形態を詳しく説明する。 Next, embodiments of the present invention will be described in detail.
本発明の電子デバイスの製法に用いられる無機粒子含有機能膜形成用組成物（以下、「機能膜形成用組成物」と略記する。）は、下記の（Ａ）〜（Ｃ）成分を用いて得ることができる。
（Ａ）ホウ素、リチウム、ナトリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、ジルコニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、鉄、コバルト、ニッケル、テルル、銅、亜鉛、アルミニウム、ケイ素、リン、ガリウム、インジウム、スズ、鉛およびビスマスからなる群から選ばれた少なくとも一つの元素を含む無機粒子であって、その平均粒径が１００ｎｍ〜３０μｍである無機粒子。
（Ｂ）数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的にカルボキシル基、アルデヒド基，およびケトン基のいずれかに酸化変性されており、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇ、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であるとともに、そのセルロースの非晶領域量が１０〜２５％である、セルロース繊維。
（Ｃ）極性溶媒。
The composition for forming an inorganic particle-containing functional film (hereinafter abbreviated as “functional film-forming composition”) used in the method for producing an electronic device of the present invention includes the following components (A) to (C). Can be obtained.
(A) Boron, lithium, sodium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, tellurium, copper, zinc, aluminum, silicon Inorganic particles containing at least one element selected from the group consisting of phosphorous, gallium, indium, tin, lead and bismuth, and having an average particle size of 100 nm to 30 μm.
(B) Cellulose fibers having a number average fiber diameter of 2 to 150 nm, wherein the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively oxidized and modified to any of a carboxyl group, an aldehyde group, and a ketone group. The content of carboxyl groups is 1.2 to 2.5 mmol / g, the total content of aldehyde groups and ketone groups as measured by the semicarbazide method is less than 0.3 mmol / g, and the amorphous region of the cellulose Cellulose fiber, the amount of which is 10-25%.
(C) Polar solvent.
《無機粒子（Ａ）》
上記無機粒子（Ａ）は、平均粒径が１００ｎｍ〜３０μｍの範囲であることが必要であり、好ましくは０．３〜１５μｍ、特に好ましくは０．５〜８μｍである。すなわち、平均粒径が小さすぎると、分散に必要なセルロース繊維が多く必要となり、焼結の際の緻密性が悪くなり、逆に、平均粒径が大きすぎると、無機粒子の種類に応じた機能発現性が悪くなるからである。
<< Inorganic particles (A) >>
The inorganic particles (A) are required to have an average particle size in the range of 100 nm to 30 μm, preferably 0.3 to 15 μm, particularly preferably 0.5 to 8 μm. That is, if the average particle size is too small, a large amount of cellulose fibers necessary for dispersion is required, and the denseness during sintering deteriorates. Conversely, if the average particle size is too large, it depends on the type of inorganic particles. This is because the function expression becomes worse.
なお、上記平均粒径は、例えば、レーザー回折・光散乱式粒度分布測定装置を用いて測定することができる。 The average particle diameter can be measured, for example, using a laser diffraction / light scattering particle size distribution measuring apparatus.
そして、上記無機粒子（Ａ）としては、機能膜形成用途の観点から、ホウ素（Ｂ）、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、バナジウム（Ｖ）、ニオブ（Ｎｂ）、タンタル（Ｔａ）、クロム（Ｃｒ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、テルル（Ｔｅ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、アルミニウム（Ａｌ）、ケイ素（Ｓｉ）、リン（Ｐ）、ガリウム（Ｇａ）、インジウム（Ｉｎ）、スズ（Ｓｎ）、鉛（Ｐｂ）およびビスマス（Ｂｉ）からなる群から選ばれた少なくとも一つの元素を含む無機粒子が用いられる。 And as said inorganic particle (A), from a viewpoint of a functional film formation use, boron (B), lithium (Li), sodium (Na), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), zirconium (Zr), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), tellurium (Te), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), phosphorus (P), gallium (Ga), indium Inorganic particles containing at least one element selected from the group consisting of (In), tin (Sn), lead (Pb), and bismuth (Bi) are used.
また、上記無機粒子（Ａ）は、加熱により酸化された無機粒子や、加熱によりガラス化された無機粒子であってもよく、それらの混合粒子であってもよい。なお、上記無機粒子（Ａ）が、加熱により酸化された無機粒子であると、焼結の際の反応性に富み、低温で焼結し易くなるなどの観点から優れており、上記無機粒子（Ａ）が、加熱によりガラス化された無機粒子であると、機能膜としての緻密性、密閉性に優れた膜が形成されるため、電気絶縁性の観点から優れている。 The inorganic particles (A) may be inorganic particles oxidized by heating, vitrified inorganic particles, or mixed particles thereof. In addition, when the inorganic particles (A) are inorganic particles oxidized by heating, the inorganic particles (A) are excellent from the viewpoint of being highly reactive during sintering and easy to sinter at a low temperature. When A) is inorganic particles vitrified by heating, a film excellent in denseness and sealing property as a functional film is formed, which is excellent from the viewpoint of electrical insulation.
上記無機粒子（Ａ）の含有量は、均一分散性、皮膜性能の点から、機能膜形成用組成物全体の０．０１〜９０重量％の範囲が好ましく、特に好ましくは０．１〜７０重量％の範囲である。 The content of the inorganic particles (A) is preferably in the range of 0.01 to 90% by weight, particularly preferably 0.1 to 70% by weight based on the entire composition for forming a functional film, from the viewpoint of uniform dispersibility and film performance. % Range.
《セルロース繊維（Ｂ）》
上記セルロース繊維（Ｂ）としては、数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的にカルボキシル基、アルデヒド基，およびケトン基のいずれかに酸化変性されており、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇ、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であるとともに、そのセルロースの非晶領域量が１０〜２５％である、微細なセルロース繊維が用いられる。上記セルロース繊維において、その非晶領域量は、好ましくは１５〜２０％である。そして、この非晶領域は、例えば、原料セルロースを限定することや、反応前処理である粉砕条件を限定することにより形成することができる。通常、天然由来のセルロース固体原料は、そのままでは、Ｉ型結晶構造を１００％〜５０％有する。またこれまでの調製方法では非晶領域量を１０％〜２５％の範囲内にコントロールできなかったが、本発明においては、例えば上記手法にもとづき、上記特定範囲内の非晶領域量を設けたセルロース繊維が用いられる。
<< Cellulose fiber (B) >>
The cellulose fiber (B) is a cellulose fiber having a number average fiber diameter of 2 to 150 nm, and the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively a carboxyl group, an aldehyde group, and a ketone group. And the carboxyl group content is 1.2 to 2.5 mmol / g, the total content of aldehyde groups and ketone groups as measured by the semicarbazide method is less than 0.3 mmol / g, Fine cellulose fibers having an amorphous region amount of 10 to 25% are used. In the cellulose fiber, the amount of the amorphous region is preferably 15 to 20%. And this amorphous area | region can be formed by limiting raw material cellulose and limiting the grinding | pulverization conditions which are pre-reaction processes, for example. Usually, a naturally-derived cellulose solid raw material has an I-type crystal structure of 100% to 50% as it is. Moreover, although the amount of amorphous regions could not be controlled within the range of 10% to 25% by the conventional preparation methods, in the present invention, the amount of amorphous regions within the specific range was provided based on, for example, the above method. Cellulose fibers are used.
上記非晶領域量は、構造全体から結晶性部分を引いた値として求められる。セルロースの結晶化度はＸ線回折法などにより測定することができる。すなわち、セルロースにおけるＸ線回折スペクトルを測定した時、そのピーク強度ＩおよびＩａに基づき、下記の式（１）により、結晶化度を算出することができる。よって、セルロースの非晶領域量は、下記の式（２）により算出することができる。 The amount of the amorphous region is determined as a value obtained by subtracting the crystalline portion from the entire structure. The crystallinity of cellulose can be measured by an X-ray diffraction method or the like. That is, when the X-ray diffraction spectrum in cellulose is measured, the crystallinity can be calculated by the following formula (1) based on the peak intensities I and Ia. Therefore, the amorphous region amount of cellulose can be calculated by the following formula (2).
結晶化度（％）＝（Ｉ−Ｉａ）／Ｉ×１００ ……(１)
Ｉ：２θ＝１４．６０°のピーク強度
Ｉａ：２θ＝１２°と１８°の強度を結んだ直線と２θ＝１４．６０°の強度から真 直ぐ下ろした直線が交わる点の強度（非晶領域のピーク強度）
非晶領域量（％）＝１００−（Ｉ−Ｉａ）／Ｉ×１００ ……(２)
Crystallinity (%) = (I−Ia) / I × 100 (1)
I: Peak intensity at 2θ = 14.60 ° Ia: Intensity at the point where a straight line connecting the intensity of 2θ = 12 ° and 18 ° and a straight line down from the intensity of 2θ = 14.60 ° (amorphous region) Peak intensity)
Amorphous region amount (%) = 100− (I−Ia) / I × 100 (2)
また、上記特定のセルロース繊維（Ｂ成分）の数平均繊維径は、２〜１５０ｎｍであり、分散安定性の点から、好ましくは数平均繊維径が２〜１００ｎｍであり、特に好ましくは３〜８０ｎｍである。すなわち、上記数平均繊維径が上記範囲未満であると、本質的に分散媒体に溶解してしまい、逆に上記数平均繊維径が上記範囲を超えると、セルロース繊維が沈降してしまい、セルロース繊維を配合することによる機能性を発現することができないからである。また、上記セルロース繊維の最大繊維径は、１０００ｎｍ以下であることが好ましく、特に好ましくは５００ｎｍ以下である。すなわち、上記セルロース繊維の最大繊維径が上記範囲を超えると、セルロース繊維が沈降してしまい、セルロース繊維を配合することによる機能性を発現することができないからである。 The number average fiber diameter of the specific cellulose fiber (component B) is 2 to 150 nm, and from the viewpoint of dispersion stability, the number average fiber diameter is preferably 2 to 100 nm, and particularly preferably 3 to 80 nm. It is. That is, when the number average fiber diameter is less than the above range, it is essentially dissolved in the dispersion medium. Conversely, when the number average fiber diameter exceeds the above range, the cellulose fibers are precipitated, and the cellulose fibers It is because the functionality by blending cannot be expressed. The maximum fiber diameter of the cellulose fiber is preferably 1000 nm or less, and particularly preferably 500 nm or less. That is, when the maximum fiber diameter of the cellulose fiber exceeds the above range, the cellulose fiber is settled, and the functionality due to blending the cellulose fiber cannot be expressed.
上記特定のセルロース繊維（Ｂ成分）の数平均繊維径・最大繊維径は、例えば、つぎのようにして測定することができる。すなわち、固形分率で０．０５〜０．１重量％の微細セルロースの水分散体を調製し、その分散体を、親水化処理済みのカーボン膜被覆グリッド上にキャストして、透過型電子顕微鏡（ＴＥＭ）の観察用試料とする。なお、大きな繊維径の繊維を含む場合には、ガラス上へキャストした表面の走査型電子顕微鏡（ＳＥＭ）像を観察してもよい。そして、構成する繊維の大きさに応じて５０００倍、１００００倍あるいは５００００倍のいずれかの倍率で電子顕微鏡画像による観察を行う。その際に、得られた画像内に縦横任意の画像幅の軸を想定し、その軸に対し、２０本以上の繊維が交差するよう、試料および観察条件（倍率等）を調節する。そして、この条件を満たす観察画像を得た後、この画像に対し、１枚の画像当たり縦横２本ずつの無作為な軸を引き、軸に交錯する繊維の繊維径を目視で読み取っていく。このようにして、最低３枚の重複しない表面部分の画像を、電子顕微鏡で撮影し、各々２つの軸に交錯する繊維の繊維径の値を読み取る（したがって、最低２０本×２×３＝１２０本の繊維径の情報が得られる）。このようにして得られた繊維径のデータにより、最大繊維径および数平均繊維径を算出する。 The number average fiber diameter and the maximum fiber diameter of the specific cellulose fiber (component B) can be measured, for example, as follows. That is, an aqueous dispersion of fine cellulose having a solid content of 0.05 to 0.1% by weight was prepared, and the dispersion was cast on a carbon film-coated grid that had been subjected to a hydrophilization treatment. (TEM) observation sample. In addition, when the fiber of a big fiber diameter is included, you may observe the scanning electron microscope (SEM) image of the surface cast on glass. Then, observation with an electron microscope image is performed at a magnification of 5000 times, 10000 times, or 50000 times depending on the size of the constituent fibers. At that time, an axis having an arbitrary vertical and horizontal image width is assumed in the obtained image, and the sample and observation conditions (magnification, etc.) are adjusted so that 20 or more fibers intersect the axis. Then, after obtaining an observation image that satisfies this condition, two random axes, vertical and horizontal, per image are drawn on this image, and the fiber diameter of the fiber that intersects the axis is visually read. In this way, images of at least three non-overlapping surface portions are taken with an electron microscope, and the fiber diameter values of the fibers intersecting with each of the two axes are read (thus, at least 20 × 2 × 3 = 120). Information on the fiber diameter of the book is obtained). The maximum fiber diameter and the number average fiber diameter are calculated from the fiber diameter data thus obtained.
そして、上記特定のセルロース繊維（Ｂ成分）は、セルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的に酸化変性されてアルデヒド基，ケトン基およびカルボキシル基のいずれかとなったものであり、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇである。好ましくは、１．５〜２．０ｍｍｏｌ／ｇの範囲のカルボキシル基含量である。このようにカルボキシル基の含量を特定範囲内に設定することにより、機能膜形成用組成物において、従来以上の、高い保存安定性、液だれ防止性等を得ることができる。なお、上記カルボキシル基量が上記範囲未満であると、上記のような本発明の効果が充分に得られず、さらにセルロース繊維の沈降や凝集を生じる場合もあり、逆に上記カルボキシル基量が上記範囲を超えると、水溶性が強くなり過ぎるおそれがある。 The specific cellulose fiber (component B) is one in which the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively oxidized and modified to become one of an aldehyde group, a ketone group, and a carboxyl group, The carboxyl group content is 1.2 to 2.5 mmol / g. The carboxyl group content is preferably in the range of 1.5 to 2.0 mmol / g. By thus setting the content of the carboxyl groups within a specific range, in machine Nomaku forming composition, it can be obtained over conventional, high storage stability, the anti-drip resistance. In addition, when the amount of the carboxyl group is less than the above range, the effects of the present invention as described above may not be sufficiently obtained, and further, precipitation or aggregation of cellulose fibers may occur. If it exceeds the range, the water solubility may become too strong.
上記特定のセルロース繊維（Ｂ成分）のカルボキシル基量の測定は、例えば、乾燥重量を精秤したセルロース試料から０．５〜１重量％スラリーを６０ｍｌ調製し、０．１Ｍの塩酸水溶液によってｐＨを約２．５とした後、０．０５Ｍの水酸化ナトリウム水溶液を滴下して、電気伝導度測定を行う。測定はｐＨが約１１になるまで続ける。電気伝導度の変化が緩やかな弱酸の中和段階において消費された水酸化ナトリウム量（Ｖ）から、下記の式（３）に従いカルボキシル基量を求めることができる。 The measurement of the carboxyl group amount of the specific cellulose fiber (component B) is, for example, preparing 60 ml of a 0.5 to 1 wt% slurry from a cellulose sample accurately weighed on the dry weight, and adjusting the pH with a 0.1 M aqueous hydrochloric acid solution. After adjusting to about 2.5, 0.05M sodium hydroxide aqueous solution is dropped and the electrical conductivity is measured. The measurement is continued until the pH is about 11. From the amount (V) of sodium hydroxide consumed in the weak acid neutralization stage where the change in electrical conductivity is gradual, the amount of carboxyl groups can be determined according to the following formula (3).
カルボキシル基量(mmol/g)＝Ｖ(ml)×〔０．０５／セルロース重量〕 ……(３) Amount of carboxyl groups (mmol / g) = V (ml) × [0.05 / cellulose weight] (3)
なお、カルボキシル基量の調整は、後述するように、セルロース繊維の酸化工程で用いる共酸化剤の添加量や反応時間を制御することにより行うことができる。 In addition, adjustment of a carboxyl group amount can be performed by controlling the addition amount and reaction time of the co-oxidant used at the oxidation process of a cellulose fiber so that it may mention later.
また、上記特定のセルロース繊維（Ｂ成分）は、前記酸化変性後、還元剤により還元させることが好ましい。これにより、アルデヒド基およびケトン基の一部ないし全部は還元され、水酸基に戻る。なお、カルボキシル基は還元されない。そして、上記還元により、上記特定のセルロース繊維（Ｂ成分）の、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量を、０．３ｍｍｏｌ／ｇ未満とすることが好ましく、より好ましくは０〜０．１ｍｍｏｌ／ｇの範囲であり、さらに好ましくは実質的に０ｍｍｏｌ／ｇである。これにより、単に酸化変性させたものよりも、増粘性、分散安定性が増し、特に気温等に左右されず長期にわたり分散安定性に優れるようになる。また、上記のように、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であるセルロース繊維を、上記（Ｂ）成分のセルロース繊維として機能膜形成用組成物に用いると、長期保存による凝集物の発生をより抑えることができる。なお、アルデヒド基とケトン基の合計が０．３ｍｍｏｌ／ｇ以上であると、長期保存による凝集物の発生や、機能膜形成用組成物の粘度が時間経過と共に著しく低下するといったおそれがある。 The specific cellulose fiber (component B) is preferably reduced with a reducing agent after the oxidative modification. As a result, part or all of the aldehyde group and the ketone group are reduced to return to the hydroxyl group. Note that the carboxyl group is not reduced. And by the said reduction | restoration, it is preferable that the sum total content of the aldehyde group and ketone group by the measurement by the semicarbazide method of the said specific cellulose fiber (B component) shall be less than 0.3 mmol / g, More preferably, it is 0- The range is 0.1 mmol / g, more preferably substantially 0 mmol / g. As a result, the viscosity and dispersion stability are increased compared to those obtained by simply oxidative modification, and the dispersion stability is excellent over a long period of time regardless of the temperature. Further, as described above, the cellulose fibers total content of aldehyde groups and ketone groups as measured by the semicarbazide method is less than 0.3 mmol / g, the (B) for and with the cellulose fibers machine Nomaku forming component composition When used in a product, the generation of aggregates due to long-term storage can be further suppressed. When the total of aldehyde groups and ketone groups is 0.3 mmol / g or more, there is a possibility that aggregates are generated due to long-term storage and the viscosity of the functional film forming composition is remarkably lowered with time.
そして、上記特定のセルロース繊維（Ｂ成分）が、２，２，６，６−テトラメチルピペリジン（ＴＥＭＰＯ）等のＮ−オキシル化合物の存在下、共酸化剤を用いて酸化されたものであり、上記酸化反応により生じたアルデヒド基およびケトン基が、還元剤により還元されたものであると、上記特定のセルロース繊維を容易に得ることができるようになり、機能膜形成用組成物として、より良好な結果を得ることができるようになるため、好ましい。また、上記還元剤による還元が、水素化ホウ素ナトリウム（ＮａＢＨ4）によるものであると、上記観点から、より好ましい。 And the specific cellulose fiber (component B) is oxidized using a co-oxidant in the presence of an N-oxyl compound such as 2,2,6,6-tetramethylpiperidine (TEMPO), When the aldehyde group and the ketone group generated by the oxidation reaction are reduced by a reducing agent, the specific cellulose fiber can be easily obtained, and is better as a composition for forming a functional film. Therefore, it is preferable because a satisfactory result can be obtained. Also, reduction with the reducing agent, the is by hydrogenation sodium borohydride (NaBH 4), from the viewpoint, more preferable.
ところで、セミカルバジド法による、アルデヒド基とケトン基との合計含量の測定は、例えば、つぎのようにして行われる。すなわち、まず、乾燥させた試料に、リン酸緩衝液によりｐＨ＝５に調整したセミカルバジド塩酸塩３ｇ／ｌ水溶液を正確に５０ｍｌ加え、密栓し、二日間振とうする。ついで、この溶液１０ｍｌを正確に１００ｍｌビーカーに採取し、５Ｎ硫酸を２５ｍｌ、０．０５Ｎヨウ素酸カリウム水溶液５ｍｌを加え、１０分間撹拌する。その後、５％ヨウ化カリウム水溶液１０ｍｌを加えて、直ちに自動滴定装置を用いて、０．１Ｎチオ硫酸ナトリウム溶液にて滴定し、その滴定量等から、下記の式（４）に従い、試料中のカルボニル基量（アルデヒド基とケトン基との合計含量）を求めることができる。なお、セミカルバジドは、アルデヒド基やケトン基と反応しシッフ塩基（イミン）を形成するが、カルボキシル基とは反応しないことから、上記測定により、アルデヒド基とケトン基のみを定量できると考えられる。 Incidentally, measurement of the total content of aldehyde groups and ketone groups by the semicarbazide method is performed, for example, as follows. That is, first, 50 ml of a semicarbazide hydrochloride 3 g / l aqueous solution adjusted to pH = 5 with a phosphate buffer is added to a dried sample, sealed, and shaken for 2 days. Next, 10 ml of this solution is accurately collected in a 100 ml beaker, 25 ml of 5N sulfuric acid and 5 ml of 0.05N potassium iodate aqueous solution are added and stirred for 10 minutes. Thereafter, 10 ml of 5% potassium iodide aqueous solution was added, and immediately titrated with a 0.1N sodium thiosulfate solution using an automatic titrator. From the titration amount and the like, according to the following formula (4), The amount of carbonyl groups (total content of aldehyde groups and ketone groups) can be determined. Semicarbazide reacts with an aldehyde group or a ketone group to form a Schiff base (imine), but does not react with a carboxyl group. Therefore, it is considered that only the aldehyde group and the ketone group can be quantified by the above measurement.
カルボニル基量(mmol/g)＝（Ｄ−Ｂ）×ｆ×〔０.１２５／ｗ〕 ……(４)
Ｄ：サンプルの滴定量（ｍｌ）
Ｂ：空試験の滴定量（ｍｌ）
ｆ：０.１Ｎチオ硫酸ナトリウム溶液のファクター（−）
ｗ：試料量（ｇ）
Carbonyl group amount (mmol / g) = (D−B) × f × [0.125 / w] (4)
D: Sample titration (ml)
B: Titrate of blank test (ml)
f: Factor (-) of 0.1N sodium thiosulfate solution
w: Sample amount (g)
本発明における上記特定のセルロース繊維（Ｂ成分）は、繊維表面上のセルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的に酸化変性されてアルデヒド基，ケトン基およびカルボキシル基のいずれかとなっている。このセルロース繊維表面上のグルコースユニットのＣ６位の水酸基が選択的に酸化されているかどうかは、例えば、13Ｃ−ＮＭＲチャートにより確認することができる。すなわち、酸化前のセルロースの13Ｃ−ＮＭＲチャートで確認できるグルコース単位の１級水酸基のＣ６位に相当する６２ｐｐｍのピークが、酸化反応後は消失し、代わりにカルボキシル基等に由来するピーク（１７８ｐｐｍのピークはカルボキシル基に由来するピーク）が現れる。このようにして、グルコース単位のＣ６位水酸基が選択的にカルボキシル基等に酸化されていることを確認することができる。 In the specific cellulose fiber (B component) in the present invention, the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule on the fiber surface is selectively oxidized and modified to become one of an aldehyde group, a ketone group and a carboxyl group. ing. Whether or not the hydroxyl group at the C6 position of the glucose unit on the surface of the cellulose fiber is selectively oxidized can be confirmed by, for example, a 13 C-NMR chart. That is, a 62 ppm peak corresponding to the C6 position of the primary hydroxyl group of the glucose unit, which can be confirmed by a 13 C-NMR chart of cellulose before oxidation, disappears after the oxidation reaction, and instead a peak derived from a carboxyl group or the like (178 ppm) The peak of is a peak derived from a carboxyl group). In this way, it can be confirmed that the C6 hydroxyl group of the glucose unit is selectively oxidized to a carboxyl group or the like.
また、上記特定のセルロース繊維（Ｂ成分）におけるアルデヒド基の検出は、例えば、フェーリング試薬により行うこともできる。すなわち、例えば、乾燥させた試料に、フェーリング試薬（酒石酸ナトリウムカリウムと水酸化ナトリウムとの混合溶液と、硫酸銅五水和物水溶液）を加えた後、８０℃で１時間加熱したとき、上澄みが青色、セルロース繊維部分が紺色を呈するものは、アルデヒド基は検出されなかったと判断することができ、上澄みが黄色、セルロース繊維部分が赤色を呈するものは、アルデヒド基は検出されたと判断することができる。 Moreover, the detection of the aldehyde group in the said specific cellulose fiber (B component) can also be performed with a Faring reagent, for example. That is, for example, after adding a Fering reagent (a mixed solution of sodium potassium tartrate and sodium hydroxide and an aqueous solution of copper sulfate pentahydrate) to a dried sample, the supernatant is obtained when heated at 80 ° C. for 1 hour. When blue and cellulose fiber parts are amber, it can be determined that aldehyde groups have not been detected, and when the supernatant is yellow and cellulose fiber parts are red, it can be determined that aldehyde groups have been detected. .
上記特定のセルロース繊維（Ｂ成分）は、例えば、(1)酸化反応工程、(2)還元工程、(3)精製工程、(4)分散工程（微細化処理工程）等を行うことにより得ることができる。以下、各工程を順に説明する。 The specific cellulose fiber (component B) is obtained, for example, by performing (1) an oxidation reaction step, (2) a reduction step, (3) a purification step, (4) a dispersion step (a refinement treatment step), etc. Can do. Hereinafter, each process is demonstrated in order.
(1)酸化反応工程
天然セルロースと、Ｎ−オキシル化合物とを水（分散媒体）に分散させた後、共酸化剤を添加して、反応を開始する。反応中は０．５Ｍの水酸化ナトリウム水溶液を滴下してｐＨを１０〜１１に保ち、ｐＨに変化が見られなくなった時点で反応終了と見なす。ここで、共酸化剤とは、直接的にセルロース水酸基を酸化する物質ではなく、酸化触媒として用いられるＮ−オキシル化合物を酸化する物質のことである。
(1) Oxidation reaction step After natural cellulose and an N-oxyl compound are dispersed in water (dispersion medium), a cooxidant is added to start the reaction. During the reaction, a 0.5 M aqueous sodium hydroxide solution is added dropwise to maintain the pH at 10 to 11, and the reaction is regarded as completed when no change in pH is observed. Here, the co-oxidant is not a substance that directly oxidizes a cellulose hydroxyl group but a substance that oxidizes an N-oxyl compound used as an oxidation catalyst.
上記天然セルロースは、植物，動物，バクテリア産生ゲル等のセルロースの生合成系から単離した精製セルロースを意味する。より具体的には、針葉樹系パルプ、広葉樹系パルプ、コットンリンター，コットンリント等の綿系パルプ、麦わらパルプ，バガスパルプ等の非木材系パルプ、バクテリアセルロース（ＢＣ）、ホヤから単離されるセルロース、海草から単離されるセルロース等をあげることができる。これらは単独でもしくは二種以上併せて用いられる。これらのなかでも、針葉樹系パルプ、広葉樹系パルプ、コットンリンター、コットンリント等の綿系パルプ、麦わらパルプ，バガスパルプ等の非木材系パルプが好ましい。上記天然セルロースは、叩解等の表面積を高める処理を施すと、反応効率を高めることができ、生産性を高めることができるため好ましい。また、上記天然セルロースとして、単離、精製の後、乾燥させない（ネバードライ）で保存していたものを使用すると、ミクロフィブリルの集束体が膨潤しやすい状態であるため、反応効率を高め、微細化処理後の数平均繊維径を小さくすることができるため好ましい。 The natural cellulose means purified cellulose isolated from a cellulose biosynthetic system such as a plant, animal, or bacteria-producing gel. More specifically, softwood pulp, hardwood pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as straw pulp and bagasse pulp, bacterial cellulose (BC), cellulose isolated from sea squirt, seaweed Cellulose isolated from can be mentioned. These may be used alone or in combination of two or more. Among these, soft wood pulp, hardwood pulp, cotton pulp such as cotton linter and cotton lint, and non-wood pulp such as straw pulp and bagasse pulp are preferable. The natural cellulose is preferably subjected to a treatment for increasing the surface area such as beating, because the reaction efficiency can be increased and the productivity can be increased. In addition, if the natural cellulose that has been stored after being isolated and purified and not dried (never dry) is used, the microfibril bundles are likely to swell. This is preferable because the number average fiber diameter after the crystallization treatment can be reduced.
上記反応における天然セルロースの分散媒体は水であり、反応水溶液中の天然セルロース濃度は、試薬（天然セルロース）の充分な拡散が可能な濃度であれば任意である。通常は、反応水溶液の重量に対して約５％以下であるが、機械的撹拌力の強い装置を使用することにより反応濃度を上げることができる。 The dispersion medium of natural cellulose in the above reaction is water, and the concentration of natural cellulose in the reaction aqueous solution is arbitrary as long as the reagent (natural cellulose) can be sufficiently diffused. Usually, it is about 5% or less based on the weight of the reaction aqueous solution, but the reaction concentration can be increased by using a device having a strong mechanical stirring force.
また、上記Ｎ−オキシル化合物としては、例えば、一般に酸化触媒として用いられるニトロキシラジカルを有する化合物があげられる。上記Ｎ−オキシル化合物は、水溶性の化合物が好ましく、なかでもピペリジンニトロキシオキシラジカルが好ましく、特に２，２，６，６−テトラメチルピペリジノオキシラジカル（ＴＥＭＰＯ）または４−アセトアミド−ＴＥＭＰＯが好ましい。上記Ｎ−オキシル化合物の添加は、触媒量で充分であり、好ましくは０．１〜４ｍｍｏｌ／ｌ、さらに好ましくは０．２〜２ｍｍｏｌ／ｌの範囲で反応水溶液に添加する。 Examples of the N-oxyl compound include compounds having a nitroxy radical generally used as an oxidation catalyst. The N-oxyl compound is preferably a water-soluble compound, more preferably a piperidine nitroxyoxy radical, particularly 2,2,6,6-tetramethylpiperidinooxy radical (TEMPO) or 4-acetamido-TEMPO. preferable. The N-oxyl compound is added in a catalytic amount, preferably 0.1 to 4 mmol / l, more preferably 0.2 to 2 mmol / l.
上記共酸化剤としては、例えば、次亜ハロゲン酸またはその塩、亜ハロゲン酸またはその塩、過ハロゲン酸またはその塩、過酸化水素、過有機酸等があげられる。これらは単独でもしくは二種以上併せて用いられる。なかでも、次亜塩素酸ナトリウム、次亜臭素酸ナトリウム等のアルカリ金属次亜ハロゲン酸塩が好ましい。そして、上記次亜塩素酸ナトリウムを使用する場合は、臭化ナトリウム等の臭化アルカリ金属の存在下で反応を進めることが、反応速度の点において好ましい。上記臭化アルカリ金属の添加量は、上記Ｎ−オキシル化合物に対して約１〜４０倍モル量、好ましくは約１０〜２０倍モル量である。 Examples of the co-oxidant include hypohalous acid or a salt thereof, hypohalous acid or a salt thereof, perhalogen acid or a salt thereof, hydrogen peroxide, a perorganic acid, and the like. These may be used alone or in combination of two or more. Of these, alkali metal hypohalites such as sodium hypochlorite and sodium hypobromite are preferable. And when using the said sodium hypochlorite, it is preferable in terms of reaction rate to advance reaction in presence of alkali bromide metals, such as sodium bromide. The addition amount of the alkali metal bromide is about 1 to 40 times mol, preferably about 10 to 20 times mol for the N-oxyl compound.
上記反応水溶液のｐＨは約８〜１１の範囲で維持されることが好ましい。水溶液の温度は約４〜４０℃において任意であるが、反応は室温（２５℃）で行うことが可能であり、特に温度の制御は必要としない。 The pH of the aqueous reaction solution is preferably maintained in the range of about 8-11. The temperature of the aqueous solution is arbitrary at about 4 to 40 ° C., but the reaction can be performed at room temperature (25 ° C.), and the temperature is not particularly required to be controlled.
目的とするカルボキシル基量等を得るために、酸化の程度を共酸化剤の添加量と反応時間により制御する。通常、反応時間は約５〜１２０分、長くとも２４０分以内に完了する。 In order to obtain the target amount of carboxyl groups and the like, the degree of oxidation is controlled by the amount of co-oxidant added and the reaction time. Usually, the reaction time is completed within about 5 to 120 minutes, at most 240 minutes.
(2)還元工程
前記特定のセルロース繊維（Ｂ成分）は、上記酸化反応後、更に還元反応を行うことが好ましい。具体的には、酸化反応後の微細酸化セルロースを精製水に分散し、水分散体のｐＨを約１０に調整し、各種還元剤により還元反応を行う。本発明に使用する還元剤としては、一般的なものを使用することが可能であるが、好ましくは、ＬｉＢＨ4、ＮａＢＨ3ＣＮ、ＮａＢＨ4があげられる。なかでも、ＮａＢＨ4は、コスト及び利用可能性という観点から特に好ましい。
(2) Reduction step The specific cellulose fiber (component B) is preferably further subjected to a reduction reaction after the oxidation reaction. Specifically, fine oxidized cellulose after the oxidation reaction is dispersed in purified water, the pH of the aqueous dispersion is adjusted to about 10, and the reduction reaction is performed with various reducing agents. As the reducing agent used in the present invention, a general reducing agent can be used, and preferred examples include LiBH 4 , NaBH 3 CN, and NaBH 4 . Among these, NaBH 4 is particularly preferable from the viewpoint of cost and availability.
微細酸化セルロースを基準として、還元剤の量は、０．１〜４重量％の範囲が好ましく、特に好ましくは１〜３重量％の範囲内である。反応条件は室温または室温より若干高い温度で、１０分〜１０時間、好ましくは３０分〜２時間行なわれる。 The amount of reducing agent is preferably in the range of 0.1 to 4% by weight, particularly preferably in the range of 1 to 3% by weight, based on finely oxidized cellulose. The reaction is carried out at room temperature or slightly higher than room temperature for 10 minutes to 10 hours, preferably 30 minutes to 2 hours.
上記の反応終了後、各種の酸により反応混合物のｐＨを約２に調整し、精製水をふりかけながら遠心分離機で固液分離を行い、ケーキ状の微細酸化セルロースを得る。固液分離は濾液の電気伝導度が５ｍＳ／ｍ以下となるまで行う。 After completion of the above reaction, the pH of the reaction mixture is adjusted to about 2 with various acids, and solid-liquid separation is performed with a centrifuge while sprinkling purified water to obtain cake-like fine oxidized cellulose. Solid-liquid separation is performed until the electric conductivity of the filtrate is 5 mS / m or less.
(3)精製工程
つぎに、未反応の共酸化剤（次亜塩素酸等）や、各種副生成物等を除く目的で精製を行う。反応物繊維は通常、この段階ではナノファイバー単位までばらばらに分散しているわけではないため、通常の精製法、すなわち水洗とろ過を繰り返すことで高純度（９９重量％以上）の反応物繊維と水の分散体とする。
(3) Purification step Next, purification is performed for the purpose of removing unreacted co-oxidant (such as hypochlorous acid) and various by-products. At this stage, the reactant fibers are usually not dispersed evenly to the nanofiber unit. Therefore, by repeating the usual purification method, that is, washing with water and filtration, the reactant fibers are highly purified (99% by weight or more). Use water dispersion.
上記精製工程における精製方法は、遠心脱水を利用する方法（例えば、連続式デカンダー）のように、上述した目的を達成できる装置であればどのような装置を利用しても構わない。こうして得られる反応物繊維の水分散体は、絞った状態で固形分（セルロース）濃度としておよそ１０重量％〜５０重量％の範囲にある。この後の分散工程を考慮すると、５０重量％よりも高い固形分濃度とすると、分散に極めて高いエネルギーが必要となることから好ましくない。 As the purification method in the purification step, any device may be used as long as it can achieve the above-described object, such as a method using centrifugal dehydration (for example, a continuous decanter). The aqueous dispersion of the reactant fibers thus obtained is in the range of approximately 10 wt% to 50 wt% as the solid content (cellulose) concentration in the squeezed state. Considering the subsequent dispersion step, if the solid content concentration is higher than 50% by weight, it is not preferable because extremely high energy is required for dispersion.
(4)分散工程（微細化処理工程）
上記精製工程にて得られる水を含浸した反応物繊維（水分散体）を、分散媒体中に分散させ分散処理を行う。処理に伴って粘度が上昇し、微細化処理されたセルロース繊維の分散体を得ることができる。その後、上記セルロース繊維の分散体を乾燥することによって、特定のセルロース繊維（Ｂ成分）を得ることができる。なお、上記セルロース繊維の分散体を乾燥することなく、分散体の状態で機能膜形成用組成物に用いても差し支えない。
(4) Dispersion process (miniaturization process)
The reaction fiber (water dispersion) impregnated with water obtained in the purification step is dispersed in a dispersion medium and subjected to a dispersion treatment. With the treatment, the viscosity increases, and a dispersion of finely pulverized cellulose fibers can be obtained. Then, the specific cellulose fiber (B component) can be obtained by drying the dispersion of the cellulose fiber. The cellulose fiber dispersion may be used in the functional film-forming composition in the state of dispersion without drying.
そして、上記のようにして得られた特定のセルロース繊維（Ｂ成分）の分散媒体には、水や、水と有機溶媒の混合溶液が用いられる。 For the dispersion medium of the specific cellulose fiber (component B) obtained as described above, water or a mixed solution of water and an organic solvent is used.
上記分散工程で使用する分散機としては、高速回転下でのホモミキサー、高圧ホモジナイザー、超高圧ホモジナイザー、超音波分散処理、ビーター、ディスク型レファイナー、コニカル型レファイナー、ダブルディスク型レファイナー、グラインダー等の強力で叩解能力のある装置を使用することにより、より効率的かつ高度なダウンサイジングが可能となり、経済的に有利に機能膜形成用組成物を得ることができる点で好ましい。なお、上記分散機としては、例えば、スクリュー型ミキサー、パドルミキサー、ディスパー型ミキサー、タービン型ミキサー等を用いても差し支えない。 Dispersers used in the above dispersion process include high-powered homomixers, high-pressure homogenizers, ultra-high-pressure homogenizers, ultrasonic dispersion processing, beaters, disk type refiners, conical type refiners, double disk type refiners, grinders, etc. By using an apparatus having a beating ability, it is preferable in that a more efficient and advanced downsizing is possible, and a functional film forming composition can be obtained economically advantageously. As the disperser, for example, a screw mixer, a paddle mixer, a disper mixer, a turbine mixer, or the like may be used.
上記セルロース繊維の分散体の乾燥法としては、例えば、分散媒体が水である場合は、スプレードライ，凍結乾燥法等が用いられ、分散媒体が水と有機溶媒の混合溶液である場合は、ドラムドライヤーによる乾燥法，スプレードライヤーによる噴霧乾燥法等が用いられる。 Examples of the method for drying the cellulose fiber dispersion include spray drying, freeze drying, and the like when the dispersion medium is water, and drums when the dispersion medium is a mixed solution of water and an organic solvent. A drying method using a dryer, a spray drying method using a spray dryer, or the like is used.
以上のようにして得られたセルロース繊維（Ｂ成分）をバインダーとし、本発明の電子デバイスの製法に用いられる機能膜形成用組成物は調製される。そして、上記機能膜形成用組成物において、より一層、保存安定性、スプレー性、液だれ防止性に優れるようになる観点から、上記セルロース繊維（Ｂ成分）の固形分の含有量が、前記無機粒子（Ａ成分）の固形分１００重量部に対して、０．１〜２重量部の範囲であることが好ましい。 Using the cellulose fiber (component B) obtained as described above as a binder, a composition for forming a functional film used in the method for producing an electronic device of the present invention is prepared. Then, in the functional film forming composition, more, storage stability, sprayability, from the viewpoint of so excellent sag prevention of liquid, the solid content of the cellulose fibers (B component), the inorganic The amount is preferably in the range of 0.1 to 2 parts by weight with respect to 100 parts by weight of the solid content of the particles (component A).
そして、本発明の電子デバイスの製法に用いられる機能膜形成用組成物の分散媒としては、極性溶媒（Ｃ成分）が用いられる。上記極性溶媒は、プロトン性であっても非プロトン性であってもよいが、セルロース繊維（Ｂ成分）が有する水酸基およびカルボキシル基との親和性の観点から、好ましくは、誘電率が６Ｆ／ｍ以上の極性溶媒が用いられる。このような極性溶媒としては、具体的には、水、メタノール、エタノール、１−プロパノール、２−プロパノール、アセトン等があげられる。これらは単独でもしくは二種以上併せて用いられる。 And as a dispersion medium of the composition for functional film formation used for the manufacturing method of the electronic device of this invention, a polar solvent (C component) is used. The polar solvent may be protic or aprotic, but preferably has a dielectric constant of 6 F / m from the viewpoint of affinity with the hydroxyl group and carboxyl group of the cellulose fiber (component B). The above polar solvents are used. Specific examples of such a polar solvent include water, methanol, ethanol, 1-propanol, 2-propanol, and acetone. These may be used alone or in combination of two or more.
ここで、本発明の電子デバイスの製法に用いられる機能膜形成用組成物の調製は、例えば、無機粒子（Ａ成分）とともに、上記特定のセルロース繊維（Ｂ成分）を分散媒中に配合し、さらに必要に応じてその他の材料を配合した後、これらを混合処理等することにより行われる。 Here, preparation of the composition for functional film formation used for the manufacturing method of the electronic device of this invention mix | blends the said specific cellulose fiber (B component) with a dispersion medium with an inorganic particle (A component), for example, Furthermore, it mix | blends by mixing these etc., after mix | blending other materials as needed.
上記その他の材料としては、例えば、防腐剤、防菌剤、酸化防止剤、熱安定剤、界面活性剤、耐候剤、セルロース系材料（微粉砕セルロース、カルボキシメチルセルロース、多価カルボキシメチルセルロース、長鎖カルボキシセルロース、１級アミノセルロース、カチオン化セルロース、２級アミノセルロース、ヒドロキシアルキルセルロース、メチルセルロース、長鎖アルキルセルロース、酢酸セルロース、硝酸セルロース等）、水溶性ポリアクリル系樹脂（ポリアクリル酸、メタアクリル酸アルキルエステル等）、天然系水溶性ポリマー（キサンタンガム、デキストラン、プルラン、マンナン、ペクチン、植物性由来ガム類、寒天、アルギン酸、ヒアルロン酸、デンプン、ゼラチン等）、合成系水溶性ポリマー（カルボキシビニルポリマー、ポリビニルアルコール、ポリアクリルアミド、ポリアクリル酸ナトリウム、ポリエチレンオキシド、ポリエチレンイミン等）、ウレタン樹脂，アクリル樹脂，エポキシ樹脂などのポリマーエマルジョン等を配合しても差し支えない。 Examples of the other materials include preservatives, antibacterial agents, antioxidants, heat stabilizers, surfactants, weathering agents, and cellulose materials (finely pulverized cellulose, carboxymethylcellulose, polyvalent carboxymethylcellulose, long chain carboxy Cellulose, primary amino cellulose, cationized cellulose, secondary amino cellulose, hydroxyalkyl cellulose, methyl cellulose, long chain alkyl cellulose, cellulose acetate, cellulose nitrate, etc.), water-soluble polyacrylic resin (polyacrylic acid, alkyl methacrylate) Esters), natural water-soluble polymers (xanthan gum, dextran, pullulan, mannan, pectin, plant-derived gums, agar, alginic acid, hyaluronic acid, starch, gelatin, etc.), synthetic water-soluble polymers (carboxyvinyl polymer) , Polyvinyl alcohol, polyacrylamide, sodium polyacrylate, polyethylene oxide, polyethyleneimine, etc.), urethane resins, no problem be compounded polymer emulsion or the like, such as an acrylic resin, an epoxy resin.
上記混合処理としては、例えば、真空ホモミキサー、ディスパー、プロペラミキサー、ニーダー等の各種混練器、ブレンダー、ホモジナイザー、超音波ホモジナイザー、コロイドミル、ペブルミル、ビーズミル粉砕機、高圧ホモジナイザー（超高圧ホモジナイザー等）、等を用いた混合処理があげられる。 Examples of the mixing treatment include various kneaders such as vacuum homomixers, dispersers, propeller mixers, kneaders, blenders, homogenizers, ultrasonic homogenizers, colloid mills, pebble mills, bead mill grinders, high-pressure homogenizers (such as ultra-high pressure homogenizers), Etc. are mixed.
なお、本発明の電子デバイスの製法に用いられる機能膜形成用組成物の、Ｂ型粘度計（回転数２．５ｒｐｍ）による２０℃環境下での粘度は、１０,０００〜１００，０００ｍＰａ・ｓの範囲であることが好ましく、特に好ましくは４０，０００〜８０，０００ｍＰａ・ｓの範囲である。 The viscosity of the composition for forming a functional film used in the method for producing an electronic device of the present invention in a 20 ° C. environment measured by a B-type viscometer (rotation speed: 2.5 rpm) is 10,000 to 100,000 mPa · s. The range is preferably 40,000 to 80,000 mPa · s.
本発明の電子デバイスの製法に用いられる機能膜形成用組成物は、ウェットコート方式、凸版印刷方式、フレクソ印刷方式、ドライオフセット印刷方式、グラビア印刷方式、グラビアオフセット印刷方式、オフセット印刷方式、スクリーン印刷方式、スプレー塗装方式、ダイコーター方式、インクジェット印刷方式、浸漬方式、刷毛塗り、バーコーター方式等により、機能膜形成に供されるものであり、その粘度の調整等により、上記各種の使用形態に適した態様をとることができる。さらに、本発明の電子デバイスの製法に用いられる機能膜形成用組成物は、無機粒子（Ａ成分）の選択や配合割合等により、電気絶縁膜、半導体膜、誘電体膜といった各種の機能膜の形成用途に用いることができる。なお、上記機能膜の厚みは、その機能膜の使用用途により異なるが、通常、０．５μｍ〜１００μｍ、好ましくは１．０〜２５μｍである。 The functional film forming composition used in the manufacturing method of the electronic device of the present invention includes a wet coating method, a relief printing method, a flexographic printing method, a dry offset printing method, a gravure printing method, a gravure offset printing method, an offset printing method, and a screen printing. System, spray coating method, die coater method, ink jet printing method, dipping method, brush coating, bar coater method, etc., are used for functional film formation. Appropriate embodiments can be taken. Furthermore, the composition for forming a functional film used in the method for producing an electronic device according to the present invention has various functional films such as an electrical insulating film, a semiconductor film, and a dielectric film, depending on the selection and blending ratio of inorganic particles (component A). It can be used for forming applications. In addition, although the thickness of the said functional film changes with uses of the functional film, it is 0.5 micrometer-100 micrometers normally, Preferably it is 1.0-25 micrometers.
つぎに、上記機能膜形成用組成物を用いた、電子デバイスの製法の一例について説明する。すなわち、まず、無機基材上の一部もしくは全面に、上記機能膜形成用組成物を塗布し、その塗膜を加熱により焼結させて、電気絶縁膜，半導体膜または誘電体膜である機能膜を形成し、その機能膜上の一部もしくは無機基材上に電極層を形成する。上記機能膜形成用組成物の塗布方法は、スプレー法、超音波スプレー法により行うことが好ましい。また、上記電極層の形成は、無機粒子含有機能膜上に金属層を形成し、その金属層にエッチング処理して配線パターンを形成することにより行うことが好ましい。なお、上記無機基材としては、金属基板、金属箔、コイルやインダクタ等の金属部材等があげられる。 Next, using the above functional film forming composition, an example of a manufacturing method of an electronic device will be described. That is, first, a part or entire surface of the inorganic substrate, coating the functional film forming composition, the coating film is sintered by heating, an electrically insulating film, a semiconductor film or a dielectric film functions A film is formed, and an electrode layer is formed on a part of the functional film or on an inorganic substrate. The functional film-forming composition is preferably applied by a spray method or an ultrasonic spray method. The electrode layer is preferably formed by forming a metal layer on the inorganic particle-containing functional film and etching the metal layer to form a wiring pattern. Examples of the inorganic base material include metal members such as metal substrates, metal foils, coils and inductors.
そして、上記機能膜と電極層とを形成した後の無機基材には、さらに、半導体チップを実装するようにしてもよい。 And you may make it mount a semiconductor chip further on the inorganic base material after forming the said functional film and an electrode layer.
なお、上記無機基材が、アルミニウム、銅、または鉄といった金属を主成分とするものであり、上記機能膜が、電気絶縁膜、半導体膜、または誘電体膜であるといった組合せの場合、電子デバイスの用途上、好ましい。このような電子デバイスとしては、例えば、ＬＥＤ素子、ＤＣ−ＤＣコンバータ、オーディオアンプ、モーターインバータ等があげられる。 In the case of a combination in which the inorganic base material is mainly composed of a metal such as aluminum, copper, or iron, and the functional film is an electrical insulating film, a semiconductor film, or a dielectric film, an electronic device It is preferable for use. Examples of such electronic devices include LED elements, DC-DC converters, audio amplifiers, motor inverters, and the like.
また、上記無機基材が、鉄を主成分とする磁性基材であり、上記機能膜が、ガラスからなる電気絶縁膜であるといった組合せの場合も、電子デバイスの用途上、好ましい。このような電子デバイスとしては、例えば、パワー用電源デバイス、インダクタ素子、チョークコイル、コモンモードフィルター等があげられる。
また、上記無機基材が、金属酸化物を主成分とするセラミック基材であり、上記機能膜が、ガラスからなる電気絶縁膜であるといった組合せの場合も、電子デバイスの用途上、好ましい。このような電子デバイスとしては、例えば、アレスタ素子、バリスタ素子、インダクタ素子、チョークコイル、コモンモードフィルター等があげられる。
A combination in which the inorganic base material is a magnetic base material containing iron as a main component and the functional film is an electrical insulating film made of glass is also preferable for use in electronic devices. Examples of such electronic devices include power supply devices for power, inductor elements, choke coils, and common mode filters.
A combination in which the inorganic base material is a ceramic base material containing a metal oxide as a main component and the functional film is an electrical insulating film made of glass is also preferable for use in electronic devices. Examples of such electronic devices include arrester elements, varistor elements, inductor elements, choke coils, common mode filters, and the like.
ここで、酸化亜鉛バリスタからなるセラミックアレスタ素子（避雷器）は、酸化亜鉛を主成分とし、酸化ビスマス、酸化コバルト、酸化マンガン、酸化アンチモンなどの添加物を加えて空気中で焼結させると、ｎ型半導体である酸化亜鉛からなるグレイン（粒子）と、酸化ビスマスを主成分とする液相の粒界（バウンダリー）から構成される多結晶体のセラミックスが得られる。このセラミックス焼結体に電圧を印加すると、比較的抵抗が低い酸化亜鉛粒子間に存在する高い絶縁性の酸化ビスマス系粒界に電界が掛かり、一定電圧を超えるとトンネル効果により一気に低抵抗となる。この特性を利用して、電源ラインに並列に接続することで、電源に一定電圧以上の電圧が掛かると短絡する特性から、数百Ｖ以下の低電圧領域ではバリスタ素子とし、１千Ｖ以上では避雷器として利用されている。酸化亜鉛バリスタをアレスタ（避雷器）として利用する場合、常に電源電圧が印加された状態となり、大気中の水分や不純物により焼結体の縁面が低抵抗となり沿面で放電が起こると、漏れ電流として損失となる。また一定電流以上の漏れ電流が発生すると、それを起点として絶縁破壊に至るケースが生じる場合がある。そのためアレスタ素子の縁面に高い絶縁抵抗を有するガラス層を塗布焼成し、漏れ電流の発生を抑制している。しかしこの縁面のガラス絶縁層は刷毛塗りで行うため、均一とはならず絶縁性にばらつきを有している。一方で均一に塗布する目的でスプレー法が検討されたが、スプレー液の沈降により塗布できなくなる場合や、塗布してもダレが生じて均一な絶縁機能膜にはならない場合が多発した。そのため、上記セラミックアレスタ素子の絶縁機能膜材料として、本発明の電子デバイスの製法に用いられる機能膜形成用組成物が有効となる。 Here, a ceramic arrester element (lightning arrester) composed of a zinc oxide varistor has zinc oxide as a main component, and when an additive such as bismuth oxide, cobalt oxide, manganese oxide, antimony oxide is added and sintered in air, n A polycrystalline ceramic composed of grains (particles) made of zinc oxide, which is a type semiconductor, and liquid-phase grain boundaries (boundaries) mainly composed of bismuth oxide is obtained. When a voltage is applied to this ceramic sintered body, an electric field is applied to the highly insulating bismuth oxide-based grain boundary existing between the zinc oxide particles having a relatively low resistance. When the voltage exceeds a certain voltage, the tunnel effect causes a low resistance at a stretch. . By using this characteristic, the varistor element is used in the low voltage region of several hundred volts or less, and is connected to the power supply line in parallel. It is used as a lightning arrester. When a zinc oxide varistor is used as an arrester (lightning arrester), the power supply voltage is always applied, and when the edge of the sintered body becomes low resistance due to moisture and impurities in the atmosphere and discharge occurs along the creepage, leakage current occurs. Loss. In addition, when a leakage current of a certain current or more is generated, there may be a case where dielectric breakdown starts from that current. Therefore, a glass layer having a high insulation resistance is applied and baked on the edge surface of the arrester element to suppress the occurrence of leakage current. However, since the glass insulating layer on the edge surface is formed by brushing, it is not uniform and has variations in insulating properties. On the other hand, the spray method has been studied for the purpose of uniform application, but there are many cases where application cannot be performed due to sedimentation of the spray liquid, or even when the application is applied, a uniform insulating functional film cannot be obtained. Therefore, the functional film forming composition used in the manufacturing method of the electronic device of the present invention is effective as the insulating functional film material of the ceramic arrester element.
また、アルミニウム箔からなる基材上に半導体膜と電極層とが形成されてなる、太陽光発電機能を有する電子デバイスの製法においても、上記機能膜形成用組成物を用いることができる。すなわち、上記基材の少なくとも一方の面に、上記機能膜形成用組成物であって、その無機粒子の主成分をケイ素とするものを塗布した後、その塗膜を加熱により焼結させて半導体膜を形成し、さらにその半導体膜に不純物をドープさせてＰ型及びＮ型の半導体部分を形成し、上記Ｐ型及びＮ型の半導体部分が形成された半導体膜上に電極層を形成することにより、上記電子デバイスを製造することができる。 Moreover, the said functional film formation composition can be used also in the manufacturing method of the electronic device which has a semiconductor film and an electrode layer on the base material which consists of aluminum foil, and has a solar power generation function. That is, on at least one surface of the substrate, and a said functional film forming composition was applied to those that the main component of the inorganic particles with silicon, is sintered by heating the coated film semiconductor Forming a film, further doping the semiconductor film with impurities to form P-type and N-type semiconductor portions, and forming an electrode layer on the semiconductor film on which the P-type and N-type semiconductor portions are formed; Thus, the electronic device can be manufactured.
上記各種製法において、上記のように特殊な機能膜形成用組成物を用いることにより、優れた作業性で、均一な機能膜や半導体膜を形成することができ、さらに、その皮膜性能（強度、絶縁性、導電性、熱伝導性等）を良好に得ることができることから、従来よりも優れた電子デバイスを製造することができる。 In the various production methods described above, by using a special functional film forming composition as described above, a uniform functional film or a semiconductor film can be formed with excellent workability, and the film performance (strength, Insulating properties, electrical conductivity, thermal conductivity, etc.) can be obtained satisfactorily, so that an electronic device superior to the conventional one can be manufactured.
つぎに、実施例について比較例と併せて説明する。ただし、本発明はこれら実施例に限定されるものではない。 Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.
まず、実施例および比較例に先立ち、無機粒子Ｇ００１〜Ｇ００５を作製した。 First, prior to Examples and Comparative Examples, inorganic particles G001 to G005 were produced.
〔無機粒子Ｇ００１〜Ｇ００５の作製〕
無機粒子Ｇ００１〜Ｇ００５を、下記の表１に示す添加量で所定のガラス粉末および所定の無機添加物を混合することにより得た。
上記所定の無機添加物としては、表１に示すように、Ａｌ2Ｏ3粉末（平均粒径５μｍ）、ＢａＴｉＯ3粉末（平均粒径０．３μｍ）、Ｓｉ粉末（平均粒径０．２μｍ）のいずれかを用いた。
また、上記所定のガラス粉末は、以下のようにして作製した。すなわち、まず、表１に示すガラス組成（ｗｔ％）となるよう、ガラス原料を雷潰機に入れ、６０分間混合した。次いで、上記混合した原料を、ＳＳＡ−Ｈアルミナ坩堝につめ、そのアルミナ坩堝を、予め１３００℃に加熱保持した電気炉に入れ、上記原料を２０分間溶融させた。そして、上記原料が充分ガラス状態となったときに、電気炉より坩堝を取り出し、蒸留水を入れたステンレス容器内に溶融滴下させ、急冷することで、ガラス固化させた。このようにして冷却させた固化ガラスを、蒸留水と共にアルミトレーに取り出し、１５０℃で１時間、乾燥機中で乾燥させた。そして、乾燥後のガラス塊を、雷潰機に投入し、１時間粗粉砕した。このようにして粗粉砕したガラス粉から、７０メッシュ篩により粗粒を取り除いた後、さらに二次粉砕を行った。なお、上記二次粉砕は、円筒状のアルミナ容器にガラス粗粉（約１００ｇ程度）を投入し、メタノール（１５０ｃｃ）を入れ、更にアルミナ玉石（１０ｍｍφのものと、１５ｍｍφのものとを、各２００ｇ）を入れ、ガラス粗粉を投入したアルミナ容器を回転架台に載せて、８０回転／分で７２時間の粉砕を行った。そして、二次粉砕後、ビーカーに粉砕済みガラス（メタノール含む）を入れ、防爆型乾燥機中にてメタノールを蒸発させて、さらに３００メッシュ篩により粗粒を除去することにより、目的とするガラス粉末を得た。
なお、無機粒子Ｇ００１〜Ｇ００５中のガラス粉末及び無機添加物の平均粒径は、レーザー回折・光散乱式粒度分布測定装置を用いて測定した。
また、表１に示すガラス原料について、ＢａＯは、ＢａＣＯ3、ＣａＯはＣａＣＯ3、Ｂ2Ｏ3は、ホウ酸（Ｈ3ＢＯ3）を用いた。すなわち、これらが、化学的に安定な材料であり、焼成後も酸化物となり、安定なガラスが形成できるからである。
[Preparation of inorganic particles G001 to G005]
Inorganic particles G001 to G005 were obtained by mixing a predetermined glass powder and a predetermined inorganic additive in the addition amounts shown in Table 1 below.
As the predetermined inorganic additive, as shown in Table 1, Al 2 O 3 powder (average particle size 5 μm), BaTiO 3 powder (average particle size 0.3 μm), Si powder (average particle size 0.2 μm) Any one of was used.
The predetermined glass powder was produced as follows. That is, first, glass raw materials were put into a thunder crusher and mixed for 60 minutes so that the glass composition (wt%) shown in Table 1 was obtained. Next, the mixed raw material was packed in an SSA-H alumina crucible, and the alumina crucible was put in an electric furnace previously heated and held at 1300 ° C., and the raw material was melted for 20 minutes. And when the said raw material became a sufficient glass state, the crucible was taken out from the electric furnace, it was made to melt and dripped in the stainless steel container containing distilled water, and it was made to solidify by quenching. The solidified glass thus cooled was taken out into an aluminum tray together with distilled water and dried in a dryer at 150 ° C. for 1 hour. And the glass lump after drying was thrown into the thunder crusher and coarsely pulverized for 1 hour. From the coarsely pulverized glass powder, coarse particles were removed with a 70 mesh sieve, and then secondary pulverization was performed. In the secondary pulverization, glass coarse powder (about 100 g) is put into a cylindrical alumina container, methanol (150 cc) is added, and alumina cobblestones (10 mmφ and 15 mmφ are each 200 g each. ), And the alumina container into which the coarse glass powder was put was placed on a rotating base and pulverized at 80 rpm for 72 hours. Then, after the secondary pulverization, crushed glass (including methanol) is put into a beaker, methanol is evaporated in an explosion-proof dryer, and coarse particles are removed with a 300-mesh sieve to obtain a desired glass powder. Got.
In addition, the average particle diameter of the glass powder and inorganic additive in the inorganic particles G001 to G005 was measured using a laser diffraction / light scattering particle size distribution measuring apparatus.
Further, the glass raw materials shown in Table 1, BaO is BaCO 3, CaO is CaCO 3, B 2 O 3 was used boric acid (H 3 BO 3). That is, these are chemically stable materials, and become oxides even after firing, and a stable glass can be formed.
また、実施例および比較例に先立ち、実施例用のセルロース水分散体Ａ１〜Ａ４および比較例用のセルロース水分散体Ｂ１〜Ｂ４を、以下のようにして作製した。 Prior to the examples and comparative examples, cellulose aqueous dispersions A1 to A4 for examples and cellulose aqueous dispersions B1 to B4 for comparative examples were prepared as follows.
〔セルロース水分散体Ａ１（実施例用）の作製〕
(1)酸化工程
ＴＥＭＰＯを０．５ｇ（０．０８ｍｍｏｌ／ｇ）と、臭化ナトリウム５．０ｇ(１．２１５ｍｍｏｌ／ｇ)を、精製水１６００ｇに溶解させ、１０℃に冷却した。この溶液に、乾燥重量で２００ｇ相当分の未乾燥の亜硫酸漂白針葉樹パルプ（ＮＢＫＰ）（主に１０００ｎｍを超える繊維径の繊維からなる）を分散させた後、１２重量％次亜塩素酸ナトリウム水溶液を、固形分換算で１５．０ｇ（５ｍｍｏｌ／ｇ）を加えて反応を開始した。反応の進行に伴いｐＨが低下するので、２４％ＮａＯＨ水溶液を適宜加えながらｐＨ＝１０〜１０．５となるように調整し０．５時間反応させた。
(2)還元工程
上記反応物を遠心分離機で固液分離した後、精製水を加え固形分濃度４％に調整した。その後、２４％ＮａＯＨ水溶液にてスラリーのｐＨを１０に調整した。スラリーの温度を３０℃としてＮａＢＨ4を０．３ｇ（０．２ｍｍｏｌ／ｇ）を加え２時間反応させた。(3)精製工程
上記反応物をガラスフィルターにてろ過した後、充分な量のイオン交換水による水洗、ろ過を行い、得られたろ液の電気伝導度を測定した。水洗を繰り返しても、ろ液の電気伝導度に変化がなくなった時点で精製工程を終了した。このようにして、水を含んだ固形分量１５重量％のセルロース繊維を得た。
(4)水分散工程
上記セルロース繊維に水を加え２重量％のスラリーとして、ディスパー型ミキサーを用いて回転数８０００ｒｐｍで１０分間微細化処理を行い、セルロース水分散体Ａ１を得た。
[Production of Cellulose Aqueous Dispersion A1 (for Examples)]
(1) Oxidation step 0.5 g (0.08 mmol / g) of TEMPO and 5.0 g (1.215 mmol / g) of sodium bromide were dissolved in 1600 g of purified water and cooled to 10 ° C. In this solution, an undried sulfite bleached softwood pulp (NBKP) equivalent to 200 g in dry weight (mainly composed of fibers having a fiber diameter exceeding 1000 nm) was dispersed, and then a 12 wt% sodium hypochlorite aqueous solution was added. The reaction was started by adding 15.0 g (5 mmol / g) in terms of solid content. Since the pH decreased with the progress of the reaction, the pH was adjusted to 10 to 10.5 while appropriately adding a 24% NaOH aqueous solution, and the reaction was carried out for 0.5 hours.
(2) Reduction step After the above reaction product was subjected to solid-liquid separation with a centrifuge, purified water was added to adjust the solid content concentration to 4%. Thereafter, the pH of the slurry was adjusted to 10 with a 24% NaOH aqueous solution. The temperature of the slurry was set to 30 ° C., 0.3 g (0.2 mmol / g) of NaBH 4 was added and reacted for 2 hours. (3) Purification step After the reaction product was filtered through a glass filter, it was washed with a sufficient amount of ion-exchanged water and filtered, and the electrical conductivity of the obtained filtrate was measured. The purification process was completed when the electrical conductivity of the filtrate ceased to change even after repeated washing with water. Thus, a cellulose fiber having a solid content of 15% by weight containing water was obtained.
(4) Water Dispersion Step Water was added to the cellulose fiber to make a 2 wt% slurry, and a finer treatment was performed at a rotation speed of 8000 rpm for 10 minutes using a disper mixer to obtain a cellulose aqueous dispersion A1.
〔セルロース水分散体Ａ２〜Ａ４（実施例用）、セルロース水分散体Ｂ１〜Ｂ４（比較例用）の作製〕
セルロースの原料種（ＮＢＫＰ、リンターパルプ（再生セルロース））や、酸化工程の際に添加する次亜塩素酸ナトリウム（ＮａＣｌＯ）仕込量（ｍｍｏｌ／ｇ）や、還元工程の際に添加する水素化ホウ素ナトリウム（ＮａＢＨ4）仕込量（ｍｍｏｌ／ｇ）を、下記の表２に示すように変更する以外は、セルロース水分散体Ａ１の作製に準じて、セルロース水分散体Ａ２〜Ａ４，Ｂ１〜Ｂ４を、それぞれ作製した。
[Production of Cellulose Aqueous Dispersions A2 to A4 (for Examples) and Cellulose Aqueous Dispersions B1 to B4 (for Comparative Examples)]
Cellulose raw materials (NBKP, linter pulp (regenerated cellulose)), sodium hypochlorite (NaClO) charge added during the oxidation process (mmol / g), boron hydride added during the reduction process Cellulose aqueous dispersions A2 to A4 and B1 to B4 were prepared in accordance with the preparation of cellulose aqueous dispersion A1, except that the amount of sodium (NaBH 4 ) charged (mmol / g) was changed as shown in Table 2 below. , Respectively.
なお、上記表２に示す、セルロース水分散体Ａ１〜Ａ４，Ｂ１〜Ｂ４に関する各項目の測定は、下記の基準に従って行った。 In addition, the measurement of each item regarding the cellulose aqueous dispersion A1-A4 and B1-B4 shown in the said Table 2 was performed according to the following reference | standard.
〔ＣＯＯＨ量（カルボキシル基量）の測定〕
セルロース水分散体を６０ｍｌ（セルロース重量：０．２５ｇ）調製し、０．１Ｍの塩酸水溶液によってｐＨを約２．５とした後、０．０５Ｍの水酸化ナトリウム水溶液を滴下して、電気伝導度測定を行った。測定はｐＨが約１１になるまで続けた。電気伝導度の変化が緩やかな弱酸の中和段階において消費された水酸化ナトリウム量（Ｖ）から、下の式（６）に従いカルボキシル基量を求めた。
[Measurement of COOH amount (carboxyl group amount)]
After preparing 60 ml of cellulose aqueous dispersion (cellulose weight: 0.25 g) and adjusting the pH to about 2.5 with 0.1 M hydrochloric acid aqueous solution, 0.05 M sodium hydroxide aqueous solution was added dropwise to obtain electric conductivity. Measurements were made. The measurement was continued until the pH was about 11. The amount of carboxyl groups was determined from the amount of sodium hydroxide consumed in the neutralization step of the weak acid with a slow change in electrical conductivity (V) according to the following equation (6).
カルボキシル基量 (mmol/g)＝Ｖ(ml)×〔０．０５／セルロース重量〕 ……(６) Amount of carboxyl group (mmol / g) = V (ml) × [0.05 / cellulose weight] (6)
〔カルボニル基量の測定（セミカルバジド法）〕
セルロース水分散体を乾燥させた試料を約０．２ｇ精秤し、これに、リン酸緩衝液によりｐＨ＝５に調整したセミカルバジド塩酸塩３ｇ／ｌ水溶液を正確に５０ｍｌ加え、密栓し、二日間振とうした。ついで、この溶液１０ｍｌを正確に１００ｍｌビーカーに採取し、５Ｎ硫酸を２５ｍｌ、０．０５Ｎヨウ素酸カリウム水溶液５ｍｌを加え、１０分間撹拌した。その後、５％ヨウ化カリウム水溶液１０ｍｌを加えて、直ちに自動滴定装置を用いて、０．１Ｎチオ硫酸ナトリウム溶液にて滴定し、その滴定量等から、下記の式（７）に従い、試料中のカルボニル基量（アルデヒド基とケトン基との合計含量）を求めた。
カルボニル基量(mmol/g)＝（Ｄ−Ｂ）×ｆ×〔０.１２５／ｗ〕 ……(７)
Ｄ：サンプルの滴定量（ｍｌ）
Ｂ：空試験の滴定量（ｍｌ）
ｆ：０.１Ｎチオ硫酸ナトリウム溶液のファクター（−）
ｗ：試料量（ｇ）
[Measurement of amount of carbonyl group (semicarbazide method)]
About 0.2 g of a sample obtained by drying the cellulose aqueous dispersion was precisely weighed, and to this was accurately added 50 ml of a 3 g / l aqueous solution of semicarbazide hydrochloride adjusted to pH = 5 with a phosphate buffer, sealed, and sealed for 2 days. Shake. Then, 10 ml of this solution was accurately collected in a 100 ml beaker, 25 ml of 5N sulfuric acid and 5 ml of 0.05N potassium iodate aqueous solution were added, and the mixture was stirred for 10 minutes. Thereafter, 10 ml of a 5% potassium iodide aqueous solution was added, and immediately titrated with a 0.1N sodium thiosulfate solution using an automatic titrator. From the titration amount and the like, according to the following formula (7), The amount of carbonyl groups (total content of aldehyde groups and ketone groups) was determined.
Carbonyl group amount (mmol / g) = (D−B) × f × [0.125 / w] (7)
D: Sample titration (ml)
B: Titrate of blank test (ml)
f: Factor (-) of 0.1N sodium thiosulfate solution
w: Sample amount (g)
〔アルデヒド基の検出（フェーリング反応法）〕
セルロース繊維を０．４ｇ精秤し、日本薬局方に従って調製したフェーリング試薬（酒石酸ナトリウムカリウムと水酸化ナトリウムとの混合溶液５ｍｌと、硫酸銅五水和物水溶液５ｍｌ）を加えた後、８０℃で１時間加熱した。そして、上澄みが青色、セルロース繊維部分が紺色を呈するものはアルデヒド基が検出されなかったと判断し、「無し」と評価した。また、上澄みが黄色、セルロース繊維部分が赤色を呈するものは、アルデヒド基が検出されたと判断し、「有り」と評価した。
[Detection of aldehyde groups (Fering reaction method)]
0.4 g of cellulose fiber was precisely weighed and added with a Fering reagent prepared according to the Japanese Pharmacopoeia (5 ml of a mixed solution of sodium potassium tartrate and sodium hydroxide and 5 ml of an aqueous copper sulfate pentahydrate solution) at 80 ° C. Heated for 1 hour. The supernatant blue, those of cellulose fiber sections exhibits a dark blue determines that aldehyde groups were not detected was evaluated as "edentulous". Moreover, when the supernatant was yellow and the cellulose fiber portion was red, it was judged that an aldehyde group was detected, and was evaluated as “present”.
〔数平均繊維径の測定〕
セルロース水分散体におけるセルロース繊維の数平均繊維径を、透過型電子顕微鏡（ＴＥＭ）（日本電子社製、ＪＥＭ−１４００）を用いて観察した。すなわち、各セルロース繊維を親水化処理済みのカーボン膜被覆グリッド上にキャストした後、２％ウラニルアセテートでネガティブ染色したＴＥＭ像（倍率：１００００倍）から、先に述べた方法に従い、数平均繊維径を算出した。
[Measurement of number average fiber diameter]
The number average fiber diameter of the cellulose fibers in the cellulose aqueous dispersion was observed using a transmission electron microscope (TEM) (manufactured by JEOL Ltd., JEM-1400). That is, after each cellulose fiber was cast on a hydrophilized carbon film-coated grid and negatively stained with 2% uranyl acetate, the number average fiber diameter was determined according to the method described above. Was calculated.
〔非晶領域量の測定〕
Ｘ線回折装置（リガク社製、ＲＩＮＴ−Ｕｌｔｉｍａ３）を用いて、セルロース水分散体におけるセルロース繊維のＸ線回折スペクトルを測定し、そのピーク強度ＩおよびＩａに基づき、下記の式（８）により、結晶化度を算出した。その結果をもとに、下記の式（９）により、セルロースの非晶領域量を算出した。
(Measurement of amount of amorphous region)
Using an X-ray diffractometer (Rigaku Corporation, RINT-Utima3), the X-ray diffraction spectrum of the cellulose fiber in the cellulose aqueous dispersion was measured. Based on the peak intensity I and Ia, the following formula (8): Crystallinity was calculated. Based on the result, the amorphous region amount of cellulose was calculated by the following formula (9).
結晶化度（％）＝（Ｉ−Ｉａ）／Ｉ×１００ ……(８)
Ｉ：２θ＝１４．６０°のピーク強度
Ｉａ：２θ＝１２°と１８°の強度を結んだ直線と２θ＝１４．６０°の強度から真 直ぐ下ろした直線が交わる点の強度（非晶領域のピーク強度）
非晶領域量（％）＝１００−（Ｉ−Ｉａ）／Ｉ×１００ ……(９)
Crystallinity (%) = (I−Ia) / I × 100 (8)
I: Peak intensity at 2θ = 14.60 ° Ia: Intensity at the point where a straight line connecting the intensity of 2θ = 12 ° and 18 ° and a straight line down from the intensity of 2θ = 14.60 ° (amorphous region) Peak intensity)
Amorphous region amount (%) = 100− (I−Ia) / I × 100 (9)
［実施例１〜１０、比較例１〜４］
前記作製の無機粒子Ｇ００１〜Ｇ００５と、前記作製のセルロース水分散体Ａ１〜Ａ４，Ｂ１〜Ｂ４と、極性溶剤（Ｃ−１、Ｃ−２）と、添加剤（Ｄ−１、Ｄ−２）とを、後記の表３および表４に示す割合で、合計量が３００ｇになるよう配合し、それを、撹拌部にホモミキサーＭＡＲＫIIをとりつけたＰＲＩＭＩＸ社製ロボミックスで、８０００ｒｐｍで５分撹拌し、目的とする機能膜形成用組成物を調製した。なお、上記極性溶剤（Ｃ−１、Ｃ−２）、添加剤（Ｄ−１、Ｄ−２）は、下記に示すものである。
Ｃ−１：水
Ｃ−２：エタノール
Ｄ−１：レバナックスＢＡ−２００（１，２−ベンゾチアゾリン−３−オン）、昌栄化学社製
Ｄ−２：ノイゲンＸＬ−４０、第一工業製薬社製
[Examples 1 to 10, Comparative Examples 1 to 4]
The prepared inorganic particles G001 to G005, the prepared cellulose aqueous dispersions A1 to A4, B1 to B4, the polar solvents (C-1, C-2), and the additives (D-1, D-2). Were mixed in the proportions shown in Table 3 and Table 4 below so that the total amount was 300 g, and the mixture was stirred at 8000 rpm for 5 minutes with a PRIMIX Robomix with a homomixer MARKII attached to the stirring section. A target functional film-forming composition was prepared. The polar solvents (C-1, C-2) and additives (D-1, D-2) are shown below.
C-1: Water C-2: Ethanol D-1: Revanax BA-200 (1,2-benzothiazoline-3-one), manufactured by Changei Chemical Co. D-2: Neugen XL-40, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
上記のようにして得られた実施例および比較例の機能膜形成用組成物に関し、下記の基準に従って、各特性の評価を行った。その結果を、後記の表３および表４に併せて示す。 With respect to the functional film forming compositions of Examples and Comparative Examples obtained as described above, each characteristic was evaluated according to the following criteria. The results are also shown in Table 3 and Table 4 below.
〔分散度の測定〕
機能膜形成用組成物の一部を試験管にうつして一日室温で静置後、無機粒子が均一に分散しているか確認した。試験管中の系全体に対して、無機粒子が分散している層（分散層）の割合を試験管の目盛または定規等により長さを測定し、分散度合をパーセンテージで表記した。なお、本発明では、上記分散度が６０％以上であることが望ましく、より望ましくは、分散度が８０％以上である。
(Measurement of degree of dispersion)
A part of the functional film-forming composition was transferred to a test tube and allowed to stand at room temperature for one day, and then it was confirmed whether the inorganic particles were uniformly dispersed. The length of the layer in which the inorganic particles are dispersed (dispersed layer) was measured with respect to the entire system in the test tube using a test tube scale or a ruler, and the degree of dispersion was expressed as a percentage. In the present invention, the degree of dispersion is desirably 60% or more, and more desirably, the degree of dispersion is 80% or more.
〔再分散性の測定〕
機能膜形成用組成物の一部を試験管にうつして一日室温で静置後、無機粒子分散スラリーが沈降している場合に試験管を手動で激しく上下に２０回振とうして、振とう直後の再分散性を評価した。すなわち、上記のようにして再分散させた後、上記分散度の評価基準に準じ、８０％以上の分散度と同等になった場合を再分散性があると判断し、「○」と表記し、８０％未満の分散度と同等になった場合を再分散性が無いと判断し、「×」と表記した。
(Measurement of redispersibility)
A part of the functional film-forming composition is transferred to a test tube and allowed to stand at room temperature for one day, and when the inorganic particle-dispersed slurry has settled, the test tube is shaken vigorously up and down 20 times manually. The redispersibility immediately after the evaluation was evaluated. That is, after redispersion as described above, according to the above evaluation criteria for the degree of dispersion, a case where the degree of dispersion is equal to or greater than 80% is judged to be redispersible, and is described as “◯”. When the degree of dispersion was less than 80%, it was determined that there was no redispersibility, and was indicated as “x”.
〔粘度の測定〕
機能膜形成用組成物を、ＢＨ型粘度計（Ｎｏ．４ローター）（東機産業社製、ＢＨ型粘度計）を用いて、回転数２．５ｒｐｍ（３分）で、２０℃環境下での粘度（Ｐａ・ｓ）を測定した。
(Measurement of viscosity)
Using a BH type viscometer (No. 4 rotor) (manufactured by Toki Sangyo Co., Ltd., BH type viscometer), the composition for forming a functional film was rotated at 2.5 rpm (3 minutes) in an environment of 20 ° C. The viscosity (Pa · s) of was measured.
〔保存安定性の測定〕
機能膜形成用組成物を、４０℃の温度環境下で長期間（３０日間）放置し、放置前後での分散度および粘度を、前記のようにして測定し、それらの変動率を「保存安定性（％）」とし、下記の式（１１）および（１２）により算出した。
[Measurement of storage stability]
The composition for forming a functional film is allowed to stand for a long time (30 days) in a temperature environment of 40 ° C., and the dispersity and viscosity before and after being left are measured as described above. Calculated by the following formulas (11) and (12).
保存安定性（分散性）＝（放置後の分散度／放置前の分散度）×１００ ……(11)
保存安定性（粘度）＝（放置後の粘度／放置前の粘度）×１００ ……(12)
Storage stability (dispersibility) = (dispersion after leaving / dispersion before leaving) x 100 (11)
Storage stability (viscosity) = (viscosity after standing / viscosity before standing) x 100 (12)
〔スプレー性の評価〕
三谷バルブのスプレー（ノズルタイプＺ−７５−１１−１）に、機能膜形成用組成物を入れて、ノズルを一定の圧力で押して１０センチメートル離れた板に吹き付けた。そして、水をポジティブコントロール、１％キサンタンガム水溶液をネガティブコントロールとして、スプレー性の比較を行った。すなわち、水に近い使用感でスプレー状に吹き付けることができたものを「○」、１％キサンタンガム水溶液に近い使用感で、一部しかスプレー状に吹き付けることができなかったもの（直射状の吹き付けとなったもの）を「×」と評価した。
[Evaluation of sprayability]
The functional film-forming composition was placed in a Mitani valve spray (nozzle type Z-75-11-1), and the nozzle was pushed at a constant pressure and sprayed on a plate 10 cm away. Then, spray properties were compared using water as a positive control and 1% xanthan gum aqueous solution as a negative control. In other words, “○” indicates that the spray can be sprayed with a feeling close to that of water, and only a portion of the spray can be sprayed with a feeling close to that of a 1% xanthan gum aqueous solution (direct spraying) Was evaluated as “×”.
上記表３および表４の結果より、実施例の機能膜形成用組成物は、比較例のものに比べ、分散度が高く、再分散性も良好であり、保存安定性に優れている。さらに、実施例の機能膜形成用組成物は、比較例のものに比べ、粘度が高いにもかかわらず、そのＴＩが高いことから、スプレー性において良好な結果が得られていることがわかる。 From the results of Tables 3 and 4, the functional film-forming compositions of the examples have a higher degree of dispersion, better redispersibility, and better storage stability than the comparative examples. Further, it can be seen that the functional film-forming compositions of the examples have good results in sprayability because their TI is high despite the higher viscosity than the comparative examples.
上記結果は、実施例で用いられているセルロース水分散体Ａ１〜Ａ４が、本発明に規定されたセルロースの規定を全て満たしているのに対し、セルロース水分散体Ｂ１〜Ｂ４は、本発明に規定されたセルロースの規定を一部満たしていないことによるものである（前記表２の分析結果を参照）。 The above results show that the cellulose aqueous dispersions A1 to A4 used in the examples satisfy all the regulations of cellulose defined in the present invention, whereas the cellulose aqueous dispersions B1 to B4 are included in the present invention. This is because some of the prescribed cellulose regulations are not satisfied (see the analysis results in Table 2 above).
なお、セルロース水分散体Ａ１〜Ａ４に関し、セルロース繊維表面上のグルコースユニットのＣ６位の水酸基のみが選択的にカルボキシル基等に酸化されているかどうかについて、13Ｃ−ＮＭＲチャートで確認した。すなわち、酸化前のセルロースの13Ｃ−ＮＭＲチャートで確認できるグルコース単位の１級水酸基のＣ６位に相当する６２ｐｐｍのピークが、酸化反応後は消失し、代わりに１７８ｐｐｍにカルボキシル基に由来するピークが現れていた。このことから、上記セルロース繊維は、いずれもグルコース単位のＣ６位水酸基のみがカルボキシル基等に酸化されていることが確認された。 In addition, regarding the cellulose aqueous dispersions A1 to A4, whether or not only the hydroxyl group at the C6 position of the glucose unit on the cellulose fiber surface was selectively oxidized to a carboxyl group or the like was confirmed by a 13 C-NMR chart. That is, the 62 ppm peak corresponding to the C6 position of the primary hydroxyl group of the glucose unit, which can be confirmed on the 13 C-NMR chart of cellulose before oxidation, disappears after the oxidation reaction, and instead a peak derived from the carboxyl group at 178 ppm. It was appearing. From this, it was confirmed that in the cellulose fibers, only the C6 hydroxyl group of the glucose unit was oxidized to a carboxyl group or the like.
また、実施例に使用されている無機粒子に代えて、所定の無機粒子（ホウ素、リチウム、ナトリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、ジルコニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、鉄、コバルト、ニッケル、テルル、銅、亜鉛、アルミニウム、ケイ素、リン、ガリウム、インジウム、スズ、鉛およびビスマスからなる群から選ばれた少なくとも一つの元素を含む無機粒子であって、その平均粒径が１００ｎｍ〜３０μｍである無機粒子）を用いた場合であっても、実施例と同様に優れた保存安定性、スプレー性等が得られることが確認された。 Further, instead of the inorganic particles used in the examples, predetermined inorganic particles (boron, lithium, sodium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, An inorganic particle containing at least one element selected from the group consisting of manganese, iron, cobalt, nickel, tellurium, copper, zinc, aluminum, silicon, phosphorus, gallium, indium, tin, lead and bismuth, and its average Even when inorganic particles having a particle diameter of 100 nm to 30 μm were used, it was confirmed that excellent storage stability, sprayability and the like were obtained as in the examples.
〔電源デバイス用チョークコイル〕
つぎに、下記の製造法に従い製造された電源デバイス用チョークコイルにおいて、その絶縁膜の形成材料に、実施例１の機能膜形成用組成物をスプレー塗布して用いたところ、比較例１〜４の機能膜形成用組成物をスプレー塗布して用いた場合に比べ、緻密で塗布時のダレが少なく均一な絶縁膜が金属磁性体表面に形成され、極めて高い絶縁性能が得られた。また金属磁性体の複雑な形状表面、特に鋭角に形成されたエッジにも均一に塗布されており、エッジ部分の金属磁性体が露出していないといった結果が得られた。なお、下記の製造法で、金属酸化物を主成分とするＦｅ−Ｎｉ−Ｚｎ−Ｏ系フェライト磁性体を用い、磁性体コアを焼成して作製した場合でも、同様の結果が得られた。
[Choke coils for power devices]
Next, in the choke coil for a power supply device manufactured according to the following manufacturing method, the functional film forming composition of Example 1 was spray applied to the insulating film forming material, and Comparative Examples 1 to 4 were used. Compared with the case where the composition for forming a functional film was applied by spray coating, a uniform insulating film was formed on the surface of the metal magnetic material, which was dense and less sagging during coating, and an extremely high insulating performance was obtained. In addition, it was uniformly applied to the complicatedly shaped surface of the metal magnetic body, particularly the edge formed at an acute angle, and the result was that the metal magnetic body at the edge portion was not exposed. In addition, the same result was obtained even when the magnetic core was baked by using the Fe—Ni—Zn—O-based ferrite magnetic body mainly composed of a metal oxide by the following manufacturing method.
≪電源デバイス用チョークコイルの製造法≫
まず、鉄、ニッケル、コバルトを主成分とする粉末に、ポリビニルアルコールを１０重量％含む水溶液を５ｗｔ％添加、混合して造粒したものを用いて、粉末プレス成型によってボビン状の成型体を得た。この成型体を窒素中１２００℃の温度で焼成することで金属磁性体コアを得た。金属磁性体コアの形状は、ボビンの最も大きい部分の径が、φ８ｍｍ、ボビンの高さが１０ｍｍ、最小の巻線部の径がφ４ｍｍとなるよう形成した。金属磁性体は高い透磁率と飽和磁束密度のため、小型なインダクタが形成でき、銅線をそのコア部に巻きつけることにより、電源用のチョークコイルに適しているものの、その金属磁性体が金属であるがゆえに導電性があり、巻線の銅線と接触するとショートすると非常に危険なことから、実施例１および比較例１〜４の機能膜形成用組成物を、スプレー法により金属磁性体コアの表面に約３０μｍの均一な厚みに塗布し、乾燥させた後、６００℃の温度で電気炉にて焼結させ、そのガラス組成物の溶融により、約２０μｍ厚みの均一な絶縁膜を形成した。次いで、この絶縁膜上に、Ａｇ粉末、ガラス、有機バインダー、および溶剤からなる導電性ペーストを、塗布し、乾燥させ、焼成させることにより、電極層を形成した。焼成温度は５５０℃とした。このようにしてガラス絶縁膜が形成された金属磁性体コア（ボビン状）の巻線部分に、表面を絶縁処理した線径１．２ｍｍの被覆銅線（エナメル線）を１０回巻線処理し、巻線の開始端と終端を、前記の電極層に半田付けした。このようにして、目的とする電源デバイス用チョークコイルを得た。
≪Method of manufacturing choke coil for power supply device≫
First, a bobbin-shaped molded body is obtained by powder press molding using a powder mainly composed of iron, nickel, and cobalt, added with 5 wt% of an aqueous solution containing 10% by weight of polyvinyl alcohol, mixed and granulated. It was. The molded body was fired in nitrogen at a temperature of 1200 ° C. to obtain a metal magnetic core. The shape of the metal magnetic core was formed so that the diameter of the largest portion of the bobbin was φ8 mm, the bobbin height was 10 mm, and the minimum winding diameter was φ4 mm. The metal magnetic body has a high magnetic permeability and saturation magnetic flux density, so that a small inductor can be formed, and it is suitable for a choke coil for power supply by winding a copper wire around its core part. Therefore, the composition for forming a functional film of Example 1 and Comparative Examples 1 to 4 is made of a metal magnetic material by a spray method. It is applied to the surface of the core to a uniform thickness of about 30 μm, dried, then sintered in an electric furnace at a temperature of 600 ° C., and a uniform insulating film having a thickness of about 20 μm is formed by melting the glass composition. did. Next, a conductive paste made of Ag powder, glass, an organic binder, and a solvent was applied on the insulating film, dried, and fired to form an electrode layer. The firing temperature was 550 ° C. A coated copper wire (enameled wire) having a wire diameter of 1.2 mm whose surface is insulated is wound 10 times on the winding portion of the metal magnetic core (bobbin shape) formed with the glass insulating film in this way. The start and end of the winding were soldered to the electrode layer. In this way, a desired power device choke coil was obtained.
〔セラミックアレスタ素子〕
また、下記の製造法に従い製造された無線中継局用セラミックアレスタ素子（避雷器）において、その絶縁膜の形成材料に、実施例７の機能膜形成用組成物をスプレー塗布して用いたところ、比較例１〜４の機能膜形成用組成物をスプレー塗布して用いた場合に比べ、緻密で塗布時のダレが少なく均一な絶縁膜がアレスタ素子縁部に形成され、極めて高い絶縁性能が得られた。またアレスタ素子の電極間の沿面放電を抑制することができるといった結果が得られた。すなわち、実施例７の機能膜形成用組成物を用いて得られたアレスタ素子は、バリスタ電圧は４００Ｖ／ｍｍであり、７．２ＫＶ以上のサージ電圧を除去できるばかりか、縁面のリークも無いことが確認できた。
[Ceramic arrester element]
Moreover, in the ceramic arrester element (lightning arrester) for a radio relay station manufactured according to the following manufacturing method, the composition for forming a functional film of Example 7 was used as the insulating film forming material by spray coating. Compared to the case where the functional film-forming composition of Examples 1 to 4 is applied by spray coating, a uniform insulating film is formed on the edge of the arrester element with a dense and less sagging during coating, and extremely high insulating performance is obtained. It was. Moreover, the result that the creeping discharge between the electrodes of the arrester element can be suppressed was obtained. That is, the arrester element obtained by using the composition for forming a functional film of Example 7 has a varistor voltage of 400 V / mm, can not only eliminate a surge voltage of 7.2 KV or more, and has no leakage at the edge. I was able to confirm.
≪アレスタ素子の製造法≫
まず、酸化亜鉛粉末に対し、酸化ビスマス、酸化コバルト、酸化マンガン、酸化アンチモン、酸化チタンを各０．５ｍｏｌ％添加した組成物を造粒し、φ３０ｍｍ高さ２５ｍｍの円筒状に粉末プレスにより成型体を得た。成型体を大気中１２５０℃の温度で焼成し、アレスタ素子を得た。焼成後のアレスタ素子は焼結収縮により、φ２５ｍｍ高さ２０ｍｍの焼結体となった。このようにして作製されたアレスタ素子の縁面部（円筒状の部分）に、実施例７および比較例１〜４の機能膜形成用組成物をスプレー塗布した。その塗膜を乾燥後、６００℃の温度で熱処理し、ガラス化した約３０μｍ厚みの機能膜を形成した。次いで表裏面を研磨して１８ｍｍ厚みにし、さらにその研磨面にアルミ線を溶射することで電極層を形成した。これにより両面にアルミ電極層と、縁面部に高絶縁機能膜ガラス層を有するアレスタ素子を得た。
≪Method for manufacturing arrester element≫
First, a composition obtained by adding 0.5 mol% each of bismuth oxide, cobalt oxide, manganese oxide, antimony oxide, and titanium oxide to zinc oxide powder is granulated, and formed into a cylindrical shape having a diameter of 30 mm and a height of 25 mm by a powder press. Got. The molded body was fired in the atmosphere at a temperature of 1250 ° C. to obtain an arrester element. The arrester element after firing became a sintered body having a diameter of 25 mm and a height of 20 mm due to sintering shrinkage. The composition for forming a functional film of Example 7 and Comparative Examples 1 to 4 was spray-coated on the edge portion (cylindrical portion) of the arrester element thus produced. The coating film was dried and then heat treated at a temperature of 600 ° C. to form a vitrified functional film having a thickness of about 30 μm. Next, the front and back surfaces were polished to a thickness of 18 mm , and an aluminum layer was sprayed on the polished surface to form an electrode layer. As a result, an arrester element having an aluminum electrode layer on both sides and a highly insulating functional film glass layer on the edge portion was obtained.
〔ＬＥＤ素子〕
また、下記の製造法に従い製造されたＬＥＤ素子用高放熱基板を用い、下記のようにして製造されたＬＥＤ素子において、その絶縁膜の形成材料に、実施例８の機能膜形成用組成物をスプレー塗布して用いたところ、比較例１〜４の機能膜形成用組成物をスプレー塗布して用いた場合に比べ、高い電気絶縁性を保ちながら、高い熱伝導性と高い反射率のＬＥＤ素子用高放熱デバイスが得られた。特に従来の有機系絶縁膜にない高い絶縁信頼性、接着強度の劣化、耐熱性といった良好な結果が得られた。
なお、実施例８の機能膜形成用組成物を用いて作製された高放熱基板の電極上に半導体素子を実装し、その発熱によりどのように放熱されるかを評価したところ、１０Ｗ／ｍＫと有機系絶縁膜では得られない高い熱伝導性が得られ、さらに、銅電極とアルミ板間の絶縁耐圧を評価したところ、１５ＫＶ以上の極めて高い絶縁耐圧が得られた。
また、実施例８の機能膜形成用組成物を用いて作製されたＬＥＤ素子に、低電流電源により２５０ｍＡの電流を印加し、ＬＥＤ素子の端子電圧ＶＢＥを評価したところ、ＶＢＥは０．７Ｖであり、０．１７５Ｗの消費電力であった。この時ＬＥＤ素子の端子電圧から、ＬＥＤチップの発熱量が約２５℃の上昇しかしないことがわかった。ＬＥＤチップは低電流であれば、端子電圧ＶＢＥは温度に比例することがわかっており、アルミ放熱基板で無い場合は、約５０℃の温度上昇があるが、本実施例では約２５℃の温度上昇となり、熱抵抗が小さいことがわかる。同時に熱伝導性が良好と言え、同じＬＥＤチップであればより高い輝度を発光させることができることを意味する。
[LED element]
Moreover, in the LED element manufactured as follows using the high heat dissipation substrate for LED element manufactured according to the following manufacturing method, the functional film forming composition of Example 8 was used as the insulating film forming material. Compared with the case where the composition for forming a functional film of Comparative Examples 1 to 4 is used by spray coating, the LED element has high thermal conductivity and high reflectance while maintaining high electrical insulation. A high heat dissipation device was obtained. In particular, good results such as high insulation reliability, deterioration of adhesive strength, and heat resistance, which are not found in conventional organic insulating films, were obtained.
In addition, when a semiconductor element was mounted on the electrode of the high heat dissipation substrate manufactured using the composition for forming a functional film of Example 8, and how it was dissipated by the heat generation was evaluated as 10 W / mK. High thermal conductivity that cannot be obtained with an organic insulating film was obtained. Furthermore, when the withstand voltage between the copper electrode and the aluminum plate was evaluated, an extremely high withstand voltage of 15 KV or more was obtained.
Moreover, when a current of 250 mA was applied to the LED element produced using the functional film forming composition of Example 8 by a low current power source and the terminal voltage VBE of the LED element was evaluated, VBE was 0.7V. Yes, the power consumption was 0.175W. At this time, it was found from the terminal voltage of the LED element that the amount of heat generated by the LED chip only increased by about 25 ° C. If the LED chip has a low current, it is known that the terminal voltage VBE is proportional to the temperature. If the LED chip is not an aluminum heat dissipation substrate, the temperature rises by about 50 ° C., but in this embodiment, the temperature is about 25 ° C. It turns out that the thermal resistance is small. At the same time, it can be said that the thermal conductivity is good, and the same LED chip can emit higher luminance.
≪ＬＥＤ素子用高放熱基板の製造法≫
まず金属アルミニウム板（Ａ５０５２）２００×２００ｍｍ、厚み２ｍｍを用意し、これに対し、実施例８および比較例１〜４の機能膜形成用組成物を用い超音波スプレー法で、均一塗布した。超音波スプレー装置では、広角にスプレーするノズルでアルミ板をベルトコンベアーで搬送して自動的に塗布する方法を利用した。これにより大きなサイズのアルミ板であっても均一塗布が可能となった。そして、上記のように機能膜形成用組成物を塗布したアルミ板を、約１０ｐｐｍの酸素分圧に制御された窒素雰囲気中で５００℃の温度で焼成を行った。その結果、機能膜形成用組成物中のガラスが溶解し、アルミナ粉末を取り込んで焼結した。焼結した絶縁膜は厚みが約１０μｍであり、均一でボイド、クラックの無い均一な絶縁膜が得られた。このようにして作製された機能膜を形成したアルミ板の高熱伝導機能膜上に、真空スパッタ装置でチタン膜と銅膜をそれぞれ１００Åと１０００Å形成した。次いで、スパッタ装置により形成したＴｉ，Ｃｕ層を下地層として、その上に更に１００μｍの厚みになるまで電解銅めっきを行い、電極層を形成した。Ｔｉ及びＣｕの下地層の導電性を利用して電解銅めっきを効率的に実施できた。またＴｉ／Ｃｕの下地層は上部の銅めっき層の接着強度を良好に保つ働きもある。このようにして作製された電解銅めっき層をフォトリソグラフィー法でパターン形成した。すなわち、電解銅めっき層を形成した、アルミ板の両面に、感光性のドライフィルムレジストを形成し、所望の配線パターンとなるようにフォトマスクを利用してＵＶ露光した。そして、ＵＶ露光された部分以外をアルカリ現像液で処理して現像処理を行い、所定の部分のドライフィルムレジストを除去し、更に塩化第二鉄水溶液中で銅めっき層をエッチングし、さらにＴｉ層をＴｉ用エッチング液（低濃度硫酸水溶液）で除去することで配線パターン形成した。その後残ったドライフィルムレジストを水酸化ナトリウム溶液で剥離除去することで、アルミ板の高熱伝導機能膜上に銅の配線パターンが形成された。このようにして、目的とするＬＥＤ素子用高放熱基板を得た。
≪Method of manufacturing high heat dissipation substrate for LED element≫
First, a metal aluminum plate (A5052) of 200 × 200 mm and a thickness of 2 mm was prepared, and applied uniformly by the ultrasonic spray method using the functional film forming compositions of Example 8 and Comparative Examples 1 to 4. In the ultrasonic spray device, an aluminum plate is conveyed by a belt conveyor with a nozzle spraying at a wide angle and automatically applied. As a result, even a large size aluminum plate can be applied uniformly. And the aluminum plate which apply | coated the composition for functional film formation as mentioned above was baked at the temperature of 500 degreeC in the nitrogen atmosphere controlled to the oxygen partial pressure of about 10 ppm. As a result, the glass in the composition for forming a functional film was dissolved, and alumina powder was taken in and sintered. The sintered insulating film had a thickness of about 10 μm, and a uniform insulating film having no voids and cracks was obtained. On the high thermal conductive functional film of the aluminum plate on which the functional film thus produced was formed, a titanium film and a copper film were formed in a thickness of 100 mm and 1000 mm, respectively, using a vacuum sputtering apparatus. Next, using the Ti and Cu layers formed by the sputtering apparatus as an underlayer, electrolytic copper plating was further performed thereon to a thickness of 100 μm to form an electrode layer. Electrolytic copper plating could be carried out efficiently using the conductivity of the underlying layer of Ti and Cu. The Ti / Cu underlayer also has a function of maintaining the adhesive strength of the upper copper plating layer. The electrolytic copper plating layer thus produced was patterned by a photolithography method. That is, a photosensitive dry film resist was formed on both surfaces of an aluminum plate on which an electrolytic copper plating layer was formed, and UV exposure was performed using a photomask so as to obtain a desired wiring pattern. Then, a portion other than the UV-exposed portion is processed with an alkali developer to perform development, the dry film resist in a predetermined portion is removed, the copper plating layer is further etched in a ferric chloride aqueous solution, and a Ti layer is further removed. Was removed with an etching solution for Ti (low concentration sulfuric acid aqueous solution) to form a wiring pattern. Thereafter, the remaining dry film resist was peeled and removed with a sodium hydroxide solution, whereby a copper wiring pattern was formed on the high thermal conductive functional film of the aluminum plate. Thus, the target high heat dissipation board | substrate for LED elements was obtained.
≪高放熱基板を用いたＬＥＤ素子の製造法≫
上記のようにして作製された高熱放熱基板を用い、以下のようにして高輝度発光ダイオード（ＬＥＤ）を作製した。なお、高輝度ＬＥＤ（１００ｌｍ（ルーメン）／Ｗ以上）は、蛍光灯に比べ高効率ではあるが、それでもエネルギー変換効率は２５〜３０％程度であり、そのほとんどが熱として放熱される。これら高輝度ＬＥＤであれば更に発熱が大きいため効率よく放熱しないと自らの発熱で熱暴走して破壊してしまうおそれがある。そのため実装する基板には高い放熱性（熱伝導性）が必要とされる。
まず、配線パターンを形成し、ＬＥＤチップを実装する部分以外に白色のレジストを塗布した。白色レジストは、酸化チタン粉末を含む熱硬化エポキシ樹脂ペーストをスクリーン印刷することで得られた。２００℃の温度で熱処理することで硬化膜が得られ、３０μｍ程度の厚みで約９０％の反射率が得られた。白色レジストを形成していない部分の銅配線パターン上のＬＥＤチップを実装する部分を含め５μｍ厚みにＡｇめっき処理を行った。次いでＬＥＤ素子を前記基板の配線パターン上にダイボンドした。具体的には、Ａｇめっき処理した配線パターン上にＡｇ粉とエポキシ樹脂からなる導電性接着剤ペーストをディスペンサにより所望の量を滴下し、更にその上にＬＥＤチップ（チップサイズ０．６ｍｍ角）を位置合せして配置し、１０ｇ程度の荷重で押さえた。その後２００℃の温度で加熱して導電性接着剤ペーストを硬化させ、ＬＥＤチップをダイボンドした。ダイボンドされたＬＥＤチップ上の電極と、前記のＡｇめっき処理した配線パターンに、Ａｕワイヤー (径φ２５μｍ)でワイヤーボンディングした。ＬＥＤチップはＧａＮ系の青色ＬＥＤであり、白色ＬＥＤ素子とするため黄色の蛍光体で覆うものであった。具体的には黄色の蛍光体粉末と液状シリコーン樹脂をペースト状に加工し、所望の印刷形状にくり抜いたメタルマスクを用いて、蛍光体ペースとをスキージ印刷することでメタルマスクの開口部に充填し、メタルマスクを除去することで、ＬＥＤチップを覆い、加熱処理（２００℃３０分）で硬化させて得られた。このようにして得られたＬＥＤチップを搭載したアルミ放熱基板を透明なシリコーン樹脂で更に封止して、ＬＥＤ素子を得た。
≪Method of manufacturing LED element using high heat dissipation board≫
A high-intensity light-emitting diode (LED) was produced as follows using the high heat dissipation substrate produced as described above. High-brightness LEDs (100 lm (lumens) / W or more) are more efficient than fluorescent lamps, but still have an energy conversion efficiency of about 25 to 30%, and most of them are dissipated as heat. These high is Re emesis destroy and thermal runaway in their heating Otherwise efficiently radiated for luminance further large heat generation if an LED. Therefore, high heat dissipation (thermal conductivity) is required for the substrate to be mounted.
First, a wiring pattern was formed, and a white resist was applied to a portion other than the portion where the LED chip was mounted. The white resist was obtained by screen printing a thermosetting epoxy resin paste containing titanium oxide powder. A cured film was obtained by heat treatment at a temperature of 200 ° C., and a reflectance of about 90% was obtained with a thickness of about 30 μm. Ag plating treatment was performed to a thickness of 5 μm including a portion where the LED chip on the portion of the copper wiring pattern where the white resist was not formed was mounted. Subsequently, the LED element was die-bonded on the wiring pattern of the substrate. Specifically, a desired amount of a conductive adhesive paste made of Ag powder and epoxy resin is dropped on a Ag-plated wiring pattern by a dispenser, and an LED chip (chip size 0.6 mm square) is further formed thereon. They were aligned and pressed with a load of about 10 g. Thereafter, the conductive adhesive paste was cured by heating at a temperature of 200 ° C., and the LED chip was die-bonded. Wire bonding was performed on the electrode on the die-bonded LED chip and the wiring pattern subjected to the Ag plating treatment with an Au wire (diameter: 25 μm). The LED chip is a GaN-based blue LED and is covered with a yellow phosphor in order to obtain a white LED element. Specifically, the yellow phosphor powder and liquid silicone resin are processed into a paste, and the metal mask opening is filled by squeegee printing the phosphor pace using a metal mask hollowed out to the desired print shape. Then, by removing the metal mask, the LED chip was covered and cured by heat treatment (200 ° C. for 30 minutes). The aluminum heat dissipation substrate on which the LED chip thus obtained was mounted was further sealed with a transparent silicone resin to obtain an LED element.
〔誘電体素子〕
また、下記の製造法に従い製造された誘電体素子において、その機能膜の形成材料に、実施例９の機能膜形成用組成物をスプレー塗布して用いたところ、比較例１〜４の機能膜形成用組成物をスプレー塗布して用いた場合に比べ、緻密で塗布時のダレが少なく均一な誘電体膜が金属基材に形成され、極めて高い絶縁性能と誘電性能が得られた。また得られた誘電体膜を用いることで、簡易にコンデンサを内蔵したプリント基板が得られるといった結果が得られた。
なお、実施例９の機能膜形成用組成物を用いて作製された誘電体素子の評価のため、蒸着法でアルミ電極を誘電体上に形成し、銅箔とアルミ電極間の誘電特性を評価した。その結果、周波数１０ＫＨｚ〜１ＭＨｚの範囲で比誘電率が約２０００、誘電損失（Ｔａｎδ）が０．０１％と極めて良好な誘電特性が得られた。
また、実施例の誘電体素子を用いて、下記の製造法に従い作製されたコンデンサ内蔵プリント基板は、簡易な方法で、電源回路や高周波回路に影響を与える電源ノイズ（リップル）や、高周波ノイズを除去するため、信号回路と電源回路において有用である。
[Dielectric element]
In addition, in the dielectric element manufactured according to the following manufacturing method, when the functional film forming composition of Example 9 was spray applied to the functional film forming material, the functional film of Comparative Examples 1 to 4 was used. Compared to the case where the forming composition is applied by spray coating, a uniform dielectric film with a dense and less sagging at the time of coating was formed on the metal substrate, and extremely high insulation performance and dielectric performance were obtained. In addition, by using the obtained dielectric film, it was possible to obtain a printed board with a built-in capacitor easily.
In addition, in order to evaluate the dielectric element produced using the composition for forming a functional film of Example 9, an aluminum electrode was formed on the dielectric by a vapor deposition method, and the dielectric characteristics between the copper foil and the aluminum electrode were evaluated. did. As a result, in the frequency range of 10 KHz to 1 MHz, a very good dielectric characteristic was obtained with a relative dielectric constant of about 2000 and a dielectric loss (Tanδ) of 0.01%.
In addition, the printed circuit board with built-in capacitor using the dielectric element of the example according to the following manufacturing method can reduce power supply noise (ripple) and high frequency noise that affect the power supply circuit and high frequency circuit by a simple method. This is useful in signal circuits and power supply circuits.
≪誘電体素子の製造法≫
まず、両面を粗化した銅箔（プリント基板用電解銅箔：古川電工社製 ＤＴ−ＧＬＤ−ＭＰ−３５μｍ厚み、３５０×３５０ｍｍサイズ）を準備し、実施例９および比較例１〜４の機能膜形成用組成物を用い超音波スプレー法で、銅箔の表面に均一塗布した。超音波スプレー装置では、広角にスプレーするノズルで、銅箔をベルトコンベアーで搬送して自動的に塗布する方法を適用した。実施例９および比較例１〜４の機能膜形成用組成物を塗布、乾燥した銅箔を、約１０ｐｐｍの酸素分圧に制御された窒素雰囲気中で９００℃の温度で焼成を行った。その結果、組成物中に含まれる少量のガラスが溶解し、チタン酸バリウム粉末を取り込んで焼結した。焼結した絶縁膜は厚みが約１０μｍであり、均一でボイド、クラックの無い均一な絶縁膜が得られた。このようにして、目的とする、プリント基板にコンデンサを内蔵するための誘電体素子を得た。
≪Dielectric element manufacturing method≫
First, copper foil with roughened both sides (electrolytic copper foil for printed circuit board: DT-GLD-MP-35 μm thickness, 350 × 350 mm size manufactured by Furukawa Electric Co., Ltd.) was prepared, and the functions of Example 9 and Comparative Examples 1 to 4 were prepared. The film-forming composition was uniformly applied to the surface of the copper foil by ultrasonic spraying. In the ultrasonic spray device, a method of applying a copper foil by a belt conveyor and applying it automatically with a nozzle spraying at a wide angle was applied. The copper foil dried by applying the functional film-forming composition of Example 9 and Comparative Examples 1 to 4 was fired at a temperature of 900 ° C. in a nitrogen atmosphere controlled to an oxygen partial pressure of about 10 ppm. As a result, a small amount of glass contained in the composition was dissolved, and barium titanate powder was taken in and sintered. The sintered insulating film had a thickness of about 10 μm, and a uniform insulating film having no voids and cracks was obtained. In this manner, a target dielectric element for incorporating a capacitor in a printed circuit board was obtained.
≪誘電体素子を用いたコンデンサ内蔵プリント基板の製造法≫
エポキシ樹脂とガラス織布からなるプリント基板用プリプレグ（パナソニック製、プリプレグ：Ｒ１４１０Ｗ ＦＲ−５基材、３００×３００ｍｍ、０．１ｍｍ厚み）を用い、以下のように、コンデンサ内蔵プリント基板を製造した。まず、片面を粗化した銅箔（古河電工社製、ＧＴＳ−ＭＰ−１８μｍ厚み、３２５×３２５ｍｍサイズ）を配置し、粗化面上に上記プリプレグを重ね、更に前記の誘電体を形成した誘電体素子を、誘電体素子の銅箔側がプリプレグ側となるように位置合せして重ね、加熱加圧して積層した。積層の条件は、加熱プレスにて５０Ｋｇ／ｃｍ2の荷重で、２００℃の温度で、真空中に２時間保持することで、目的とするコンデンサ内蔵プリント基板を得た。
≪Manufacturing method of printed circuit board with built-in capacitor using dielectric element≫
A printed circuit board with a built-in capacitor was manufactured as follows using a prepreg for a printed circuit board made of an epoxy resin and a glass woven fabric (manufactured by Panasonic, prepreg: R1410W FR-5 base material, 300 × 300 mm, 0.1 mm thickness). First, a copper foil having a roughened one side (Furukawa Electric Co., Ltd., GTS-MP-18 μm thickness, 325 × 325 mm size) is placed, the prepreg is stacked on the roughened surface, and the dielectric is formed. The body elements were aligned and overlapped so that the copper foil side of the dielectric element was the prepreg side, and heated and pressed to laminate. The lamination conditions were as follows: a target printed circuit board with a built-in capacitor was obtained by holding in a vacuum at a temperature of 200 ° C. under a load of 50 kg / cm 2 with a heating press for 2 hours.
〔太陽電池〕
また、下記の製造法に従い製造された太陽電池において、その半導体膜の形成材料に、実施例９の機能膜形成用組成物をスプレー塗布して用いたところ、使用するケイ素材料が少なく薄いこと、あるいは低コストな基板を電極に使用できることで、低コストな太陽電池が得られるといった結果が得られた。
また、銅箔上に形成するので裏面電極にそのまま利用できるため、低コストで低抵抗な電極となり、このことでも発電効率が良く、低コストな太陽電池が得られるという格別の効果がみられた。
[Solar cell]
Moreover, in the solar cell manufactured according to the following manufacturing method, when the composition for forming a functional film of Example 9 was spray applied to the semiconductor film forming material, the silicon material used was thin and thin, Alternatively, a low-cost solar cell can be obtained by using a low-cost substrate for the electrode.
In addition, since it is formed on the copper foil, it can be used as it is for the back electrode, resulting in a low-cost and low-resistance electrode. This also has a remarkable effect that the power generation efficiency is good and a low-cost solar cell can be obtained. .
≪太陽電池の製造法≫
まず、太陽電池用の裏面電極としてコストの安いアルミ箔もしくは銅箔を利用し、その表面に実施例９の機能膜形成組成物をスプレー塗布し、熱処理によって簡易に堆積、焼結させることで薄いケイ素機能層を得た。具体的に述べると、使用したケイ素粉末は、平均粒径０．２μｍのケイ素微粉末を用いた実施例９よりなる機能膜形成用組成物を用い超音波スプレー法で、銅箔（三井金属鉱業社製、両面光沢箔 ＤＦＦ−１５μｍ厚み、１５０×１５０ｍｍサイズ）の表面に均一塗布した。次いで塗布した機能膜形成用組成物を乾燥処理（１５０℃×３０分）したところ、機能膜形成用組成物中のケイ素粉末とセルロース繊維により固化し、銅箔をある程度曲げても銅箔上から脱落することは無かった。乾燥膜の厚みは約４５μｍであり、銅箔片面全体に均一に塗布されていることが確認できた。次に機能膜形成用組成物を塗布した銅箔を雰囲気コントロール可能な電気炉で焼成した。条件は、窒素雰囲気に水素ガスを２００ｐｐｍ流入させ、更に水温を３０℃に保つ容器をバブリングすることで窒素雰囲気中に水蒸気を加えることで、酸素分圧を制御しながら、９００℃の温度で３時間保持して銅箔上のケイ素粉末を焼結させた。焼成後の膜厚は３５μｍであった。次いで、太陽電池としての機能を発揮させるため、Ｐ型層とＮ型層を熱処理と不純物ドーピングにより行った。本実施例ではまずケイ素焼結膜を水素希釈したＳｉ2Ｈ6を原料とし、Ｐ型ドーピングガスとしてはＢ2Ｈ6を用いた雰囲気に制御して行った。また、Ｎ型ケイ素層の形成は、前記Ｐ型ケイ素層を形成した後に、ＰＯＣｌ3をドーピングガスとした熱拡散法で形成した。このようにして多結晶質シリコーン太陽電池用の多結晶質ケイ素焼結膜が銅箔上に形成された。なお、本実施例では、９００℃で雰囲気焼成を実施したが、焼結性が不充分な場合は更にレーザーを照射することでケイ素焼結体の一部を再結晶化させることも有効であることが確認された。
このようにして作製された多結晶ケイ素焼結膜の表面に、反射防止膜、表面電極を形成し、目的とする太陽電池を得た。
≪Solar cell manufacturing method≫
First, a low-cost aluminum foil or copper foil is used as a back electrode for a solar cell, and the functional film-forming composition of Example 9 is spray-applied on the surface thereof. A silicon functional layer was obtained. More specifically, the silicon powder used was a copper foil (Mitsui Metals Mining) by using an ultrasonic spray method using a functional film-forming composition comprising Example 9 using silicon fine powder having an average particle size of 0.2 μm. Co., Ltd., double-sided glossy foil DFF-15 μm thickness, 150 × 150 mm size). Next, when the applied functional film forming composition was dried (150 ° C. × 30 minutes), it was solidified by the silicon powder and cellulose fibers in the functional film forming composition, and even if the copper foil was bent to some extent, There was no dropout. The thickness of the dry film was about 45 μm, and it was confirmed that it was uniformly applied to the entire surface of the copper foil. Next, the copper foil coated with the functional film forming composition was fired in an electric furnace capable of controlling the atmosphere. The conditions are as follows: 200 ppm of hydrogen gas was introduced into the nitrogen atmosphere, and water vapor was added to the nitrogen atmosphere by bubbling a vessel that kept the water temperature at 30 ° C., and the oxygen partial pressure was controlled, and a temperature of 900 ° C. The silicon powder on the copper foil was sintered by holding for a time. The film thickness after firing was 35 μm. Subsequently, in order to exhibit the function as a solar cell, the P-type layer and the N-type layer were subjected to heat treatment and impurity doping. In this example, first, Si 2 H 6 diluted with hydrogen was used as a raw material for the silicon sintered film, and the atmosphere was controlled using B 2 H 6 as the P-type doping gas. The N-type silicon layer was formed by a thermal diffusion method using POCl 3 as a doping gas after forming the P-type silicon layer. In this way, a polycrystalline silicon sintered film for a polycrystalline silicone solar cell was formed on the copper foil. In this example, atmosphere firing was performed at 900 ° C. However, if the sinterability is insufficient, it is also effective to recrystallize a part of the silicon sintered body by further irradiating a laser. It was confirmed.
An antireflection film and a surface electrode were formed on the surface of the polycrystalline silicon sintered film thus produced, and the intended solar cell was obtained.
本発明の電子デバイスの製法に用いられる機能膜形成用組成物は、ＬＥＤ素子、パワー用電源デバイス、太陽電池等の、各種電子デバイスにおける機能膜（電気絶縁膜、半導体膜、誘電体膜）の形成材料として使用することができ、特にスプレー法によって塗膜形成する際に有利な効果が得られることから、そのような産業分野への利用において有用である。 The functional film-forming composition used in the method for producing an electronic device of the present invention is a functional film (electrical insulating film, semiconductor film, dielectric film) in various electronic devices such as LED elements, power supply devices for power, solar cells, etc. Since it can be used as a forming material, and an advantageous effect can be obtained particularly when a coating film is formed by a spray method, it is useful in such industrial fields.
Claims (9)
（α）下記の（Ａ）〜（Ｃ）成分を含有する無機粒子含有機能膜形成用組成物。
（Ａ）ホウ素、リチウム、ナトリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、ジルコニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、鉄、コバルト、ニッケル、テルル、銅、亜鉛、アルミニウム、ケイ素、リン、ガリウム、インジウム、スズ、鉛およびビスマスからなる群から選ばれた少なくとも一つの元素を含む無機粒子であって、その平均粒径が１００ｎｍ〜３０μｍである無機粒子。
（Ｂ）数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的にカルボキシル基、アルデヒド基，およびケトン基のいずれかに酸化変性されており、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇ、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であるとともに、そのセルロースの非晶領域量が１０〜２５％である、セルロース繊維。
（Ｃ）極性溶媒。 A method for producing an electronic device comprising an inorganic base material , an inorganic particle-containing functional film that is an electrical insulating film, a semiconductor film, or a dielectric film, and an electrode layer, wherein a part of the inorganic base material or on the entire surface, a step of applying the inorganic particles-containing functional film forming composition shown in the following (alpha), is sintered by heating the coated film, a step of forming the inorganic particles-containing functional film, the functional film preparation of an electronic device characterized by comprising a step of forming the electrode layer above and / or on the inorganic substrate.
(Α) A composition for forming an inorganic particle-containing functional film containing the following components (A) to (C).
(A) Boron, lithium, sodium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, tellurium, copper, zinc, aluminum, silicon Inorganic particles containing at least one element selected from the group consisting of phosphorous, gallium, indium, tin, lead and bismuth, and having an average particle size of 100 nm to 30 μm.
(B) Cellulose fibers having a number average fiber diameter of 2 to 150 nm, wherein the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively oxidized and modified to any of a carboxyl group, an aldehyde group, and a ketone group. The content of carboxyl groups is 1.2 to 2.5 mmol / g, the total content of aldehyde groups and ketone groups as measured by the semicarbazide method is less than 0.3 mmol / g, and the amorphous region of the cellulose Cellulose fiber, the amount of which is 10-25%.
(C) Polar solvent.
（α）下記の（Ａ）〜（Ｃ）成分を含有する無機粒子含有機能膜形成用組成物。
（Ａ）ホウ素、リチウム、ナトリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、ジルコニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、鉄、コバルト、ニッケル、テルル、銅、亜鉛、アルミニウム、ケイ素、リン、ガリウム、インジウム、スズ、鉛およびビスマスからなる群から選ばれた少なくとも一つの元素を含む無機粒子であって、その平均粒径が１００ｎｍ〜３０μｍである無機粒子。
（Ｂ）数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロース分子中の各グルコースユニットのＣ６位の水酸基が選択的にカルボキシル基、アルデヒド基，およびケトン基のいずれかに酸化変性されており、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇ、セミカルバジド法による測定でのアルデヒド基とケトン基の合計含量が０．３ｍｍｏｌ／ｇ未満であるとともに、そのセルロースの非晶領域量が１０〜２５％である、セルロース繊維。
（Ｃ）極性溶媒。 A method for producing an electronic device having a photovoltaic power generation function, in which a semiconductor film and an electrode layer are formed on a base material made of aluminum foil, wherein at least one surface of the base material has the following (α) A composition for forming an inorganic particle-containing functional film, the step of applying a silicon-based component of the inorganic particles, the step of sintering the coating film by heating, and forming a semiconductor film, comprising a step of forming a semiconductor portion of the P-type and N-type impurity is doped in the semiconductor film, a step of forming the electrode layer on the P-type and N-type semiconductor film semiconductor portion is formed of a The manufacturing method of the electronic device characterized by the above-mentioned.
(Α) A composition for forming an inorganic particle-containing functional film containing the following components (A) to (C).
(A) Boron, lithium, sodium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, tellurium, copper, zinc, aluminum, silicon Inorganic particles containing at least one element selected from the group consisting of phosphorous, gallium, indium, tin, lead and bismuth, and having an average particle size of 100 nm to 30 μm.
(B) Cellulose fibers having a number average fiber diameter of 2 to 150 nm, wherein the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively oxidized and modified to any of a carboxyl group, an aldehyde group, and a ketone group. The content of carboxyl groups is 1.2 to 2.5 mmol / g, the total content of aldehyde groups and ketone groups as measured by the semicarbazide method is less than 0.3 mmol / g, and the amorphous region of the cellulose Cellulose fiber, the amount of which is 10-25%.
(C) Polar solvent.
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