JP5921960B2 - Composition containing inorganic fine particles and film using the same - Google Patents
Composition containing inorganic fine particles and film using the same Download PDFInfo
- Publication number
- JP5921960B2 JP5921960B2 JP2012127293A JP2012127293A JP5921960B2 JP 5921960 B2 JP5921960 B2 JP 5921960B2 JP 2012127293 A JP2012127293 A JP 2012127293A JP 2012127293 A JP2012127293 A JP 2012127293A JP 5921960 B2 JP5921960 B2 JP 5921960B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- inorganic fine
- cellulose fiber
- fine particles
- film
- 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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- 239000010419 fine particle Substances 0.000 title claims description 94
- 239000000203 mixture Substances 0.000 title claims description 46
- 229920003043 Cellulose fiber Polymers 0.000 claims description 114
- 229920002678 cellulose Polymers 0.000 claims description 45
- 239000001913 cellulose Substances 0.000 claims description 45
- 239000000835 fiber Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 44
- 125000003172 aldehyde group Chemical group 0.000 claims description 36
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 33
- 125000000468 ketone group Chemical group 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 15
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 150000001299 aldehydes Chemical group 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000010408 film Substances 0.000 description 43
- 239000006185 dispersion Substances 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000004220 aggregation Methods 0.000 description 10
- 239000005708 Sodium hypochlorite Substances 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000011122 softwood Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- -1 ThO 2 Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 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
- 239000011701 zinc Substances 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920002201 Oxidized cellulose Polymers 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229940107304 oxidized cellulose Drugs 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011787 zinc oxide Substances 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
- 241000609240 Ambelania acida Species 0.000 description 2
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000005016 bacterial cellulose Substances 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000004020 conductor Substances 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
- 230000006866 deterioration Effects 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 210000001724 microfibril Anatomy 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 2
- 239000001230 potassium iodate Substances 0.000 description 2
- 235000006666 potassium iodate Nutrition 0.000 description 2
- 229940093930 potassium iodate Drugs 0.000 description 2
- 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
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000001476 sodium potassium tartrate Substances 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910017563 LaCrO Inorganic materials 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241001311547 Patina Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical compound CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- COQLPRJCUIATTQ-UHFFFAOYSA-N Uranyl acetate Chemical compound O.O.O=[U]=O.CC(O)=O.CC(O)=O COQLPRJCUIATTQ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- 238000010907 mechanical stirring Methods 0.000 description 1
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- 238000005121 nitriding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 229910052600 sulfate mineral Inorganic materials 0.000 description 1
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- 239000010455 vermiculite Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
本発明は、無機微粒子含有組成物およびそれを用いた被膜に関するものであり、詳しくは、高屈折率材料、高硬度材料、透明導電性材料等に使用される無機微粒子含有組成物およびそれを用いた被膜に関するものである。 The present invention, inorganic fine particle-containing composition and relates the film using the same, particularly, a high refractive index material, high hardness materials, inorganic fine particle-containing composition used in the transparent conductive material, and the like, and it it relates the membrane used.
無機微粒子はこれを含有する被膜（無機微粒子含有被膜）として、高屈折率材料、高硬度材料、透明導電性材料、高熱伝導性材料、絶縁材料、耐蝕材料、半導体材料、磁性材料、誘電材料、生体適合材料等に使われている。従来、このような無機微粒子含有被膜を形成する方法としては、蒸着やスパッタリングによるドライコーティング法（特許文献１参照）や、金属アルコキシドの加水分解物、部分縮合物を含む組成物を塗布、乾燥するウェットコーティング法（特許文献２参照）が行われている。上記スパッタリング法は、緻密で均質な金属化合物薄膜を形成することが可能であるが、基板表面が入り組んだ形状を有する場合、影となっている部分に金属化合物薄膜を形成させることは不可能である。また、上記ドライコーティング法では、高真空の大型設備が必要で、生産性も低いという問題がある。一方、上記ウェットコーティング法は、設備が簡便で、大面積化も容易であり、生産性にも優れているが、塗布液の安定性、塗布環境の制御等の工業的課題が多い。 As the film inorganic fine particles containing the same (inorganic fine particles containing the film), a high refractive index material, high hardness material, a transparent conductive material, high thermal conductivity materials, insulating materials, corrosion-resistant material, a semiconductor material, a dielectric Used in materials and biocompatible materials. As a method of forming such an inorganic fine particle containing the film coating dry coating method by vapor deposition or sputtering or (see Patent Document 1), a metal alkoxide hydrolyzate, a composition comprising a partial condensate, dried A wet coating method (see Patent Document 2) is performed. The above sputtering method can form a dense and homogeneous metal compound thin film, but when the substrate surface has an intricate shape, it is impossible to form the metal compound thin film in the shaded part. is there. Further, the dry coating method requires a large facility with high vacuum and has a problem of low productivity. On the other hand, the wet coating method is simple in equipment, easy to increase in area, and excellent in productivity, but has many industrial problems such as stability of coating solution and control of coating environment.
そこで、無機微粒子とバインダーとを複合化した塗布液を用いる技術が提案されている。しかしながら、無機微粒子をバインダーに添加すると、無機微粒子が凝集しやすくなる。特に高機能化を達成する目的で粒子径１μｍ以下の無機微粒子を添加した場合は、その比表面積が大きいため非常に凝集しやすい。このような無機微粒子の凝集は、透明性の低下や、膜の均一性の悪化に起因する強度、抵抗の低下等、被膜性能劣化の原因となる。したがって、上記塗布液には、無機微粒子が充分な分散性（均一分散性）を有する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が求められている。 Therefore, a technique using a coating solution in which inorganic fine particles and a binder are combined has been proposed. However, when inorganic fine particles are added to the binder, the inorganic fine particles easily aggregate. In particular, when inorganic fine particles having a particle diameter of 1 μm or less are added for the purpose of achieving high functionality, they are very likely to aggregate because of their large specific surface area. Aggregation of such inorganic fine particles, or reduction in transparency, strength due to deterioration of the uniformity of the film, lowering of resistance, etc., causing the membrane performance degradation. Accordingly, the coating liquid is required to have sufficient dispersibility (uniform dispersibility) of the inorganic fine particles. In addition, it is 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、無機微粒子に表面処理を施す方法（特許文献３参照）や、分散剤を添加する方法（特許文献４，５参照）等が提案されている。 As means for solving these problems, a method of performing surface treatment on inorganic fine particles (see Patent Document 3), a method of adding a dispersant (see Patent Documents 4 and 5), and the like have been proposed.
しかしながら、上記無機微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、無機微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、無機微粒子が小さいほどその表面積が増大するため、無機微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、形成した被膜にも分散剤が残存するため、屈折率、硬度、導電性、熱伝導性等の被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 fine particles, it is very difficult to perform the surface treatment to a level at which aggregation of the inorganic fine particles is completely suppressed while maintaining the required performance. In addition, in the method of adding the dispersant, the surface area increases as the inorganic fine particles are small, so that a large amount of dispersant is required to sufficiently stabilize the inorganic fine particles. However, when blending a large amount of dispersing agent to the coating liquid, since the dispersing agent in the film formed remains, refractive index, hardness, conductivity, there is a problem deterioration of the membrane performance of the thermal conductivity and the like occur .
本発明は、このような事情に鑑みなされたもので、無機微粒子の均一分散性に優れた無機微粒子含有組成物およびそれを用いた被膜の提供をその目的とする。 The present invention has been made in view of such circumstances, the provision of the film and an object using an inorganic fine particle-containing composition excellent in uniform dispersibility of inorganic fine particles and it.
本発明者らは、無機微粒子の凝集を抑制して、均一分散性に優れた無機微粒子含有組成物を得るため、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、そのセルロースが、セルロースＩ型結晶構造を有すると共に、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の範囲である、微細なセルロース繊維に着目した。そして、このセルロース繊維を更に還元させて、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以下であり、フェーリング試薬によるアルデヒド基の検出が認められない、特殊なセルロース繊維とし、それをバインダーとして、無機微粒子と組み合わせてなる無機微粒子含有組成物を使用すると、無機微粒子の凝集が抑制されて、均一に分散するとともに、透明性、屈折率、導電性、硬度等に優れた被膜が得られることを見いだし、本発明に到達した。 The inventors of the present invention have made extensive studies in order to obtain an inorganic fine particle-containing composition excellent in uniform dispersibility by suppressing aggregation of inorganic fine particles. In the course of the research, the cellulose fiber has a number average fiber diameter of 2 to 150 nm, and the cellulose has a cellulose I-type crystal structure, and the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively used. Attention was focused on fine cellulose fibers that were oxidized and modified to become aldehyde groups, ketone groups, or carboxyl groups, and the carboxyl group content was in the range of 1.2 to 2.5 mmol / g. The cellulose fiber is further reduced to a special cellulose having a total content of aldehyde groups and ketone groups of 0.3 mmol / g or less as measured by the semicarbazide method, and no detection of aldehyde groups by a failing reagent is observed. When using an inorganic fine particle-containing composition that is made into a fiber and used as a binder in combination with inorganic fine particles, the aggregation of inorganic fine particles is suppressed and uniformly dispersed, and the transparency, refractive index, conductivity, hardness, etc. found that excellent target film is obtained, we have reached the present invention.
すなわち、本発明は、下記の（Ａ）および（Ｂ）を含有する無機微粒子含有組成物を第１の要旨とする。
（Ａ）平均粒径が１μｍ以下の無機微粒子。
（Ｂ）数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロースが、セルロースＩ型結晶構造を有すると共に、セルロース分子中の各グルコースユニットのＣ６位が選択的にアルデヒド基，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、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以下であり、フェーリング試薬によるアルデヒド基の検出が認められない、セルロース繊維。
That is, this invention makes the 1st summary the composition containing inorganic fine particles containing the following (A) and (B).
(A) Inorganic fine particles having an average particle size of 1 μm or less.
(B) a number average fiber diameter of 2~150nm cellulose fibers, the cellulose, which has a cellulose I type crystal structure, C6-position selectively aldehydes groups of each glucose unit in a molecule of the cellulose, ketone A carboxyl group content of 1.2 to 2.5 mmol / g, and a total content of aldehyde groups and ketone groups as measured by the semicarbazide method of 0.3 mmol / g or less. Cellulose fiber , which does not have aldehyde group detection by a Fehring reagent .
また、本発明は、上記無機微粒子含有組成物からなる被膜を第２の要旨とする。 The present invention is directed to a target film made of the inorganic fine particle-containing composition and the second aspect.
このように、本発明の無機微粒子含有組成物は、数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロースが、セルロースＩ型結晶構造を有すると共に、セルロース分子中の各グルコースユニットのＣ６位が選択的にアルデヒド基，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、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以下であり、フェーリング試薬によるアルデヒド基の検出が認められない、特殊なセルロース繊維（Ｂ）を、無機微粒子（Ａ）とともに含有している。本発明の無機微粒子含有組成物においては、上記セルロース繊維（Ｂ）が無機微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、上記無機微粒子（Ａ）の凝集を抑制することができ、上記無機微粒子（Ａ）が均一に分散する。また、本発明の無機微粒子含有組成物は、上記無機微粒子（Ａ）の均一分散状態を長期間保持することができるため、長期の保存性にも優れている。このような本発明の無機微粒子含有組成物を用いてなる被膜（無機微粒子含有被膜）は、透明性に優れ、膜厚が均一であるとともに、被膜中に界面活性剤等の分散剤が残存しないため、屈折率、硬度、導電性、熱伝導性等の被膜性能にも優れている。 As described above, the inorganic fine particle-containing composition of the present invention is a cellulose fiber having a number average fiber diameter of 2 to 150 nm, and the cellulose has a cellulose I-type crystal structure and each glucose unit in the cellulose molecule. C6-position selectively aldehydes groups, which has become one of the ketone group and a carboxyl group, an aldehyde group and ketone group at the measurement content of carboxyl group 1.2~2.5mmol / g, by semicarbazide method The total content of is 0.3 mmol / g or less, and the special cellulose fiber (B) in which the detection of the aldehyde group by the Fehring reagent is not observed is contained together with the inorganic fine particles (A). In the inorganic fine particle-containing composition of the present invention, since the cellulose fiber (B) stably supports the inorganic fine particles, the aggregation of the inorganic fine particles (A) is suppressed without using a dispersant such as a surfactant. And the inorganic fine particles (A) are uniformly dispersed. Moreover, since the inorganic fine particle containing composition of this invention can hold | maintain the uniform dispersion state of the said inorganic fine particle (A) for a long period of time, it is excellent also in long-term preservability. Such target film formed by using the inorganic fine particle-containing composition of the present invention (inorganic fine particles containing the film) has excellent transparency, with the film thickness is uniform, dispersing agent such as a surfactant in the film because but do not remain, the refractive index, hardness, conductivity, and excellent in the film properties of thermal conductivity and the like.
また、上記無機微粒子（Ａ）が、Ｂ、Ｃ、Ｎ、Ｃｅ、Ｃｏ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｃｒ、Ｗ、Ｆｅ、Ｎｉ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、ＳｎおよびＳｂからなる群から選ばれた少なくとも一つの元素、またはその化合物からなる無機物であると、均一分散性が向上するとともに、化合物の種類に応じた屈折率、硬度、導電性、熱伝導性等の被膜性能も向上する。 The inorganic fine particles (A) are B, C, N, Ce, Co, Mg, Ca, Sr, Ba, Y, Ti, Zr, Hf, Nb, Ta, Cr, W, Fe, Ni, Pt, Uniform dispersibility is improved and the compound is an inorganic substance comprising at least one element selected from the group consisting of Cu, Ag, Au, Zn, Al, Ga, In, Si, Sn and Sb, or a compound thereof, and a compound refractive index corresponding to the type, hardness, conductivity, also the membrane performance of the thermal conductivity and the like is improved.
そして、上記（Ａ）と（Ｂ）の固形分の比が、（Ａ）／（Ｂ）＝１／９９〜８５／１５の範囲であると、均一分散性と被膜性能のバランスが良好となる。 Then, the ratio of the solid content of the (A) and (B), (A) / (B) = 1 / 99~85 / 15 When in the range of balance of uniform dispersibility and the film performance and good Become.
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.
本発明の無機微粒子含有組成物は、下記の（Ａ）および（Ｂ）を用いて得ることができる。
（Ａ）平均粒径が１μｍ以下の無機微粒子。
（Ｂ）数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロースが、セルロースＩ型結晶構造を有すると共に、セルロース分子中の各グルコースユニットのＣ６位が選択的にアルデヒド基，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、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以下であり、フェーリング試薬によるアルデヒド基の検出が認められない、セルロース繊維。
The inorganic fine particle-containing composition of the present invention can be obtained using the following (A) and (B).
(A) Inorganic fine particles having an average particle size of 1 μm or less.
(B) a number average fiber diameter of 2~150nm cellulose fibers, the cellulose, which has a cellulose I type crystal structure, C6-position selectively aldehydes groups of each glucose unit in a molecule of the cellulose, ketone A carboxyl group content of 1.2 to 2.5 mmol / g, and a total content of aldehyde groups and ketone groups as measured by the semicarbazide method of 0.3 mmol / g or less. Cellulose fiber , which does not have aldehyde group detection by a Fehring reagent .
《無機微粒子（Ａ）》
上記無機微粒子（Ａ）は、平均粒径が１μｍ以下であることが必要であり、好ましくは０．００１〜１μｍ、特に好ましくは０．００２〜０．５μｍである。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。
<< Inorganic fine particles (A) >>
The inorganic fine particles (A) must have an average particle size of 1 μm or less, preferably 0.001 to 1 μm, and particularly preferably 0.002 to 0.5 μm. When the average particle size is too large, the function expression depending on the type of inorganic particles is deteriorated.
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.
上記平均粒径が１μｍ以下の無機微粒子（Ａ）の具体例としては、例えば金属微粒子、金属酸化物微粒子、セラミックス微粒子、天然の粘土鉱物、その他の無機化合物等があげられる。これらは単独でもしくは２種以上併せて用いられる。 Specific examples of the inorganic fine particles (A) having an average particle size of 1 μm or less include metal fine particles, metal oxide fine particles, ceramic fine particles, natural clay minerals, and other inorganic compounds. These may be used alone or in combination of two or more.
上記金属微粒子としては、例えば、Ａｇ（銀）、Ａｕ（金）、Ｃｕ（銅）、Ａｌ（アルミニウム）、Ｔａタンタル、Ｗ（タングステン）、Ｓｉ（ケイ素）、Ｔｉ（チタン）、Ｖ（バナジウム）、Ｃｒ（クロム）、Ｍｎ（マンガン）、Ｆｅ（鉄）、Ｃｏ（コバルト）、Ｎｉ（ニッケル）、Ｚｎ（亜鉛）、Ｇａ（ガリウム）、Ｇｅ（ゲルマニウム）、Ａｓ（ヒ素）、Ｓｅ（セレン）、Ｙ（イットリウム）、Ｚｒ（ジルコニウム）、Ｎｂ（ニオブ）、Ｍｏ（モリブデン）、Ｔｃ（テクネチウム）、Ｒｕ（ルテニウム）、Ｒｈ（ロジウム）、Ｐｄ（パラジウム）、Ｃｄ（カドミウム）、Ｉｎ（インジウム）、Ｓｎ（スズ）、Ｓｂ（アンチモン）、Ｔｅ（テルル）、Ｈｆ（ハフニウム）、Ｒｅ（レニウム）、Ｏｓ（オスミウム）、Ｉｒ（イリジウム）、Ｐｔ（白金）、Ｔｌ（タリウム）、Ｐｂ（鉛）、Ｂｉ（ビスマス）、およびこれら金属を含む合金等があげられる。 Examples of the metal fine particles include Ag (silver), Au (gold), Cu (copper), Al (aluminum), Ta tantalum, W (tungsten), Si (silicon), Ti (titanium), and V (vanadium). Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Zn (zinc), Ga (gallium), Ge (germanium), As (arsenic), Se (selenium) Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Tc (technetium), Ru (ruthenium), Rh (rhodium), Pd (palladium), Cd (cadmium), In (indium) Sn (tin), Sb (antimony), Te (tellurium), Hf (hafnium), Re (rhenium), Os (osmium), Ir (iridium), t (platinum), Tl (thallium), Pb (lead), Bi (bismuth), and alloys containing these metals and the like.
上記金属酸化物微粒子、セラミックス微粒子としては、例えば、ＢｅＯ、ＭｇＯ、Ａｌ2Ｏ3、ＳｉＯ2、ＺｎＯ、ＺｒＯ2、ＳｎＯ2、ＴｈＯ2、ＬｉＮｂＯ3、ＳｒＯ・Ｆｅ2Ｏ3、Ｙ3Ａｌ5Ｏ12、Ｙ3Ｆｅ5Ｏ12、Ｇｄ3Ｇａ5Ｏ12、ＬａＣｒＯ3、ＺｎＯ−Ｂｉ2Ｏ3、ＢａＴｉＯ3、ＰｂＴｉＯ3、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3、ＴｉＯ2、Ｆｅ2Ｏ2、Ｆｅ3Ｏ4、Ｂ4Ｃ、ＳｉＣ、ＴｉＣ、ＺｒＣ、ＨｆＣ、ＴａＣ、ＷＣ、ＴｈＣ、３ＺｒＣ・ＷＣ、４ＴａＣ・ＺｒＣ、ボラゾン、ＴｉＢ4、ＺｒＢ4、ＬａＢ6、六方晶窒化ホウ素、立方晶窒化ホウ素、熱分解窒化ホウ素、ＡｌＮ、Ｓｉ3Ｎ4、ＴｉＮ、サイアロン等があげられる。 Examples of the metal oxide fine particles and ceramic fine particles include BeO, MgO, Al 2 O 3 , SiO 2 , ZnO, ZrO 2 , SnO 2 , ThO 2 , LiNbO 3 , SrO · Fe 2 O 3 , Y 3 Al 5. O 12, Y 3 Fe 5 O 12, Gd 3 Ga 5 O 12, LaCrO 3, ZnO-Bi 2 O 3, BaTiO 3, PbTiO 3, Pb (Zr, Ti) O 3, TiO 2, Fe 2 O 2, Fe 3 O 4 , B 4 C, SiC, TiC, ZrC, HfC, TaC, WC, ThC, 3ZrC · WC, 4TaC · ZrC, borazon, TiB 4 , ZrB 4 , LaB 6 , hexagonal boron nitride, cubic nitriding Examples thereof include boron, pyrolytic boron nitride, AlN, Si 3 N 4 , TiN, and sialon.
上記天然の粘土鉱物としては、例えば、カオリン鉱物、蛇紋石、パイロフェライト、タルク、雲母粘土鉱物、緑泥石、バーミキュライト、スメクタイト、セピオライト、パリゴルスカイト、アロフェン、イモゴライト、シリカ鉱物、長石、沸石、チタンの酸化鉱物、鉄およびアルミニウムの酸化鉱物と含水酸化鉱物、硫化鉱物、炭酸塩鉱物、硫酸塩鉱物等があげられる。 Examples of the natural clay mineral include, for example, kaolin mineral, serpentine, pyroferrite, talc, mica clay mineral, chlorite, vermiculite, smectite, sepiolite, palygorskite, allophane, imogolite, silica mineral, feldspar, zeolite, and titanium. Examples include minerals, oxide minerals and hydrous minerals of iron and aluminum, sulfide minerals, carbonate minerals, sulfate minerals, and the like.
上記その他の無機化合物としては、例えば、ＣａＣＯ3、ＢａＳＯ4、塩基性炭酸マグネシウム、カーボンブラック、カーボンナノチューブ、フラーレン、鉛丹、黄鉛、黄色酸化鉄、チタンエロー、カドミウムエロー、モリブデートオレンジ、カドミウムレッド、群青、紺青、コバルトブルー、Ｃｒ2Ｏ3、コバルトグリーン、コバルト紫、緑青、辰砂等があげられる。 Examples of the other inorganic compounds include CaCO 3 , BaSO 4 , basic magnesium carbonate, carbon black, carbon nanotube, fullerene, red lead, yellow lead, yellow iron oxide, titanium yellow, cadmium yellow, molybdate orange, cadmium red. , Ultramarine, bituminous, cobalt blue, Cr 2 O 3 , cobalt green, cobalt purple, patina, dredged sand and the like.
これらの中でも、均一分散性が向上するとともに、化合物の種類に応じた屈折率、硬度、導電性、熱伝導性等の被膜性能も向上するという点から、上記無機微粒子（Ａ）としては、Ｂ、Ｃ、Ｎ、Ｃｅ、Ｃｏ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｃｒ、Ｗ、Ｆｅ、Ｎｉ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、ＳｎおよびＳｂからなる群から選ばれた少なくとも一つの元素、またはその化合物からなる無機物が好ましい。 Among these, as well as improved uniform dispersibility, the refractive index in accordance with the type of compound, hardness, conductivity, from the viewpoint also improved the film performance of the heat conductivity, etc., as the inorganic fine particles (A) are B, C, N, Ce, Co, Mg, Ca, Sr, Ba, Y, Ti, Zr, Hf, Nb, Ta, Cr, W, Fe, Ni, Pt, Cu, Ag, Au, Zn, Al, An inorganic substance composed of at least one element selected from the group consisting of Ga, In, Si, Sn and Sb, or a compound thereof is preferable.
上記無機微粒子（Ａ）の含有量は、均一分散性、被膜性能の点から、無機微粒子含有組成物全体の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 fine particles (A) are uniform dispersibility, in view of the membrane performance, the range of 0.01 to 90 wt% of the total inorganic particulate-containing compositions are preferred, particularly preferably 0.1 to 70 weight % 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、そのセルロースが、セルロースＩ型結晶構造を有すると共に、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、上記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以下であり、フェーリング試薬によるアルデヒド基の検出が認められない、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は、Ｉ型結晶構造を有する天然由来のセルロース固体原料を表面酸化し微細化した繊維である。すなわち、天然セルロースの生合成の過程においては、ほぼ例外なくミクロフィブリルと呼ばれるナノファイバーがまず形成され、これらが多束化して高次な固体構造を構成するが、上記ミクロフィブリル間の強い凝集力の原動となっている表面間の水素結合を弱めるために、その水酸基（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）の一部が酸化され、カルボキシル基やアルデヒド基やケトン基に変換されている。
<< Cellulose fiber (B) >>
The cellulose fiber (B) is a cellulose fiber having a number average fiber diameter of 2 to 150 nm. The cellulose has a cellulose I-type crystal structure, and the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule. It is selectively oxidized and modified to become one of an aldehyde group, a ketone group and a carboxyl group, and part or all of the aldehyde group and the ketone group are reduced, and the carboxyl group content is 1.2 to A fine cellulose fiber having a total content of aldehyde groups and ketone groups of not more than 0.3 mmol / g as measured by the semicarbazide method and having no detection of aldehyde groups by a Ferring reagent is used. The cellulose fiber is a fiber obtained by subjecting a naturally-derived cellulose solid raw material having an I-type crystal structure to surface oxidation and refinement. That is, in the process of biosynthesis of natural cellulose, nanofibers called microfibrils are first formed almost without exception, and these form multiple bundles to form a higher-order solid structure. In order to weaken the hydrogen bond between the surfaces that are the driving force of the cation, a part of its hydroxyl group (the C6 hydroxyl group of each glucose unit in the cellulose molecule) is oxidized and converted into a carboxyl group, an aldehyde group, or a ketone group. ing.
ここで、上記セルロース繊維（Ｂ）を構成するセルロースがＩ型結晶構造を有することは、例えば、広角Ｘ線回折像測定により得られる回折プロファイルにおいて、２シータ＝１４〜１７°付近と、２シータ＝２２〜２３°付近の２つの位置に典型的なピークをもつことから同定することができる。 Here, the cellulose constituting the cellulose fiber (B) has an I-type crystal structure, for example, in the diffraction profile obtained by wide-angle X-ray diffraction image measurement, in the vicinity of 2 theta = 14 to 17 ° and 2 theta It can be identified by having typical peaks at two positions near = 22 to 23 °.
上記セルロース繊維（Ｂ）の数平均繊維径は２〜１５０ｎｍの範囲であることが必要であるが、分散安定性の点から、好ましくは２〜１００ｎｍであり、特に好ましくは３〜８０ｎｍである。上記数平均繊維径が小さすぎると、本質的に分散媒体に溶解してしまい、上記数平均繊維径が大きすぎると、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くなる。 Although the number average fiber diameter of the said cellulose fiber (B) needs to be the range of 2-150 nm, from the point of dispersion stability, Preferably it is 2-100 nm, Most preferably, it is 3-80 nm. If the number average fiber diameter is too small, it will essentially dissolve in the dispersion medium, and if the number average fiber diameter is too large, the cellulose fibers will settle and express functionality by blending the cellulose fibers. Can not do.
上記セルロース繊維（Ｂ）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。上記セルロース繊維（Ｂ）の最大繊維径が大きすぎると、セルロース繊維が沈降してしまい、セルロース繊維の機能性の発現が低下する傾向がみられる。 The maximum fiber diameter of the cellulose fiber (B) is preferably 1000 nm or less, and particularly preferably 500 nm or less. When the maximum fiber diameter of the cellulose fiber (B) is too large, the cellulose fiber is settled, and there is a tendency that the expression of the functionality of the cellulose fiber is lowered.
上記セルロース繊維（Ｂ）の数平均繊維径および最大繊維径は、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 cellulose fiber (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.
上記セルロース繊維（Ｂ）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（カルボキシル基量）が１．２〜２．５ｍｍｏｌ／ｇの範囲であり、好ましくは１．５〜２．０ｍｍｏｌ／ｇの範囲である。上記カルボキシル基量が小さすぎると、セルロース繊維の沈降や凝集を生じる場合があり、上記カルボキシル基量がおきすぎると、水溶性が強くなり過ぎるおそれがある。 In the cellulose fiber (B), 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 amount of carboxyl groups) is in the range of 1.2 to 2.5 mmol / g, preferably in the range of 1.5 to 2.0 mmol / g. If the amount of carboxyl groups is too small, cellulose fibers may be precipitated or aggregated. If the amount of carboxyl groups is too high, the water solubility may be too strong.
上記セルロース繊維（Ｂ）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（１）に従いカルボキシル基量を求めることができる。
カルボキシル基量(mmol/g)＝Ｖ(ml)×〔０．０５／セルロース重量〕……(１)
The measurement of the amount of carboxyl groups of the cellulose fiber (B) is performed, for example, by preparing 60 ml of a 0.5 to 1% by weight slurry from a precisely weighed dry weight sample and adjusting the pH to about 2. with 0.1 M hydrochloric acid aqueous solution. After setting to 5, 0.05M sodium hydroxide aqueous solution was dropped, and the electrical conductivity was measured. The measurement is continued until the pH is about 11. The amount of carboxyl groups can be determined from the amount (V) of sodium hydroxide consumed in the neutralization step of the weak acid whose electrical conductivity changes slowly, according to the following formula (1).
Amount of carboxyl groups (mmol / g) = V (ml) × [0.05 / cellulose weight] (1)
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.
上記セルロース繊維（Ｂ）は、上記酸化変性後、還元剤により還元させる。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が還元され、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、上記セルロース繊維（Ｂ）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以下とし、好ましくは０〜０．１ｍｍｏｌ／ｇの範囲とし、最も好ましくは実質的に０ｍｍｏｌ／ｇとする。これにより、単に酸化変性させたものよりも、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以下であるセルロース繊維を、上記（Ｂ）のセルロース繊維として本発明の無機微粒子含有組成物に用いると、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。 The cellulose fibers (B) after the oxidation-modified, Ru was reduced by a reducing agent. 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, the total content of the aldehyde group and ketone group by the measurement by the semicarbazide method of the said cellulose fiber (B) shall be 0.3 mmol / g or less , Preferably it is the range of 0-0.1 mmol / g. and then, and most preferably you substantially 0 mmol / g. As a result, the dispersion stability is higher than that obtained by simply oxidative modification, and the dispersion stability is excellent over a long period of time regardless of the temperature. In addition, as described above, the inorganic fine particle-containing composition of the present invention is obtained by using, as the cellulose fiber of the above (B), a cellulose fiber having a total content of aldehyde groups and ketone groups of 0.3 mmol / g or less as measured by the semicarbazide method. When used for, the generation of aggregates due to long-term storage can be further suppressed.
上記セルロース繊維（Ｂ）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、上記セルロース繊維（Ｂ）を容易に得ることができるようになり、無機微粒子含有組成物として、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。 The cellulose fiber (B) is oxidized using a co-oxidant in the presence of an N-oxyl compound such as 2,2,6,6-tetramethylpiperidine (TEMPO), and is generated by the oxidation reaction. When the aldehyde group and the ketone group are reduced by a reducing agent, the cellulose fiber (B) can be easily obtained, and a better result can be obtained as a composition containing inorganic fine particles. It is preferable because Also, reduction with the reducing agent, the is by hydrogenation sodium borohydride (NaBH 4), more preferable from the viewpoint.
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、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。つぎに、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（２）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。 Measurement of the total content of aldehyde groups and ketone groups by the semicarbazide method is performed, for example, as follows. Specifically, 50 ml of a semicarbazide hydrochloride 3 g / l aqueous solution adjusted to pH = 5 with a phosphate buffer is accurately added to the 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 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 (2), 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〕……(２)
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] (2)
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セルロース繊維（Ｂ）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位の水酸基のみ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位の水酸基のみ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位水酸基のみが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 cellulose fiber (B) in the present invention, only 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. . Whether or not only 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 only the C6 hydroxyl group of the glucose unit is oxidized to a carboxyl group or the like.
また、上記セルロース繊維（Ｂ）におけるアルデヒド基の検出は、フェーリング試薬により行われる。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。 The detection of the aldehyde group in the cellulose fibers (B) is Ru row cracking by full Eringu reagent. 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. .
上記セルロース繊維（Ｂ）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）等により製造することができる。以下、各工程を順に説明する。 The cellulose fiber (B) can be produced by, for example, (1) an oxidation reaction step, (2) a reduction step, (3) a purification step, (4) a dispersion step (a refinement treatment step), and the like. 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、反応速度の点から、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 to advance reaction in presence of alkali metal bromides, such as sodium bromide, from the point of reaction rate. 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。所望のカルボキシル基量等を得るためには、共酸化剤の添加量と反応時間により、酸化の程度を制御する。通常、反応時間は約５〜１２０分、長くとも２４０分以内に完了する。 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. In order to obtain a desired amount of carboxyl group 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
上記セルロース繊維（Ｂ）は、上記酸化反応後に、さらに還元反応を行う。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等があげられる。なかでも、コストや利用可能性の点から、ＮａＢＨ4が好ましい。
(2) the reduction step the cellulose fibers (B), after the oxidation reaction, intends rows further reduction 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, NaBH 4 and the like. Of these, NaBH 4 is preferable from the viewpoint of cost and availability.
還元剤の量は、微細酸化セルロースを基準として、０．１〜４重量％の範囲が好ましく、特に好ましくは１〜３重量％の範囲である。反応は、室温または室温より若干高い温度で、通常、１０分〜１０時間、好ましくは３０分〜２時間行う。 The amount of the 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 the fine oxidized cellulose. The reaction is usually carried out at room temperature or slightly higher than room temperature, usually 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差し支えない。このように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 a purification method in the purification step, any apparatus can 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 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、セルロース繊維（Ｂ）を得ることできる。なお、上記セルロース繊維の分散体を乾燥することなく、分散体の状態で無機微粒子含有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, a cellulose fiber (B) can be obtained by drying the dispersion of the cellulose fiber. The cellulose fiber dispersion may be used in the inorganic fine particle-containing composition in a dispersion state without drying.
本発明の無機微粒子含有組成物においては、上記セルロース繊維（Ｂ）の分散媒体として、水や、水と有機溶媒の混合溶液等が用いられる。 In the inorganic fine particle-containing composition of the present invention, water, a mixed solution of water and an organic solvent, or the like is used as a dispersion medium for the cellulose fiber (B).
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、超音波分散処理機、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、経済的に有利に無機微粒子含有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、ディスパー、プロペラミキサー、ニーダー、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、ビーズミル粉砕機等を用いても差し支えない。また、２種類以上の分散機を組み合わせて用いても差し支えない。 Dispersers used in the above dispersion step include homomixers under high speed rotation, high pressure homogenizers, ultra high pressure homogenizers, ultrasonic dispersion processors, beaters, disc type refiners, conical type refiners, double disc type refiners, grinders, etc. The use of a powerful and beating-capable apparatus is preferable in that more efficient and advanced downsizing is possible, and an inorganic fine particle-containing composition can be obtained economically advantageously. Examples of the disperser include a screw mixer, paddle mixer, disper mixer, turbine mixer, disper, propeller mixer, kneader, blender, homogenizer, ultrasonic homogenizer, colloid mill, pebble mill, and bead mill grinder. It can be used. Further, two or more types of dispersers may be used in combination.
必要に応じて上記セルロース繊維（Ｂ）を乾燥してもよく、上記セルロース繊維（Ｂ）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、真空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。 If necessary, the cellulose fiber (B) may be dried. Examples of the method for drying the dispersion of the cellulose fiber (B) include spray drying, freeze drying, and the like when the dispersion medium is water. A vacuum drying method or the like is used, and when the dispersion medium is a mixed solution of water and an organic solvent, a drying method using a drum dryer, a spray drying method using a spray dryer, or the like is used.
本発明の無機微粒子含有組成物における上記セルロース繊維（Ｂ）の固形分の含有量は、無機微粒子（Ａ）の均一な分散性と保存安定性の点から、組成物全体の０．０１〜１０重量％の範囲が好ましく、より好ましくは組成物全体の０．１〜１．０重量％の範囲である。 The solid content of the cellulose fiber (B) in the inorganic fine particle-containing composition of the present invention is 0.01 to 10 of the entire composition from the viewpoint of uniform dispersibility and storage stability of the inorganic fine particles (A). The range of% by weight is preferred, and the range of 0.1 to 1.0% by weight of the total composition is more preferred.
本発明の無機微粒子含有組成物における、無機微粒子（Ａ）とセルロース繊維（Ｂ）の固形分の比は、均一分散性と被膜性能のバランスの点から、（Ａ）／（Ｂ）＝１／９９〜８５／１５の範囲が好ましく、特に好ましくは（Ａ）／（Ｂ）＝５０／５０〜８０／２０の範囲、最も好ましくは（Ａ）／（Ｂ）＝６５／３５〜８０／２０の範囲である。 In the inorganic fine particle-containing composition of the present invention, the ratio of the solid content of the inorganic fine particles (A) and cellulose fibers (B) is in terms of the balance of the uniform dispersibility and the membrane performance, (A) / (B) = 1 / 99 to 85/15 is preferred, particularly preferably (A) / (B) = 50/50 to 80/20, most preferably (A) / (B) = 65/35 to 80/20. Range.
本発明の無機微粒子含有組成物には、無機微粒子（Ａ）およびセルロース繊維（Ｂ）とともに、本発明の効果を損なわない範囲内で、水、有機溶媒、防腐剤、界面活性剤、増粘剤、樹脂、着色剤、無機塩、ｐＨ調整剤、有機化合物等を必要に応じて適宜に配合することができる。 The inorganic fine particle-containing composition of the present invention includes, together with the inorganic fine particles (A) and the cellulose fibers (B), water, organic solvents, preservatives, surfactants, thickeners within a range not impairing the effects of the present invention A resin, a colorant, an inorganic salt, a pH adjuster, an organic compound, and the like can be appropriately blended as necessary.
本発明の無機微粒子含有組成物は、例えば、無機微粒子（Ａ）およびセルロース繊維（Ｂ）を配合し、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調製することができる。 The inorganic fine particle-containing composition of the present invention is prepared, for example, by blending inorganic fine particles (A) and cellulose fibers (B) and further blending other materials as necessary, followed by mixing treatment. be able to.
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. And a mixing process using.
本発明の無機微粒子含有組成物を用いてなる被膜（無機微粒子含有）は、例えば、上記無機微粒子含有組成物を、基板上に塗工し乾燥することにより得ることができる。上記無機微粒子含有組成物の塗工方法としては、例えば、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があげられる。 Inorganic fine particle-containing composition to be film formed by using the present invention (containing fine inorganic particles), for example, can be obtained by the inorganic fine particle-containing composition is coated on a substrate drying. Examples of the coating method for the inorganic fine particle-containing composition include 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, a screen printing method, and a spray. Examples thereof include a coating method, a die coater method, an ink jet printing method, a dipping method, a brush coating method, and a bar coater method.
上記被膜（無機微粒子含有）の厚みは、光学部材、電池材料、電子部品等の使用用途により異なるが、通常、０．０１〜１００μｍ、好ましくは０．１〜３０μｍである。 The thickness of the film (inorganic fine particle-containing) are optical members, battery materials, varies depending use applications such as electronic parts, typically, 0.01 to 100 [mu] m, preferably from 0.1 to 30 [mu] m.
以下、実施例をあげて本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、例中、「％」とあるのは、特に限定のない限り重量基準を意味する。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “%” means a weight basis unless otherwise specified.
まず、参考例、実施例および比較例に先立ち、参考例用、実施例用および比較例用のセルロース繊維をそれぞれ製造した。そして、各セルロース繊維の結晶構造の有無等の評価を、後述の基準に従って行い、その結果を後記の表１に併せて示した。 First, reference examples, prior to the Examples and Comparative Examples, a Reference Example, a cellulose fiber of the comparative examples and for example was prepared respectively. And the evaluation of the presence or absence of the crystal structure of each cellulose fiber was performed according to the criteria described later, and the results are also shown in Table 1 below.
〔セルロース繊維Ｂ１（参考例用）の製造〕
針葉樹パルプ２ｇに、水１５０ｍｌ、臭化ナトリウム０．２５ｇ、ＴＥＭＰＯを０．０２５ｇを加え、充分撹拌して分散させた後、１３重量％次亜塩素酸ナトリウム水溶液（共酸化剤）を、上記パルプ１．０ｇに対して次亜塩素酸ナトリウム量が５．２ｍｍｏｌ／ｇとなるように加え、反応を開始した。反応の進行に伴いｐＨが低下するため、ｐＨを１０〜１１に保持するように０．５Ｎ水酸化ナトリウム水溶液を滴下しながら、ｐＨの変化が見られなくなるまで反応させた（反応時間：１２０分）。反応終了後、０．１Ｎ塩酸を添加して中和した後、ろ過と水洗を繰り返して精製し、繊維表面が酸化されたセルロース繊維を得た。つぎに、上記セルロース繊維に純水を加えて１％に希釈し、高圧ホモジナイザー（三和エンジニアリング社製、Ｈ１１）を用いて圧力１００ＭＰａで１回処理することにより、セルロース繊維Ｂ１を製造した。
[Production of Cellulose Fiber B1 (for Reference Example)]
After adding 150 ml of water, 0.25 g of sodium bromide, and 0.025 g of TEMPO to 2 g of softwood pulp, and thoroughly stirring and dispersing, 13 wt% aqueous sodium hypochlorite solution (co-oxidant) was added to the above pulp. The reaction was started by adding sodium hypochlorite so that the amount of sodium hypochlorite was 5.2 mmol / g with respect to 1.0 g. Since the pH decreased with the progress of the reaction, the reaction was continued until no change in pH was observed while dropping a 0.5N aqueous sodium hydroxide solution so that the pH was maintained at 10-11 (reaction time: 120 minutes). ). After completion of the reaction, 0.1N hydrochloric acid was added for neutralization, followed by purification by repeated filtration and washing to obtain cellulose fibers having oxidized fiber surfaces. Next, the cellulose fiber B1 was manufactured by adding pure water to the said cellulose fiber, diluting to 1%, and processing once at a pressure of 100 MPa using a high pressure homogenizer (H11 made by Sanwa Engineering Co., Ltd.).
〔セルロース繊維Ｂ２（参考例用）の製造〕
次亜塩素酸ナトリウム水溶液の添加量を、上記パルプ１．０ｇに対して６．５ｍｍｏｌ／ｇとした以外は、セルロース繊維Ｂ１の製造に準じて、セルロース繊維Ｂ２を製造した。
[Production of Cellulose Fiber B2 (for Reference Example)]
Cellulose fiber B2 was produced according to the production of cellulose fiber B1, except that the amount of sodium hypochlorite aqueous solution added was 6.5 mmol / g with respect to 1.0 g of the pulp.
〔セルロース繊維Ｂ３（参考例用）の製造〕
次亜塩素酸ナトリウム水溶液の添加量を、上記パルプ１．０ｇに対して１２．０ｍｍｏｌ／ｇとした以外は、セルロース繊維Ｂ１の製造に準じて、セルロース繊維Ｂ３を製造した。
[Production of Cellulose Fiber B3 (for Reference Example)]
Cellulose fiber B3 was produced according to the production of cellulose fiber B1, except that the amount of sodium hypochlorite aqueous solution added was 12.0 mmol / g with respect to 1.0 g of the pulp.
〔セルロース繊維Ｂ４（実施例用）の製造〕
セルロース繊維Ｂ１の製造と同様の手法で針葉樹パルプを酸化した後、遠心分離機で固液分離し、純水を加えて固形分濃度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℃として水素化ホウ素ナトリウムをセルロース繊維に対して０．２ｍｍｏｌ／ｇ加え、２時間反応させることで還元処理した。反応後、０．１Ｎ塩酸を添加して中和した後、ろ過と水洗を繰り返して精製し、セルロース繊維を得た。つぎに、上記セルロース繊維に純水を加えて１％に希釈し、高圧ホモジナイザー（三和エンジニアリング社製、Ｈ１１）を用いて圧力１００ＭＰａで１回処理することにより、セルロース繊維Ｂ４を製造した。
[Production of Cellulose Fiber B4 (for Examples)]
Softwood pulp was oxidized by the same method as in the production of cellulose fiber B1, then solid-liquid separated with a centrifuge, and pure 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 slurry was reduced to 30 ° C. by adding 0.2 mmol / g of sodium borohydride to the cellulose fiber and reacting for 2 hours. After the reaction, 0.1N hydrochloric acid was added for neutralization, followed by purification by repeated filtration and washing to obtain cellulose fibers. Next, pure water was added to the cellulose fiber to dilute it to 1%, and the fiber was treated once with a high pressure homogenizer (manufactured by Sanwa Engineering Co., Ltd., H11) at a pressure of 100 MPa to produce cellulose fiber B4.
〔セルロース繊維Ｂ５（実施例用）の製造〕
セルロース繊維Ｂ２の製造と同様の手法で針葉樹パルプを酸化した後、セルロース繊維Ｂ４の製造と同様の手法で還元、精製した。つぎに、上記セルロース繊維に純水を加えて１％に希釈し、高圧ホモジナイザー（三和エンジニアリング社製、Ｈ１１）を用いて圧力１００ＭＰａで１回処理することにより、セルロース繊維Ｂ５を製造した。
[Production of Cellulose Fiber B5 (for Examples)]
The softwood pulp was oxidized by the same method as the production of the cellulose fiber B2, and then reduced and purified by the same method as the production of the cellulose fiber B4. Next, pure water was added to the cellulose fiber to dilute it to 1%, and the fiber was treated once with a high-pressure homogenizer (manufactured by Sanwa Engineering Co., Ltd., H11) at a pressure of 100 MPa to produce cellulose fiber B5.
〔セルロース繊維Ｂ６（実施例用）の製造〕
セルロース繊維Ｂ３の製造と同様の手法で針葉樹パルプを酸化した後、セルロース繊維Ｂ４の製造と同様の手法で還元、精製した。つぎに、上記セルロース繊維に純水を加えて１％に希釈し、高圧ホモジナイザー（三和エンジニアリング社製、Ｈ１１）を用いて圧力１００ＭＰａで１回処理することにより、セルロース繊維Ｂ６を製造した。
[Production of Cellulose Fiber B6 (for Examples)]
After coniferous pulp was oxidized by the same method as the production of cellulose fiber B3, it was reduced and purified by the same method as the production of cellulose fiber B4. Next, pure water was added to the cellulose fiber to dilute it to 1%, and the cellulose fiber B6 was produced by processing once at a pressure of 100 MPa using a high-pressure homogenizer (manufactured by Sanwa Engineering Co., Ltd., H11).
〔セルロース繊維Ｂ′１（比較例用）の製造〕
次亜塩素酸ナトリウム水溶液の添加量を、上記パルプ１．０ｇに対して４．１ｍｍｏｌ／ｇとした以外は、セルロース繊維Ｂ１の製造に準じて、セルロース繊維Ｂ′１を製造した。
[Production of Cellulose Fiber B′1 (for Comparative Example)]
Cellulose fiber B′1 was produced according to the production of cellulose fiber B1, except that the amount of sodium hypochlorite aqueous solution added was 4.1 mmol / g with respect to 1.0 g of the pulp.
〔セルロース繊維Ｂ′２（比較例用）の製造〕
原料の針葉樹パルプに替えて再生セルロースを使用するとともに、次亜塩素酸ナトリウム水溶液の添加量を、再生セルロース１．０ｇに対して２７．０ｍｍｏｌ／ｇとした以外は、セルロース繊維Ｂ１の製造に準じて、セルロース繊維Ｂ′２を製造した。
[Production of Cellulose Fiber B′2 (for Comparative Example)]
According to the production of cellulose fiber B1, except that regenerated cellulose is used in place of the raw conifer pulp and the amount of sodium hypochlorite aqueous solution added is 27.0 mmol / g with respect to 1.0 g of regenerated cellulose. Thus, cellulose fiber B′2 was produced.
上記のようして得られた各セルロース繊維について、下記の基準に従って、各特性の評価を行った。その結果を、上記表１に併せて示した。 Each cellulose fiber obtained as described above was evaluated for each characteristic according to the following criteria. The results are also shown in Table 1 above.
〔結晶構造〕
Ｘ線回折装置（リガク社製、ＲＩＮＴ−Ｕｌｔｉｍａ３）を用いて、各セルロース繊維の回折プロファイルを測定し、２シータ＝１４〜１７°付近と、２シータ＝２２〜２３°付近の２つの位置に典型的なピークが見られる場合は結晶構造（Ｉ型結晶構造）が「あり」と評価し、ピークが見られない場合は「なし」と評価した。
〔Crystal structure〕
Using an X-ray diffractometer (Rigaku Corporation, RINT-Utima3), the diffraction profile of each cellulose fiber was measured, and two positions of 2 theta = 14-17 ° and 2 theta = 22-23 ° were obtained. When a typical peak was observed, the crystal structure (type I crystal structure) was evaluated as “present”, and when no peak was observed, it was evaluated as “none”.
〔数平均繊維径〕
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。
[Number average fiber diameter]
The number average fiber diameter of the cellulose fibers 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.
〔カルボキシル基量の測定〕
セルロース繊維０．２５ｇを水に分散させたセルロース水分散体６０ｍｌを調製し、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（１）に従いカルボキシル基量を求めた。
カルボキシル基量 (mmol/g)＝Ｖ(ml)×〔０．０５／セルロース重量〕……(１)
[Measurement of carboxyl group content]
After preparing 60 ml of a cellulose aqueous dispersion in which 0.25 g of cellulose fiber was dispersed in water, the pH was adjusted to about 2.5 with 0.1 M hydrochloric acid aqueous solution, and 0.05 M sodium hydroxide aqueous solution was added dropwise. Electrical 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 (V) where the change in electrical conductivity was slow, according to the following formula (1).
Amount of carboxyl groups (mmol / g) = V (ml) × [0.05 / cellulose weight] (1)
〔カルボニル基量の測定（セミカルバジド法）〕
セルロース繊維を約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。つぎに、この溶液１０ｍｌを正確に１００ｍｌビーカーに採取し、５Ｎ硫酸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、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（２）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〕……(２)
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 cellulose fiber was precisely weighed, and precisely 50 ml of a 3 g / l aqueous solution of semicarbazide hydrochloride adjusted to pH = 5 with a phosphate buffer was added thereto, sealed, and shaken for 2 days. Next, 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 stirred for 10 minutes. Thereafter, 10 ml of 5% aqueous potassium iodide solution was added, and immediately titrated with a 0.1N sodium thiosulfate solution using an automatic titrator. From the titration, etc., the carbonyl in the sample was determined according to the following formula (2). The base amount (total content of aldehyde group and ketone group) was determined.
Carbonyl group amount (mmol / g) = (D−B) × f × [0.125 / w] (2)
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〕
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、アルデヒド基は検出されなかったと判断し、「なし」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、アルデヒド基は検出されたと判断し、「あり」と評価した。
[Detection of aldehyde group]
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. And when the supernatant was blue and the cellulose fiber part was amber, it was judged that no aldehyde group was detected, and was evaluated as “none”. Moreover, when the supernatant was yellow and the cellulose fiber part was red, it was judged that an aldehyde group was detected, and was evaluated as “present”.
前記表１の結果から、参考例用および実施例用のセルロース繊維Ｂ１〜Ｂ６は、いずれも数平均繊維径が２〜１５０ｎｍの範囲内で、セルロースＩ型結晶構造を有すると共に、カルボキシル基の含量が１．２〜２．５ｍｍｏｌ／ｇの範囲であった。これに対して、比較例用のセルロース繊維Ｂ′１は、数平均繊維径が上限を超え、カルボキシル基量は下限未満であった。セルロース繊維Ｂ′２は、数平均繊維径が小さすぎて測定不可（１ｎｍ以下）であり、カルボキシル基量は上限を超えていた。 From the results of Table 1, cellulose fibers B1 to B6 for reference examples and examples all have a number average fiber diameter of 2 to 150 nm, have a cellulose I-type crystal structure, and a carboxyl group content. Was in the range of 1.2 to 2.5 mmol / g. On the other hand, the cellulose fiber B′1 for the comparative example had a number average fiber diameter exceeding the upper limit and the carboxyl group amount being less than the lower limit. Cellulose fiber B′2 had a number average fiber diameter that was too small to be measured (1 nm or less), and the amount of carboxyl groups exceeded the upper limit.
また、セルロース繊維Ｂ１〜Ｂ６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結果、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、セルロース繊維Ｂ１〜Ｂ６は、いずれもグルコース単位のＣ６位水酸基のみがアルデヒド基等に酸化されていることが確認された。 In addition, regarding the cellulose fibers B1 to B6, 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. A 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, disappeared after the oxidation reaction, and instead a peak derived from the carboxyl group appeared at 178 ppm. From this, it was confirmed that all the cellulose fibers B1 to B6 are oxidized only at the C6 hydroxyl group of the glucose unit to an aldehyde group or the like.
つぎに、上記で得た各セルロース繊維を用い、参考例、実施例および比較例の無機微粒子含有組成物を調製するとともに、この組成物を用いて無機微粒子含有被膜を形成した（ただし、比較例の一部は、無機微粒子を含有しない）。そして、各組成物および被膜について、後記の基準に従って、各特性の評価を行い、その結果を、後記の表２〜７に併せて示した。 Next, using each cellulose fibers obtained in the above Reference Example, as well as preparing an inorganic fine particle-containing compositions of Examples and Comparative Examples, it was formed of an inorganic fine particle containing the film by using the composition (although, compared Some examples do not contain inorganic particulates). And about each composition and the film, according to the below-mentioned reference | standard, each characteristic was evaluated and the result was combined with the below-mentioned Tables 2-7, and was shown.
〔参考例１〕
バインダーとしてのセルロース繊維Ｂ１を５０ｇ（固形分量：０．５％）と、無機微粒子としての酸化ジルコニウム（ＺｒＯ2）水分散液（堺化学工業製、ＳＺＲ−ＣＷ、平均粒径５ｎｍ、固形分３０％）３．１ｇ（固形分量：０．９３％）を混合し、精製水を加えて全量を１００ｇとした後、ホモディスパーを用いて３０００ｒｐｍで１０分間撹拌し、無機微粒子含有組成物（分散液）を調製した。そして、この分散液をプラスチックシャーレにキャストし、４０℃で１５時間乾燥した後、さらに１００℃で１時間乾燥し、膜厚２０μｍの無機微粒子含有被膜を形成した。
[ Reference Example 1]
50 g of cellulose fiber B1 as a binder (solid content: 0.5%) and an aqueous dispersion of zirconium oxide (ZrO 2 ) as inorganic fine particles (manufactured by Sakai Chemical Industry, SZR-CW, average particle size 5 nm, solid content 30) %) 3.1 g (solid content: 0.93%) was mixed, purified water was added to make the total amount 100 g, and the mixture was stirred with a homodisper at 3000 rpm for 10 minutes to prepare an inorganic fine particle-containing composition (dispersion) ) Was prepared. Then, the dispersion was cast into a plastic petri dish, dried for 15 hours at 40 ° C., and further dried 1 hour at 100 ° C., to form the inorganic fine particle-containing target film having a thickness of 20 [mu] m.
〔参考例２，３、実施例１〜８、比較例１〜４〕
セルロース繊維の種類，配合量、もしくは酸化ジルコニウム水分散液の配合量を、下記の表２および表３に示すように変更した以外は、参考例１と同様にして、無機微粒子含有組成物および無機微粒子含有被膜を得た。
[ Reference Examples 2 and 3, Examples 1 to 8 , Comparative Examples 1 to 4]
The inorganic fine particle-containing composition and the inorganic material were the same as in Reference Example 1 except that the type and blending amount of the cellulose fiber or the blending amount of the zirconium oxide aqueous dispersion were changed as shown in Tables 2 and 3 below. microparticles containing thereby to prepare a film.
〔参考例４〕
無機微粒子としての酸化ジルコニウム水分散液３．１ｇ（固形分量：０．９３％）に代えて、酸化スズ（ＳｎＯ2）水分散液（ユニチカ社製、ＡＳ２０Ｉ、平均粒径１０ｎｍ、固形分２０％）４．７ｇ（固形分量：０．９３％）を使用した以外は、参考例１と同様にして、無機微粒子含有組成物および無機微粒子含有被膜を得た。
[ Reference Example 4 ]
Instead of 3.1 g of zirconium oxide aqueous dispersion (solid content: 0.93%) as inorganic fine particles, tin oxide (SnO 2 ) aqueous dispersion (manufactured by Unitika, AS20I, average particle size 10 nm, solid content 20%) ) 4.7 g (solid content: except for using 0.93%), in the same manner as in reference example 1, to obtain an inorganic fine particle-containing composition and the inorganic fine particles containing the film.
〔参考例５，６、実施例９〜１６、比較例５〜８〕
セルロース繊維の種類，配合量、もしくは酸化スズ水分散液の配合量を、下記の表４および表５に示すように変更した以外は、参考例４と同様にして、無機微粒子含有組成物および無機微粒子含有被膜を得た。
[ Reference Examples 5 and 6, Examples 9 to 16 , Comparative Examples 5 to 8]
The inorganic fine particle-containing composition and the inorganic material were the same as in Reference Example 4 except that the type and blending amount of the cellulose fiber or the blending amount of the tin oxide aqueous dispersion were changed as shown in Tables 4 and 5 below. microparticles containing thereby to prepare a film.
〔参考例７〕
無機微粒子としての酸化ジルコニウム水分散液３．１ｇ（固形分量：０．９３％）に代えて、ガリウムドープ酸化亜鉛（ＧＺＯ）分散液（ハクスイテック社製、パゼットＧＫ、平均粒径３０ｎｍ、固形分２０％）４．７ｇ（固形分量：０．９３％）を使用した以外は、参考例１と同様にして、無機微粒子含有組成物および無機微粒子含有被膜を得た。
[ Reference Example 7 ]
Instead of 3.1 g of zirconium oxide aqueous dispersion (solid content: 0.93%) as inorganic fine particles, a gallium-doped zinc oxide (GZO) dispersion (manufactured by Hux Itec Corp., passette GK, average particle size 30 nm, solid content 20 %) 4.7 g (solid content: except for using 0.93%), in the same manner as in reference example 1, to obtain an inorganic fine particle-containing composition and the inorganic fine particles containing the film.
〔参考例８，９、実施例１７〜２４、比較例９〜１１〕
セルロース繊維の種類，配合量、もしくはガリウムドープ酸化亜鉛水分散液の配合量を、下記の表６および表７に示すように変更した以外は、参考例７と同様にして、無機微粒子含有組成物および無機微粒子含有被膜を得た。
[ Reference Examples 8 and 9, Examples 17 to 24 , Comparative Examples 9 to 11]
Inorganic fine particle-containing composition in the same manner as in Reference Example 7 , except that the type and blending amount of the cellulose fiber or the blending amount of the gallium-doped zinc oxide aqueous dispersion was changed as shown in Tables 6 and 7 below. and to obtain an inorganic fine particle containing the film.
このようにして得られた無機微粒子含有組成物および無機微粒子含有被膜について、下記の基準に従って、各特性の評価を行った。その結果を、上記表２〜７に併せて示した。 This way, the inorganic fine particle-containing composition obtained and the inorganic fine particles containing the film, according to the following criteria were evaluated for each of the characteristics. The result was combined with the said Tables 2-7, and was shown.
〔分散液の凝集状態〕
各分散液の凝集状態を、目視および光学顕微鏡（オムロン社製、デジタルマイクロスコープVC1000）を用いて倍率１０００倍で観察し、以下の基準で凝集状態を判定した。
◎：光学顕微鏡観察で凝集物がみられない。
○：光学顕微鏡観察で僅かに凝集物がみられる。
△：光学顕微鏡観察で凝集物がみられるが、目視では凝集物がみられない。
×：目視で凝集物が見られる。
[Agglomeration state of dispersion]
The aggregation state of each dispersion was observed visually and using an optical microscope (digital microscope VC1000, manufactured by OMRON Corporation) at a magnification of 1000 times, and the aggregation state was determined according to the following criteria.
(Double-circle): The aggregate is not seen by optical microscope observation.
○: Slight aggregates are observed with an optical microscope.
Δ: Aggregates are observed with an optical microscope, but no agglomerates are visually observed.
X: Aggregates are visually observed.
〔透明性（ヘイズ値）〕
各被膜の透明性（ヘイズ値）を、直読ヘーズコンピューターＨＧＭ−２ＤＰ（スガ試験機社製）を用いて測定した。透明性の点からは、ヘイズ値は９％以下が好ましい。
[Transparency (haze value)]
The transparency of each of the film (haze value) was measured using a direct reading haze computer HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.). From the viewpoint of transparency, the haze value is preferably 9 % or less.
〔屈折率〕
各被膜の屈折率を、屈折率膜厚測定装置ＰＲＩＳＭＣＯＵＰＬＥＲ Ｍｏｄｅｌ２０１０／Ｍ（メトリコン社製）を用いて測定した。屈折率は、１．６６以上が好ましい。
[Refractive index]
The refractive index of each of the films was measured using a refractive index film thickness measuring device PRISMCOUPLER Model2010 / M a (Metricon Co., Ltd.). The refractive index is preferably 1.66 or more.
〔硬度〕
各被膜の硬度（アルテンス硬さ）を、微小硬度計ＥＮＢ１１００（エリオニクス社製）を用いて測定した。硬度（アルテンス硬さ）は、３００Ｎ／ｍｍ2以上が好ましい。
〔hardness〕
The hardness of each of the films (Arutensu hardness) was measured using a microhardness meter ENB1100 (Elionix Co., Ltd.). The hardness (Altens hardness) is preferably 300 N / mm 2 or more.
〔導電性（表面抵抗値）〕
各被膜について、超絶縁抵抗計（ＡＤＶＡＮＴＥＳＴ社製、Ｒ８３４０）を用いて、印加電圧５００Ｖ、２５℃、２０％ＲＨにおける表面抵抗値（Ω／□）を測定した。表面抵抗値は、１×１０10（Ω／□）以下が好ましい。
[Conductivity (surface resistance)]
For each of the films, ultra insulation resistance meter (ADVANTEST Co., R8340) with an applied voltage 500V, 25 ° C., it was measured surface resistivity at 20% RH (Ω / □) . The surface resistance value is preferably 1 × 10 10 (Ω / □) or less.
上記表２および表３の結果より、実施例１〜８品はいずれも、透明性、屈折率、硬度の全てが良好な被膜が得られた。特に参考例１〜３品と比較しても、実施例１〜８品は、カルボニル基量が０．３ｍｍｏｌ／ｇ以下で、アルデヒド基が検出されなかったセルロース繊維Ｂ４〜Ｂ６を使用していることから、凝集の抑制効果が高く、より高い透明性の被膜が得られた。 From the results of Table 2 and Table 3, any of Examples 1 8 dishes, transparency, refractive index, all hardness was obtained a good target membrane. Especially compared with the products of Reference Examples 1 to 3, Examples 1 to 8 use cellulose fibers B4 to B6 in which the amount of carbonyl groups is 0.3 mmol / g or less and no aldehyde group is detected. since, the effect of suppressing aggregation is high, greater transparency of the film was obtained.
これに対して、比較例１〜４品は、透明性、屈折率、硬度の全てが良好な被膜は得られなかった。特に、比較例１品は、繊維径が大きいセルロース繊維Ｂ′１をバインダーとして用いているため、被膜が白濁し、透明性が劣っていた。比較例２品は、結晶構造を有していないセルロース繊維Ｂ′２をバインダーとして用いているため、硬度が低い値となった。 In contrast, Comparative Examples 1 to 4 hose of transparency, refractive index, all the good target film hardness was not obtained. In particular, Comparative Example 1 goods is due to the use of fiber diameter is large cellulose fibers B'1 as a binder, the film was opaque and the transparency was poor. The product of Comparative Example 2 had a low hardness because cellulose fiber B′2 having no crystal structure was used as a binder.
また、上記表４〜７の結果より、実施例９〜２４品はいずれも、透明性、導電性、硬度の全てが良好な被膜が得られた。特に参考例４〜９品と比較しても、実施例９〜２４品は、カルボニル基量が０．３ｍｍｏｌ／ｇ以下で、アルデヒド基が検出されなかったセルロース繊維Ｂ４〜Ｂ６を使用していることから、凝集の抑制効果が高く、より高い透明性の被膜が得られた。 Further, from the results in Table 4-7, any of Examples 9-24 dishes, transparency, electrical conductivity, all the hardness is satisfactory the film was obtained. Especially compared with the products of Reference Examples 4 to 9, the products of Examples 9 to 24 use cellulose fibers B4 to B6 in which the amount of carbonyl groups is 0.3 mmol / g or less and no aldehyde group is detected. since, the effect of suppressing aggregation is high, greater transparency of the film was obtained.
これに対して、比較例５〜１１品では、透明性、導電性、硬度の全てが良好な被膜は得られなかった。特に、比較例５品，９品は、繊維径が大きいセルロース繊維Ｂ′１をバインダーとして用いているため、被膜が白濁し、さらに導電性も低かった。比較例６品，１０品は、結晶構造を有していないセルロース繊維Ｂ′２をバインダーとして用いているため、硬度が低い値となった。 In contrast, in the comparative example 5 to 11 dishes, transparency, electrical conductivity, all the good target film hardness was not obtained. In particular, Comparative Example 5 dishes, 9 dishes, due to the use of fiber diameter is large cellulose fibers B'1 as a binder, the film was opaque and was further conductivity even lower. In Comparative Examples 6 and 10, since the cellulose fiber B′2 having no crystal structure was used as a binder, the hardness was low.
本発明の無機微粒子含有組成物は、無機微粒子の凝集が抑制されて均一分散性に優れるため、屈折率、導電性、硬度等の性能に優れた被膜を形成することができる。したがって、本発明の無機微粒子含有組成物およびそれを用いてなる被膜（無機微粒子含有被膜）は、屈折率、導電性、硬度等の性能が特に必要とされる用途、例えば、光学部材、電池材料、電子部品等の用途に好適に使用することができる。 Inorganic fine particle-containing composition of the present invention is excellent in uniform dispersibility aggregation is suppressed in the inorganic fine particles can be formed refractive index, conductivity, to be film excellent in performance such as hardness. Accordingly, the inorganic fine particle-containing composition and the film (inorganic fine particles containing the film) formed by using the same of the present invention, application refractive index, conductivity, performance such as hardness is specifically required, for example, an optical member, It can be suitably used for applications such as battery materials and electronic parts.
Claims (4)
（Ａ）平均粒径が１μｍ以下の無機微粒子。
（Ｂ）数平均繊維径が２〜１５０ｎｍのセルロース繊維であって、そのセルロースが、セルロースＩ型結晶構造を有すると共に、セルロース分子中の各グルコースユニットのＣ６位が選択的にアルデヒド基，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、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以下であり、フェーリング試薬によるアルデヒド基の検出が認められない、セルロース繊維。 An inorganic fine particle-containing composition comprising the following (A) and (B):
(A) Inorganic fine particles having an average particle size of 1 μm or less.
(B) a number average fiber diameter of 2~150nm cellulose fibers, the cellulose, which has a cellulose I type crystal structure, C6-position selectively aldehydes groups of each glucose unit in a molecule of the cellulose, ketone A carboxyl group content of 1.2 to 2.5 mmol / g, and a total content of aldehyde groups and ketone groups as measured by the semicarbazide method of 0.3 mmol / g or less. Cellulose fiber , which does not have aldehyde group detection by a Fehring reagent .
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| JPH0733909A (en) * | 1993-07-20 | 1995-02-03 | Sumitomo Chem Co Ltd | Gas barrier resin composition and film |
| JP5296445B2 (en) * | 2008-07-31 | 2013-09-25 | 第一工業製薬株式会社 | Gel composition |
| JP5564867B2 (en) * | 2009-09-14 | 2014-08-06 | 凸版印刷株式会社 | Method for producing gas barrier layer forming composition |
| WO2011118360A1 (en) * | 2010-03-26 | 2011-09-29 | 凸版印刷株式会社 | Film-forming composition and sheet |
| EP2759576A4 (en) * | 2011-09-22 | 2015-02-25 | Toppan Printing Co Ltd | Carbon particle dispersion and method for producing same |
| JP2013209779A (en) * | 2012-03-30 | 2013-10-10 | Toppan Printing Co Ltd | Formed body and method for producing the same |
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| JP2019183109A (en) * | 2018-04-10 | 2019-10-24 | 第一工業製薬株式会社 | Redispersible composition containing cellulose fiber and non-cellulose granulated material |
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