JP5970915B2 - Conductive composite - Google Patents
Conductive composite Download PDFInfo
- Publication number
- JP5970915B2 JP5970915B2 JP2012078821A JP2012078821A JP5970915B2 JP 5970915 B2 JP5970915 B2 JP 5970915B2 JP 2012078821 A JP2012078821 A JP 2012078821A JP 2012078821 A JP2012078821 A JP 2012078821A JP 5970915 B2 JP5970915 B2 JP 5970915B2
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- JP
- Japan
- Prior art keywords
- modified
- dispersion
- csnf
- film
- carboxy group
- 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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- 239000002131 composite material Substances 0.000 title claims description 63
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 claims description 69
- 229920002678 cellulose Polymers 0.000 claims description 44
- 239000001913 cellulose Substances 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000002041 carbon nanotube Chemical class 0.000 claims description 20
- 239000002121 nanofiber Substances 0.000 claims description 13
- 229910021393 carbon nanotube Chemical class 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000010408 film Substances 0.000 description 75
- 239000006185 dispersion Substances 0.000 description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
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- 238000000034 method Methods 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000000835 fiber Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- -1 polyethylene terephthalate Polymers 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000002109 single walled nanotube Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
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- 239000011347 resin Substances 0.000 description 7
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 150000003839 salts Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000005016 bacterial cellulose Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012789 electroconductive film Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 230000004043 responsiveness Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- GSGLHYXFTXGIAQ-UHFFFAOYSA-M 1,3-dimethylimidazol-1-ium;dimethyl phosphate Chemical compound COP([O-])(=O)OC.CN1C=C[N+](C)=C1 GSGLHYXFTXGIAQ-UHFFFAOYSA-M 0.000 description 1
- VRFOKYHDLYBVAL-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCN1C=C[N+](C)=C1 VRFOKYHDLYBVAL-UHFFFAOYSA-M 0.000 description 1
- HZKDSQCZNUUQIF-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCN1C=C[N+](C)=C1 HZKDSQCZNUUQIF-UHFFFAOYSA-M 0.000 description 1
- IXLWEDFOKSJYBD-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;methanesulfonate Chemical compound CS([O-])(=O)=O.CC[N+]=1C=CN(C)C=1 IXLWEDFOKSJYBD-UHFFFAOYSA-M 0.000 description 1
- ZPTRYWVRCNOTAS-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound CC[N+]=1C=CN(C)C=1.[O-]S(=O)(=O)C(F)(F)F ZPTRYWVRCNOTAS-UHFFFAOYSA-M 0.000 description 1
- ZTLWMUBOQHZKNS-UHFFFAOYSA-M 1-ethyl-3-methylpyridin-1-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CC[N+]1=CC=CC(C)=C1 ZTLWMUBOQHZKNS-UHFFFAOYSA-M 0.000 description 1
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 description 1
- IVCMUVGRRDWTDK-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1 IVCMUVGRRDWTDK-UHFFFAOYSA-M 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- OXFBEEDAZHXDHB-UHFFFAOYSA-M 3-methyl-1-octylimidazolium chloride Chemical compound [Cl-].CCCCCCCCN1C=C[N+](C)=C1 OXFBEEDAZHXDHB-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
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- 229920002125 Sokalan® Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical compound CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- 241001478802 Valonia Species 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HEQWUWZWGPCGCD-UHFFFAOYSA-N cadmium(2+) oxygen(2-) tin(4+) Chemical compound [O--].[O--].[O--].[Cd++].[Sn+4] HEQWUWZWGPCGCD-UHFFFAOYSA-N 0.000 description 1
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- BXHHZLMBMOBPEH-UHFFFAOYSA-N diethyl-(2-methoxyethyl)-methylazanium Chemical compound CC[N+](C)(CC)CCOC BXHHZLMBMOBPEH-UHFFFAOYSA-N 0.000 description 1
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- 150000002367 halogens Chemical class 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Conductive Materials (AREA)
Description
本発明は、例えば導電性フィルムなどの導電性複合体に関する。 The present invention relates to a conductive composite such as a conductive film.
導電性フィルムとしては、例えば、フィルム基材(マトリックス成分)としてポリエチレンテレフタレート(PET)が用いられ、導電性物質として酸化インジウム錫(ITO)が用いられたITO−PET導電性フィルムがあり、該導電性フィルムは、フレキシブルデバイスとして広く使用されている。フィルム基材としては、PETの他に、例えばポリエチレンスルホネート(PES)、ポリカーボネート(PC)、ポリアリレート(PAR)などの樹脂が使用され、導電性物質としては、ITOの他に、例えば酸化錫(SnO)、酸化亜鉛(ZnO)、酸化錫カドミウム(CdSnO4)などの無機材料が使用されている。 Examples of the conductive film include an ITO-PET conductive film in which polyethylene terephthalate (PET) is used as a film base material (matrix component) and indium tin oxide (ITO) is used as a conductive substance. The property film is widely used as a flexible device. As the film substrate, in addition to PET, for example, a resin such as polyethylene sulfonate (PES), polycarbonate (PC), polyarylate (PAR), etc. is used. Inorganic materials such as SnO), zinc oxide (ZnO), and tin cadmium oxide (CdSnO 4 ) are used.
ところが、PETをはじめとした上記の樹脂は、化石燃料由来の材料であり、環境面、原料埋蔵量などの点で懸念がある。また、ITOについても、インジウムの埋蔵量に限界があるため、インジウムの価格高騰や枯渇という不安材料がある。
そのため、フィルム基材、導電性物質ともに、他の材料での代替が急務になっている。
However, the above-mentioned resins including PET are materials derived from fossil fuels, and there are concerns in terms of environmental aspects and raw material reserves. In addition, ITO also has an anxiety that the price of indium is rising or depleted due to its limited amount of indium.
For this reason, there is an urgent need to replace the film base material and the conductive material with other materials.
このような事情を背景として、例えば特許文献1には、表面にカルボキシ基を有する改質微細セルロースをフィルム基材として用い、導電性物質として、カーボンナノチューブなどの微細カーボンを用いた導電性フィルムが開示されている。この導電性フィルムは、改質微細セルロースと微細カーボンとが分散した分散液をプレート上にキャストし、乾燥する方法などで製造される。 Against such a background, for example, Patent Document 1 discloses a conductive film using modified fine cellulose having a carboxy group on the surface as a film base and using fine carbon such as carbon nanotubes as a conductive substance. It is disclosed. This conductive film is manufactured by a method in which a dispersion in which modified fine cellulose and fine carbon are dispersed is cast on a plate and dried.
しかしながら、改質微細セルロースと微細カーボンとが分散した分散液は、微細カーボンの分散性が充分とは言えなかった。特に、微細カーボンのうち、単層カーボンナノチューブなどの超微細なカーボンは凝集しやすい。単層カーボンナノチューブは他のカーボン材料と比べても、導電性は非常に高いが、著しく凝集しやすく、使用が制限されていた。微細カーボンの分散性が不充分な分散液から得られた導電性フィルムにおいては、微細カーボンの分散状態にムラが生じ、それに起因した透明性のムラ、導電性不良などの問題が生じやすかった。 However, a dispersion in which modified fine cellulose and fine carbon are dispersed cannot be said to have sufficient dispersibility of fine carbon. In particular, among fine carbons, ultrafine carbon such as single-walled carbon nanotubes tends to aggregate. Single-walled carbon nanotubes have a very high electrical conductivity compared to other carbon materials, but are remarkably easily aggregated, and their use has been limited. In a conductive film obtained from a dispersion with insufficient dispersibility of fine carbon, the dispersion state of fine carbon is uneven, and problems such as uneven transparency and poor conductivity are likely to occur.
本発明は、上記事情に鑑みてなされたもので、ムラのない優れた透明性や、安定した導電性を有する導電性フィルムなどの導電性複合体の提供を課題とする。 This invention is made | formed in view of the said situation, and makes it a subject to provide electroconductive composites, such as an electroconductive film which has the outstanding transparency which has nonuniformity, and the stable electroconductivity.
本発明の導電性複合体は、カルボキシ基で修飾されたセルロースナノファイバーと、カルボキシ基で修飾されたカーボンナノチューブとを含有することを特徴とする。
本発明の導電性複合材は、さらに架橋剤を含有して形成されていることが好ましい。
前記カルボキシ基で修飾されたセルロースナノファイバーは、カルボキシ基量が0.1〜3.5mmol/gであることが好ましい。
The conductive composite of the present invention is characterized by containing cellulose nanofibers modified with a carboxy group and carbon nanotubes modified with a carboxy group.
The conductive composite material of the present invention is preferably formed to further contain a crosslinking agent.
The cellulose nanofiber modified with the carboxy group preferably has a carboxy group content of 0.1 to 3.5 mmol / g.
本発明によれば、ムラのない透明性や、安定した導電性を有する導電性フィルムなどの導電性複合体を提供できる。 According to the present invention, it is possible to provide a conductive composite such as a conductive film having non-uniform transparency and stable conductivity.
以下、本発明を詳細に説明する。
本発明の導電性複合体は、カルボキシ基で修飾されたセルロースナノファイバーと、カルボキシ基で修飾されたカーボンナノチューブとを含有する。以下、セルロースナノファイバーのことをCSNF、カーボンナノチューブのことをCNTという場合がある。また、カルボキシ基で修飾されたセルロースナノファイバーを修飾CSNF、カルボキシ基で修飾されたカーボンナノチューブを修飾CNTという場合がある。
本発明の導電性複合体の好適な形態としては、例えば、水を主成分とする水性溶媒に修飾CSNFと修飾CNTとが分散した複合分散液をキャスト用基材上にキャスト、乾燥し、形成されたフィルムを剥離する方法で製造された導電性フィルム;上述の複合分散液を絶縁性基材上にキャストまたは塗布、乾燥する方法で形成された導電層;上述の複合分散液を導電性インクとして用い、絶縁性基材上に印刷する方法で形成された導電性薄膜やパターン化された導電性薄膜などが挙げられる。
Hereinafter, the present invention will be described in detail.
The conductive composite of the present invention contains cellulose nanofibers modified with carboxy groups and carbon nanotubes modified with carboxy groups. Hereinafter, cellulose nanofiber may be referred to as CSNF, and carbon nanotube may be referred to as CNT. In some cases, cellulose nanofibers modified with carboxy groups are referred to as modified CSNF, and carbon nanotubes modified with carboxy groups are referred to as modified CNTs.
As a suitable form of the conductive composite of the present invention, for example, a composite dispersion in which modified CSNF and modified CNT are dispersed in an aqueous solvent mainly containing water is cast on a base material for casting, dried, and formed. A conductive film produced by a method of peeling the formed film; a conductive layer formed by a method of casting, applying or drying the above-mentioned composite dispersion on an insulating substrate; and a conductive ink using the above-mentioned composite dispersion And a conductive thin film formed by a method of printing on an insulating substrate or a patterned conductive thin film.
本発明で使用される修飾CSNFは、導電性複合体のマトリクス成分であって、セルロース類を改質して、その表面にカルボキシ基を導入する改質工程と、該改質工程で得られた改質セルロース類をナノオーダーに微細化する微細化工程とにより製造される。
なお、修飾CSNFの有するカルボキシ基は、酸型(−COOH)であっても、塩型(−COO−)であってもよい。また、カルボキシ基の誘導体、すなわち、カルボキシ基から誘導されるアルデヒド基、エステル基、COO−NR2(RはH,アルキル基、またはベンジル基、またはフェニル基、またはヒドロキシアルキル基で、2つのRが同一でも異なっていてもよい。)で表されるアミド基などであってもよい。
The modified CSNF used in the present invention is a matrix component of a conductive composite, which is obtained by modifying a cellulose and introducing a carboxy group on the surface thereof, and the modifying step. It is manufactured by a refinement process for refined modified celluloses to the nano order.
The carboxy group of the modified CSNF may be in the acid form (—COOH) or the salt form (—COO − ). A derivative of a carboxy group, that is, an aldehyde group derived from a carboxy group, an ester group, COO-NR 2 (R is H, an alkyl group, a benzyl group, a phenyl group, or a hydroxyalkyl group, and two R May be the same as or different from each other.
CSNFは、線膨張率が低いために様々な温度条件下でも変形しにくく、安定した加工性を示す、高強度である、などの特性を有するものであるが、特に表面がカルボキシ基で修飾された修飾CSNFは、これらの特性に加えて、水中でカルボキシ基が反発しあうことで、水への分散性が非常に良好である。そのため、修飾CSNFは複合分散液中で良好に分散し、乾燥工程においても反発が維持し、修飾CSNF同士、さらには分散させたCNTの凝集を阻害することができる。特に修飾CNTでは、その反発をより大きくすることもできる。その結果、該複合分散液から形成された導電性複合体は、高い強度や安定した加工性だけでなく、ムラのない優れた透明性、安定した導電性を発現する。 Since CSNF has a low coefficient of linear expansion, it is difficult to be deformed under various temperature conditions, exhibits stable processability, and has high strength. However, the surface is particularly modified with a carboxy group. In addition to these properties, the modified CSNF has very good dispersibility in water due to repulsion of carboxy groups in water. Therefore, the modified CSNF is well dispersed in the composite dispersion, and the repulsion is maintained even in the drying step, and the aggregation of the modified CSNFs and the dispersed CNTs can be inhibited. Particularly in the case of modified CNT, the repulsion can be further increased. As a result, the conductive composite formed from the composite dispersion exhibits not only high strength and stable processability, but also excellent transparency with no unevenness and stable conductivity.
原料に用いるセルロース類としては、木材パルプ(サルファイトパルプやクラフトパルプなどの各種パルプ化法によって得られる木材パルプ。)、非木材パルプ、古紙パルプ、コットン、バクテリアセルロース、バロニアセルロース、ホヤセルロース、微細セルロース、微結晶セルロースなどを使用できるが、特に、セルロースI型の結晶構造を有する天然セルロースが好ましい。セルロースI型の結晶構造を有する天然セルロースは、その内部に結晶領域を有しているが、該結晶領域は改質工程において侵食されず、表面のみが酸化される。すなわち、天然セルロースを原料として用いると、結晶構造を保ちつつ、表面のみを酸化させることができ、その分子が個々にばらけることなく、ナノファイバー状になりやすい。 Celluloses used as raw materials include wood pulp (wood pulp obtained by various pulping methods such as sulfite pulp and kraft pulp), non-wood pulp, waste paper pulp, cotton, bacterial cellulose, valonia cellulose, squirt cellulose, fine Cellulose, microcrystalline cellulose, and the like can be used, and natural cellulose having a cellulose I type crystal structure is particularly preferable. Natural cellulose having a cellulose I-type crystal structure has a crystal region therein, but the crystal region is not eroded in the modification step, and only the surface is oxidized. That is, when natural cellulose is used as a raw material, only the surface can be oxidized while maintaining the crystal structure, and the molecules are not scattered individually, and are easily formed into nanofibers.
改質工程の具体的方法としては、N−オキシル化合物(触媒)の存在下、共酸化剤を用いて、原料のセルロース類を酸化する方法が好ましい。このような方法によれば、セルロース類の構造を可能な限り維持しつつ、その表面の一級水酸基(C6位)を選択的に酸化して、カルボキシ基とすることができる。特に、上述したように、天然セルロースの結晶構造を持つセルロース類を原料として用いると、N−オキシル化合物が結晶構造内に入り込むことなく酸化できるため、結晶構造を維持することができる。 As a specific method of the reforming step, a method of oxidizing raw material celluloses using a co-oxidant in the presence of an N-oxyl compound (catalyst) is preferable. According to such a method, the primary hydroxyl group (C6 position) on the surface can be selectively oxidized to form a carboxy group while maintaining the structure of celluloses as much as possible. In particular, as described above, when cellulose having a crystal structure of natural cellulose is used as a raw material, the N-oxyl compound can be oxidized without entering the crystal structure, so that the crystal structure can be maintained.
N−オキシル化合物としては、制限はないが、2,2,6,6−テトラメチルピペリジノオキシラジカル(TEMPO)が好ましく用いられる。
共酸化剤としては、ハロゲン、次亜ハロゲン酸、亜ハロゲン酸、過ハロゲン酸、またはこれらの塩、ハロゲン酸化物、窒素酸化物、過酸化物など、酸化反応を促進する酸化剤であれば用いることができる。具体的には、入手の容易さや反応性から、次亜塩素酸ナトリウムが好ましい。
また、酸化反応の反応系には、臭化物やヨウ化物を共存させると、酸化反応をより円滑に進行させ、カルボキシ基の導入効率を高めることができる。臭化物としては、コストや安定性から、臭化ナトリウムを用いることが好ましい。
The N-oxyl compound is not limited, but 2,2,6,6-tetramethylpiperidinooxy radical (TEMPO) is preferably used.
As the co-oxidant, halogen, hypohalous acid, halous acid, perhalogen acid, or salts thereof, halogen oxides, nitrogen oxides, peroxides, and the like are used as long as they promote the oxidation reaction. be able to. Specifically, sodium hypochlorite is preferable from the viewpoint of availability and reactivity.
In addition, when bromide or iodide coexists in the reaction system of the oxidation reaction, the oxidation reaction can proceed more smoothly and the introduction efficiency of the carboxy group can be increased. As bromide, sodium bromide is preferably used from the viewpoint of cost and stability.
TEMPOの使用量は、触媒として機能する量であればよい。共酸化剤、臭化物またはヨウ化物の使用量についても、酸化反応を促進することができる量であればよい。
酸化反応の反応系は、アルカリ性に維持されることが好ましく、pH9〜11に維持されることがより好ましい。具体的には、水酸化ナトリウム、水酸化リチウム、水酸化カリウムなどの水溶液やアンモニア水溶液などのアルカリ水溶液を、反応系に適宜することで、反応中のpH低下を抑制し、pHをアルカリ性に維持することが好ましい。アルカリ水溶液としては、コストや入手の容易さから、水酸化ナトリウムを使用することが好ましい。
なお、本明細書においてpHは、20℃における値である。
The amount of TEMPO used may be an amount that functions as a catalyst. The amount of the co-oxidant, bromide or iodide used may be an amount that can promote the oxidation reaction.
The reaction system for the oxidation reaction is preferably maintained alkaline, and more preferably pH 9-11. Specifically, an aqueous solution of sodium hydroxide, lithium hydroxide, potassium hydroxide or the like or an alkaline aqueous solution such as an aqueous ammonia solution is appropriately used in the reaction system to suppress the pH drop during the reaction and maintain the pH alkaline. It is preferable to do. As the alkaline aqueous solution, it is preferable to use sodium hydroxide from the viewpoint of cost and availability.
In addition, in this specification, pH is a value in 20 degreeC.
酸化反応を終了させるためには、系内のpHを保ちながら、アルコールを添加して、共酸化剤の反応を完全に終了させる必要がある。ここで用いるアルコールとしては、反応を迅速に終了させ得る点から、メタノール、エタノール、プロパノールなどの低分子量のアルコールが好ましい。これらのなかでは、反応により生成物する副生成物の安全性などから、メタノールが好ましい。 In order to complete the oxidation reaction, it is necessary to completely complete the reaction of the co-oxidant by adding alcohol while maintaining the pH in the system. The alcohol used here is preferably a low molecular weight alcohol such as methanol, ethanol, propanol or the like because the reaction can be completed quickly. Among these, methanol is preferable from the viewpoint of safety of by-products generated by the reaction.
酸化反応の終了は、所望のカルボキシ基が導入されたと判断されたタイミングで行う。例えば、導入されるカルボキシ基量と、pH調整のために添加され、酸化反応にともなって消費されるアルカリ量とは、非常に良好な相関関係がある。よって、使用する原料および酸化条件ごとに、導入されるカルボキシ基量と、消費されるアルカリ量との関係を示す検量線をあらかじめ作製しておく。そして、酸化反応の際に、消費されるアルカリ量をモニタリングする。これにより、所望のカルボキシ基が導入されたことを消費されたアルカリ量から判断でき、その時点で酸化反応を終了させることが可能となる。例えば、原料に針葉樹クラフトパルプを用いた場合には、約2.5mmol/gのアルカリが消費されたところでカルボキシ基量を測定すると1.6mmol/g、さらに、2.8mmol/g程度のアルカリが消費されたところでカルボキシ基量を測定すると、1.8mmol/gであった。このようにして予めデータを採り、検量線を作製しておくことで、消費されるアルカリ量から導入されたカルボキシ基量がわかる。
なお、導入されるカルボキシ基量は、原料として用いるセルロース類の種類や、添加する共酸化剤の量などに依存する。また、セルロース類の表面を膨潤させて反応を進めることにより、膨潤させずに反応を進める場合に比べて、カルボキシ基の導入量を増加させることもできる。例えば、木材パルプを原料として用いた場合、膨潤させない場合には1.6mmol/g程度であるカルボキシ基量を、その表面を膨潤させて反応を進めることにより2.0mmol/g以上とすることが可能となる。
The oxidation reaction is terminated at the timing when it is determined that the desired carboxy group has been introduced. For example, there is a very good correlation between the amount of carboxy group introduced and the amount of alkali added for pH adjustment and consumed in the oxidation reaction. Therefore, a calibration curve indicating the relationship between the amount of carboxy groups introduced and the amount of alkali consumed is prepared in advance for each raw material to be used and oxidation conditions. The amount of alkali consumed during the oxidation reaction is monitored. Thereby, it can be judged from the amount of alkali consumed that the desired carboxy group has been introduced, and the oxidation reaction can be terminated at that point. For example, when softwood kraft pulp is used as a raw material, when about 2.5 mmol / g of alkali is consumed, the amount of carboxy group is measured to obtain 1.6 mmol / g, and about 2.8 mmol / g of alkali. When it was consumed, the amount of carboxy group was measured and found to be 1.8 mmol / g. In this way, by collecting data in advance and preparing a calibration curve, the amount of carboxy groups introduced can be determined from the amount of alkali consumed.
In addition, the amount of carboxy groups introduced depends on the type of cellulose used as a raw material, the amount of co-oxidant to be added, and the like. Moreover, the amount of carboxy groups introduced can be increased by allowing the surface of celluloses to swell to advance the reaction, compared to the case where the reaction is allowed to proceed without swelling. For example, when wood pulp is used as a raw material, the amount of carboxy groups, which is about 1.6 mmol / g when not swelled, may be made 2.0 mmol / g or more by advancing the reaction by swelling the surface. It becomes possible.
酸化反応の終了後、酸化反応により表面にカルボキシ基が導入されたセルロース類を洗浄する。上述のように、アルカリ性で酸化反応を行った場合、導入されたカルボキシ基はアルカリと塩を形成しているが、洗浄は、カルボキシ基がアルカリと塩を形成している状態のまま行ってもよいし、酸を添加して酸型(カルボン酸:−COOH)にしてから、行ってもよい。また、有機溶剤を添加して、表面にカルボキシ基が導入されたセルロース類を不溶化してから、洗浄してもよい。これらのなかでは、ハンドリング性、収率などの点から、酸を添加して酸型(カルボン酸:−COOH)にしてから、洗浄する方法が好ましい。洗浄溶媒としては、水が好ましい。 After completion of the oxidation reaction, celluloses having carboxy groups introduced on the surface by the oxidation reaction are washed. As described above, when the oxidation reaction is performed in an alkaline state, the introduced carboxy group forms a salt with the alkali, but washing may be performed while the carboxy group forms a salt with the alkali. Alternatively, an acid may be added to form an acid form (carboxylic acid: —COOH). Moreover, you may wash | clean, after adding the organic solvent and making the cellulose in which the carboxy group was introduce | transduced into the surface insolubilized. Among these, from the viewpoint of handling properties and yield, a method of washing after adding an acid to form an acid form (carboxylic acid: —COOH) is preferable. As the washing solvent, water is preferred.
上述のようにして、改質工程を行った後、該改質工程で得られた改質セルロース類をナノオーダーに微細化する微細化工程を行う。
具体的には、改質セルロース類を分散媒である水に浸漬した後、アルカリを添加して、pHを6〜12にすることが好ましい。このようなpH領域において微細化工程を行うと、カルボキシ基の静電気的な反発から、改質セルロース類をナノオーダーまで解繊して、透明性の高い分散液を得ることができる。これに対して、pHが6未満では、上述のような反発が起こりにくく、得られた分散液は不透明となる。ここで使用されるアルカリとしては、水酸化ナトリウム、水酸化リチウム、水酸化カリウムなどの水溶液やアンモニア水溶液、さらには、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム、水酸化ベンジルトリメチルアンモニウムなどの有機アルカリも使用できる。
As described above, after performing the reforming step, a refining step of refining the modified celluloses obtained in the reforming step to the nano order is performed.
Specifically, it is preferable to adjust the pH to 6 to 12 by immersing the modified cellulose in water as a dispersion medium and then adding an alkali. When the micronization step is performed in such a pH range, a highly transparent dispersion liquid can be obtained by defibrating modified celluloses to the nano-order from electrostatic repulsion of carboxy groups. On the other hand, when the pH is less than 6, the above-mentioned repulsion hardly occurs and the obtained dispersion becomes opaque. Examples of the alkali used here include aqueous solutions of sodium hydroxide, lithium hydroxide, potassium hydroxide and the like, aqueous ammonia solutions, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrahydroxide hydroxide. Organic alkalis such as butylammonium and benzyltrimethylammonium hydroxide can also be used.
分散媒として、上述のように水を用いた場合、安定な分散状態を得ることができるが、その後の乾燥条件、分散液物性の改良・制御などの種々の目的に応じて、水以外の溶媒を用いてもよい。そのような溶媒としては、例えばメタノール、エタノール、イソプロピルアルコール、tert−ブタノール、エーテル類、ケトン類などが挙げられ、これらのうちの1種以上を使用できる。 When water is used as a dispersion medium as described above, a stable dispersion state can be obtained. However, depending on various purposes such as subsequent drying conditions and improvement / control of dispersion physical properties, a solvent other than water can be used. May be used. Examples of such a solvent include methanol, ethanol, isopropyl alcohol, tert-butanol, ethers, and ketones, and one or more of these can be used.
微細化方法としては、高圧ホモジナイザー、超高圧ホモジナイザー、ビーズミル、ボールミル、カッターミル、ジェットミル、グラインダー、ジューサーミキサー、ホモミキサー、超音波ホモジナイザー、ナノジナイザー、水中対向衝突などが挙げられ、任意の時間処理すればよい。
また、このようにして微細化を行うと、微細化に伴って次第に分散液が高粘度化し、高いエネルギーを要するようになる。よって、分散液中の改質セルロース類の量は、10質量%以下として、微細化を開始することが好ましい。
Examples of micronization methods include high-pressure homogenizers, ultra-high-pressure homogenizers, bead mills, ball mills, cutter mills, jet mills, grinders, juicer mixers, homomixers, ultrasonic homogenizers, nanogenizers, and underwater collisions. That's fine.
In addition, when miniaturization is performed in this way, the dispersion gradually increases in viscosity with the miniaturization and requires high energy. Therefore, it is preferable to start refinement by setting the amount of the modified cellulose in the dispersion to 10% by mass or less.
以上のように改質工程と微細化工程とを行うことにより、C6位にカルボキシ基を有する修飾CSNFを得ることができる。
修飾CSNFのカルボキシ基量(修飾CSNF1g中に含まれるカルボキシ基のモル量)は、0.1〜3.5mmol/gが好ましい。この範囲の下限値以上であると、修飾CSNFと修飾CNTとを含有する複合分散液の分散性、粘度が適度となり、取扱性の点で好適である。一方、この範囲の上限値以下であると、最終的に得られた導電性複合体の耐水性が良好となるし、修飾CSNFと修飾CNTとを含有する複合分散液中における修飾CNTの分散性を低下させるおそれもない。
このようなカルボキシ基量のうち、修飾CSNFの安定性と製造しやすさの点からは、1.0〜2.0mmol/gが好ましい。また、最終的に得られる導電性複合体の導電性が良好となり、また、複合分散液の粘度がキャスト、印刷などに適した範囲となる点からは、1.5〜3.5mmol/gが好ましい。また、導電性複合体を湿度センサーとして利用する場合には、湿度に対する応答性に優れる点から、2.0〜3.5mmol/gが好ましい。
なお、修飾CSNFのカルボキシ基量は、例えば0.5N水酸化ナトリウム水溶液を用いた電導度滴定法により測定できる。
By performing the reforming step and the miniaturization step as described above, a modified CSNF having a carboxy group at the C6 position can be obtained.
The amount of the carboxy group of the modified CSNF (the molar amount of the carboxy group contained in 1 g of the modified CSNF) is preferably 0.1 to 3.5 mmol / g. When it is at least the lower limit of this range, the dispersibility and viscosity of the composite dispersion containing the modified CSNF and the modified CNT become appropriate, which is preferable in terms of handleability. On the other hand, if it is below the upper limit of this range, the water resistance of the finally obtained conductive composite becomes good, and the dispersibility of the modified CNT in the composite dispersion containing the modified CSNF and the modified CNT There is also no risk of lowering.
Among such carboxy group amounts, 1.0 to 2.0 mmol / g is preferable from the viewpoint of the stability of the modified CSNF and the ease of production. In addition, from the point that the conductivity of the finally obtained conductive composite becomes good and the viscosity of the composite dispersion is in a range suitable for casting, printing, etc., 1.5 to 3.5 mmol / g is preferable. Moreover, when using an electroconductive composite_body | complex as a humidity sensor, 2.0-3.5 mmol / g is preferable from the point which is excellent in the responsiveness with respect to humidity.
In addition, the amount of carboxy groups of the modified CSNF can be measured by, for example, a conductivity titration method using a 0.5N aqueous sodium hydroxide solution.
修飾CSNFの繊維幅は、平均値として、1〜200nmが好ましい。このような繊維幅であると、複合分散液中での分散性がより優れ、その結果、透明性、導電性の安定性に優れた導電性複合体が得られやすい。特に1〜50nmの範囲にあると、得られる導電性複合体の透明性が高く、表面の外観も良い。また、繊維長は、平均値として、100〜3000nmが好ましい。このような繊維幅と繊維長とを有し高アスペクト比の修飾CSNFは、強度に優れ、少ない含有量で高強度の導電性複合体を形成することができる。 The fiber width of the modified CSNF is preferably 1 to 200 nm as an average value. With such a fiber width, the dispersibility in the composite dispersion is more excellent, and as a result, a conductive composite excellent in transparency and conductivity stability is easily obtained. In particular, when the thickness is in the range of 1 to 50 nm, the resulting conductive composite has high transparency and good surface appearance. The fiber length is preferably 100 to 3000 nm as an average value. The modified CSNF having such a fiber width and fiber length and having a high aspect ratio is excellent in strength and can form a high-strength conductive composite with a small content.
なお、繊維幅および繊維長の平均値は、原子間力顕微鏡(AFM)を用いて複数の修飾CSNFの繊維幅および繊維長を測定し、その平均を求めることで得られる。この際、測定するサンプル数は、少なくとも10とする。 In addition, the average value of fiber width and fiber length is obtained by measuring the fiber width and fiber length of a plurality of modified CSNFs using an atomic force microscope (AFM) and calculating the average. At this time, the number of samples to be measured is at least 10.
本発明で使用される修飾CNTは、導電性複合体の導電性物質として使用されるものであって、カーボンナノチューブの表面をカルボキシ基で修飾したものである。カルボキシ基による修飾方法としては、例えば、シュウ酸を用いた修飾方法がある。具体的には、例えばZhang X.et al.,J.Phys.Chem.B,108(2004)16435.で示される方法を採用できる。また、修飾CNTの有するカルボキシ基は、酸型(−COOH)であっても、塩型(−COO−)であってもよい。また、先に例示したようなカルボキシ基の誘導体であってもよい。 The modified CNT used in the present invention is used as a conductive substance of a conductive composite and is obtained by modifying the surface of a carbon nanotube with a carboxy group. As a modification method using a carboxy group, for example, there is a modification method using oxalic acid. Specifically, for example, the method shown by Zhang X. et al., J. Phys. Chem. B, 108 (2004) 16435. can be employed. Further, the carboxy group of the modified CNT may be acid type (—COOH) or salt type (—COO − ). Moreover, the derivative | guide_body of a carboxy group illustrated previously may be sufficient.
カーボンナノチューブには、一般に、一層のグラファイトシートを筒状の形状に丸めた構造を持つ単層カーボンナノチューブと、該単層カーボンナノチューブが同心円状に積層した構造を持つ多層カーボンナノチューブがあるが、本発明では、単層カーボンナノチューブの表面をカルボキシ基で修飾した修飾CNTを用いることが好ましい。単層カーボンナノチューブは、比表面積が大きく、高い導電性が得られやすいが、未修飾の場合には、その大きな比表面積に起因して凝集しやすい。これに対して、表面をカルボキシ基で修飾することにより、単層カーボンナノチューブであってもその分散性を高めることができる。そのため、このような修飾CNTを使用することによって、ムラのない優れた透明性、安定した導電性を示す導電性複合体を形成することができる。 Generally, carbon nanotubes include single-walled carbon nanotubes having a structure in which a single graphite sheet is rolled into a cylindrical shape, and multi-walled carbon nanotubes having a structure in which the single-walled carbon nanotubes are concentrically stacked. In the invention, it is preferable to use a modified CNT obtained by modifying the surface of a single-walled carbon nanotube with a carboxy group. Single-walled carbon nanotubes have a large specific surface area, and high electrical conductivity is easily obtained. On the other hand, by modifying the surface with a carboxy group, even the single-walled carbon nanotube can be improved in dispersibility. Therefore, by using such modified CNT, it is possible to form a conductive composite exhibiting excellent transparency with no unevenness and stable conductivity.
修飾CNTのカルボキシ基量(修飾CNT1g中に含まれるカルボキシ基のモル量)は、0.1〜2.0mmol/gが好ましく、0.2〜0.7mmol/gがより好ましい。この範囲の下限値以上であると、修飾CNTの上述の複合分散液中での分散性が良好となり、凝集しにくい。一方、上限値以下であると、導電性に優れるとともに、カーボンナノチューブの構造が維持されやすい。 0.1-2.0 mmol / g is preferable and, as for the amount of carboxy groups of modified CNT (molar amount of the carboxy group contained in 1 g of modified CNT), 0.2-0.7 mmol / g is more preferable. When it is at least the lower limit of this range, the dispersibility of the modified CNT in the above-mentioned composite dispersion becomes good, and it is difficult to aggregate. On the other hand, when it is not more than the upper limit value, the conductivity is excellent and the structure of the carbon nanotube is easily maintained.
また、修飾CNTの直径は、平均値として、4〜5nmが好ましい。このような直径であると、複合分散液中での分散性がより優れる。また、長さは、平均値として、0.5〜1.5μmが好ましい。
なお、直径および長さの平均値も、繊維幅および繊維長の場合と同様にして求められる。
The diameter of the modified CNT is preferably 4 to 5 nm as an average value. With such a diameter, the dispersibility in the composite dispersion is more excellent. The length is preferably 0.5 to 1.5 μm as an average value.
In addition, the average value of a diameter and length is calculated | required similarly to the case of fiber width and fiber length.
修飾CNTとしては市販品も使用でき、単層カーボンナノチューブの表面がカルボキシ基で修飾された修飾CNTとしては、シグマアルドリッチジャパン社から購入可能な「Single−walled carbon nanotubes,carboxylic acid functionalized(652490−250MG,1G)」などがある。この修飾CNTは、カルボキシ基量:0.22〜0.67mmol/g、直径(平均値):4〜5nm、長さ(平均値):0.5〜1.5μm、炭素基準の純度は>90%である。 Commercially available products can also be used as the modified CNT, and the modified CNT whose surface of the single-walled carbon nanotube is modified with a carboxy group is available as “Single-walled carbon nanotubes, carboxylic acid acid functionalized (65490-250MG) that can be purchased from Sigma-Aldrich Japan. , 1G) ”. This modified CNT has a carboxy group amount of 0.22 to 0.67 mmol / g, a diameter (average value): 4 to 5 nm, a length (average value): 0.5 to 1.5 μm, and a purity based on carbon> 90%.
修飾CSNFと修飾CNTとを含有する複合分散液の調製法には特に制限はないが、修飾CSNFの分散液と修飾CNTの分散液とを別々に調製した後、これらを混合する方法が好ましい。また、修飾CSNFは、一旦乾燥すると、水に再分散しにくくなるため、微細化工程後の修飾CSNFの分散液を乾燥せずに、複合分散液の調製に用いることが好ましい。
また、複合分散液には、溶媒として水以外のものが含まれてもよいが、溶媒の主成分(50質量%以上である成分)は水とすることが好ましい。
複合分散液における修飾CSNFと修飾CNTの濃度としては、導電性複合体を良好に形成できる点、複合分散液の安定性などの点から、これらの合計濃度として、0.01〜5質量%が好ましく、特に0.1〜1質量%の範囲が好ましい。0.01質量%未満では、製膜の効率が低く、5質量%を超えると分散性が低下し、一部凝集が見られる場合がある。
The method of preparing the composite dispersion containing the modified CSNF and the modified CNT is not particularly limited, but a method of mixing the modified CSNF dispersion and the modified CNT dispersion separately and then mixing them is preferable. Further, since the modified CSNF is difficult to re-disperse in water once dried, it is preferable to use the modified CSNF for preparing a composite dispersion without drying the dispersion of the modified CSNF after the refinement process.
In addition, the composite dispersion may contain a solvent other than water, but the main component of the solvent (a component of 50% by mass or more) is preferably water.
The concentration of the modified CSNF and the modified CNT in the composite dispersion is 0.01 to 5% by mass as the total concentration of these from the viewpoints of forming a conductive composite well and the stability of the composite dispersion. The range of 0.1-1 mass% is especially preferable. If it is less than 0.01% by mass, the efficiency of film formation is low, and if it exceeds 5% by mass, the dispersibility may be lowered and some aggregation may be observed.
修飾CSNFと修飾CNTとの比率としては、修飾CSNF100質量部に対して、修飾CNTが0.5〜100質量部の範囲が好ましく、より好ましくは、0.5〜20質量部の範囲である。このような範囲であると、導電性複合体を良好に形成できるとともに、形成された導電性複合体の導電性、透明性が良好となる。 The ratio of the modified CSNF to the modified CNT is preferably in the range of 0.5 to 100 parts by mass, more preferably in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass of the modified CSNF. Within such a range, the conductive composite can be formed satisfactorily, and the conductivity and transparency of the formed conductive composite are improved.
複合分散液には、得られる導電性複合体の導電性、柔軟性を向上させるために、イオン液体が添加されてもよい。イオン液体には、親水性イオン液体、疎水性イオン液体があるが、添加対象の液には分散媒として水が使用されることが望ましいため、その場合には親水性イオン液体を添加することが好ましい。
親水性イオン液体としては、特に制限はないが、例えば、1,3−ジメチルイミダゾリウムジメチルホスファート、1−ブチル−3−メチルイミダゾリウムヘキサフルオロホスファート、1−エチル−3−メチルイミダゾリウムエチルスルファート、1−エチル−3−メチルイミダゾリウム硫酸水素塩、1−エチル−3−メチルイミダゾリウムメタンスルホン酸塩、1−エチル−3−メチルイミダゾリウムトリフルオロメタンスルホナート、1−ヘキシル−3−メチルイミダゾリウムクロリド、1−メチル−3−n−オクチルイミダゾリウムクロリド、1−メチル−3−プロピルイミダゾリウムヨージド、1−エチル−3−メチルピリジニウムエチルスルファート、N,N−ジエチル−N−メチル−N−(2−メトキシエチル)アンモニウムテトラフルオロボレートなどが挙げられる。
An ionic liquid may be added to the composite dispersion in order to improve the conductivity and flexibility of the conductive composite obtained. The ionic liquid includes a hydrophilic ionic liquid and a hydrophobic ionic liquid, but it is desirable to use water as a dispersion medium for the liquid to be added. In this case, the hydrophilic ionic liquid may be added. preferable.
The hydrophilic ionic liquid is not particularly limited. For example, 1,3-dimethylimidazolium dimethyl phosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium ethyl Sulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3- Methylimidazolium chloride, 1-methyl-3-n-octylimidazolium chloride, 1-methyl-3-propylimidazolium iodide, 1-ethyl-3-methylpyridinium ethylsulfate, N, N-diethyl-N- Methyl-N- (2-methoxyethyl) ammonium Such as tigers fluoroborate and the like.
また、複合分散液には、得られる導電性複合体に耐水性、耐湿性を付与するために、架橋剤として、カルボジイミド基、オキサゾリン基、イソシアネート基、エポキシ基、アミノ基などの反応性官能基を有する化合物の1種以上を添加できる。これらのなかでも、カルボジイミド基、オキサゾリン基、イソシアネート基のうちの1つ以上を有する化合物は、修飾CSNFや修飾CNTに含まれる水酸基やカルボキシル基などとの反応が効率よく、しかも低温度で進行し得るため、より高い耐水性、耐湿性を付与できる。特に、カルボジイミド基、オキサゾリン基は、室温などの低温で緩やかに反応するため、少量で高い添加効率を発揮し、架橋剤を含んで形成される導電性複合体の導電性を低下させること無く、耐水性・耐湿性を付与できる。
これら架橋剤を添加する場合には、修飾CSNF100質量部に対して、架橋剤が0.1〜30質量部の範囲が好ましい。
In addition, in the composite dispersion, a reactive functional group such as a carbodiimide group, an oxazoline group, an isocyanate group, an epoxy group, and an amino group is used as a crosslinking agent in order to impart water resistance and moisture resistance to the obtained conductive composite. One or more of the compounds having can be added. Among these, a compound having one or more of a carbodiimide group, an oxazoline group, and an isocyanate group efficiently reacts with a hydroxyl group or a carboxyl group contained in the modified CSNF or the modified CNT, and proceeds at a low temperature. Therefore, higher water resistance and moisture resistance can be imparted. In particular, the carbodiimide group and oxazoline group react slowly at a low temperature such as room temperature, so that high addition efficiency is exhibited in a small amount without reducing the conductivity of the conductive composite formed including the crosslinking agent, Can provide water resistance and moisture resistance.
When adding these crosslinking agents, the range of 0.1-30 mass parts of crosslinking agents is preferable with respect to 100 mass parts of modified CSNF.
複合分散液には、導電性物質として、修飾CNT以外の物質、例えばITO、PEDOT、金属ナノワイヤーや金属微粒子、酸化金属微粒子、カーボンブラックなどを併用し、これらの導電性物質が導電性複合体に含まれるようにしてもよい。また、マトリックス成分として、ポリエチレン、ポリプロピレンなどのポリオレフィン、ポリエステル、ポリオール、ポリウレタン、ポリアミド、ポリカーボネート、ポリカルボジイミド、ポリアクリル酸、ポリオキサゾリンなどの樹脂を修飾CSNFの100質量部に対して100質量部以下の範囲で併用して、これらの樹脂が導電性複合体に含まれるようにしてもよい。
また、複合分散液は、ラジカル補足剤、脱泡剤、界面活性剤、アルコールなどの溶媒、着色剤、滑剤、紫外線吸収剤、金属粒子、カーボン材料、保湿剤、乾燥剤、吸着剤などを性能を阻害しない範囲で含み、これらの物質が導電性複合体に含まれるようにしてよい。
また、複合分散液には、塩酸などのゲル化剤を添加して、これをゲル化してから、導電性複合体の形成に供してもよい。
In the composite dispersion, materials other than modified CNT, such as ITO, PEDOT, metal nanowires, metal fine particles, metal oxide fine particles, carbon black, etc. are used in combination as conductive materials, and these conductive materials are conductive composites. May be included. Further, as a matrix component, a resin such as polyolefin such as polyethylene and polypropylene, polyester, polyol, polyurethane, polyamide, polycarbonate, polycarbodiimide, polyacrylic acid, polyoxazoline is 100 parts by mass or less with respect to 100 parts by mass of the modified CSNF. These resins may be included in the conductive composite in combination within the range.
In addition, composite dispersions perform radical scavengers, defoamers, surfactants, alcohol and other solvents, colorants, lubricants, UV absorbers, metal particles, carbon materials, humectants, desiccants, adsorbents, etc. These substances may be included in the conductive complex, as long as they are not inhibited.
In addition, a gelling agent such as hydrochloric acid may be added to the composite dispersion to make it gel, and then used for forming a conductive composite.
複合分散液をキャスト用基材にキャスト、乾燥し、剥離して、導電性フィルムを得る方法においては、導電性フィルムをキャスト用基材から剥離しやすくするために、キャスト用基材を構成する材料にフッ素系、シリコーン系などの離型剤を添加したり、離型剤をキャスト面に塗布したりしてもよい。また、キャスト用基材の表面に、コロナ処理、プラズマ処理、フレーム処理、オゾン処理、アンカーコート処理などの表面処理を行っておいてもよい。 In the method of casting the composite dispersion on a casting substrate, drying and peeling to obtain a conductive film, the casting substrate is configured to facilitate peeling of the conductive film from the casting substrate. A release agent such as fluorine or silicone may be added to the material, or the release agent may be applied to the cast surface. Further, surface treatment such as corona treatment, plasma treatment, flame treatment, ozone treatment, and anchor coat treatment may be performed on the surface of the base material for casting.
導電性複合体は、各種電子デバイスにも使用することができるが、導電性複合体、特に導電性フィルムは、その環境湿度と電気抵抗値との間に、良好な相関関係が認められることから、湿度センサーとしても好適に使用できる。修飾CSNFと修飾CNTとを含有して形成される導電性フィルムは、透明性が高いことから、湿度センサーとして建物の壁面などに設置した場合の意匠性に優れる。
導電性フィルムの厚みは、適宜設定でき、例えば0.1〜300μmである。
Conductive composites can be used for various electronic devices, but conductive composites, especially conductive films, have a good correlation between their environmental humidity and electrical resistance. It can also be suitably used as a humidity sensor. Since the conductive film formed by containing the modified CSNF and the modified CNT has high transparency, it is excellent in design when installed on a wall surface of a building as a humidity sensor.
The thickness of an electroconductive film can be set suitably, for example, is 0.1-300 micrometers.
本発明の導電性複合体には、上述した導電性フィルム、導電層、導電性薄膜以外に、例えば、修飾CSNFからなるフィルムの少なくとも一方の面に、修飾CNTの分散液を塗布、乾燥して得られる導電性フィルム;絶縁性基材の少なくとも一方の面に、修飾CSNFの分散液と修飾CNTの分散液をそれぞれ塗布、乾燥した導電性積層体;なども挙げられる。
また、本発明の導電性複合体は、絶縁性基材などに接着剤などで貼り合わされてもよい。
In addition to the above-described conductive film, conductive layer, and conductive thin film, for example, a dispersion of modified CNT is applied to at least one surface of a film made of modified CSNF and dried. Examples thereof also include a conductive laminate obtained by applying and drying a modified CSNF dispersion and a modified CNT dispersion on at least one surface of an insulating substrate.
In addition, the conductive composite of the present invention may be bonded to an insulating substrate or the like with an adhesive or the like.
絶縁性基材の材料としては、ガラスや、例えばポリエチレン、ポリプロピレンなどのポリオレフィン系、PET、ポリエチレンナフタレートなどのポリエステル系、トリアセチルセルロース、ジアセチルセルロース、セロファン等のセルロース系、6−ナイロン、6,6−ナイロンなどのポリアミド系、ポリメチルメタクリレートなどのアクリル系、ポリスチレン、ポリ塩化ビニル、ポリイミド、ポリビニルアルコール、ポリカーボネート、エチレンビニルアルコールなどの樹脂が挙げられる。また、これら樹脂の2種以上を含む樹脂組成物や、これら2種以上が互いに共重合した樹脂を使用できる。
また、その形態は、フィルム状基材であっても、立体的形状の基材であってもよい。
Examples of the insulating base material include glass, polyolefins such as polyethylene and polypropylene, polyesters such as PET and polyethylene naphthalate, celluloses such as triacetylcellulose, diacetylcellulose, and cellophane, 6-nylon, 6, Examples thereof include polyamides such as 6-nylon, acrylics such as polymethyl methacrylate, resins such as polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, and ethylene vinyl alcohol. Moreover, the resin composition containing 2 or more types of these resin and the resin which these 2 or more types copolymerized mutually can be used.
Moreover, the form may be a film-like base material or a three-dimensional base material.
以上説明したように、修飾CSNFおよび修飾CNTを含む導電性複合体は、該複合体中において、修飾CSNFおよび修飾CNTがいずれも良好に分散している。そのため、これらの高い分散性に基いて、ムラのない優れた透明性、安定した導電性などを発揮する。また、強度、加工性などにも優れる。 As described above, in the conductive composite containing modified CSNF and modified CNT, both modified CSNF and modified CNT are well dispersed in the composite. Therefore, on the basis of these high dispersibility, excellent transparency without unevenness, stable conductivity, etc. are exhibited. Moreover, it is excellent in strength, workability, and the like.
以下、実施例を挙げて、本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。
[製造例]
次のようにして、修飾CSNFの分散液(A)を調製した。
(1)改質工程
針葉樹晒クラフトパルプ30gを蒸留水1800gに懸濁した懸濁液を調製した。一方、蒸留水200gに、TEMPOを0.3g、臭化ナトリウムを3g溶解させた溶液を調製し、この溶液を上述の懸濁液に加え、20℃に調温した。
この懸濁液に、1NのHCl水溶液によりpH10に調整された次亜塩素酸ナトリウム水溶液(濃度2mol/L、密度1.15g/mL)を220g滴下し、酸化反応を開始した。
系内の温度は20℃に維持した。また、反応中にはpHが低下するが、その際には、0.5Nの水酸化ナトリウム水溶液を添加することで、pHを10に維持した。
セルロース1gに対して、水酸化ナトリウムの消費量が2.5mmolになったところで、所望量のカルボキシ基が導入されたものと判断し(予め作製した検量線に基く。)、充分量のエタノールを添加して反応を停止させた。その後、pH3になるまで塩酸を添加し、ついで、蒸留水で洗浄を繰り返し、改質セルロースを得た。
なお、改質セルロースを固形分質量として0.1g秤量し、1質量%濃度となるように、水分散させるとともに、塩酸を加えてpHを3とした。ついで、この液に対して、0.5N水酸化ナトリウム水溶液を用いた電導度滴定法により、カルボキシ基量を求めたところ、1gの改質セルロース(表面がカルボキシ基で修飾されたセルロース)あたり1.6mmol、すなわち、1.6mmol/gであった。
(2)微細化工程
上記(1)で得られた改質セルロース4gを396gの蒸留水に分散させ、水酸化ナトリウム水溶液を添加してpH10に調整した。ついで、ミキサーにより、この液を60分間微細化処理し、修飾CSNFの分散液(A)(修飾CSNFの濃度1質量%)を得た。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples.
[Production example]
A modified CSNF dispersion (A) was prepared as follows.
(1) Modification step A suspension of 30 g of softwood bleached kraft pulp suspended in 1800 g of distilled water was prepared. On the other hand, a solution in which 0.3 g of TEMPO and 3 g of sodium bromide were dissolved in 200 g of distilled water was prepared, and this solution was added to the above suspension, and the temperature was adjusted to 20 ° C.
To this suspension, 220 g of an aqueous sodium hypochlorite solution (concentration 2 mol / L, density 1.15 g / mL) adjusted to pH 10 with 1N HCl aqueous solution was dropped to initiate the oxidation reaction.
The temperature in the system was maintained at 20 ° C. During the reaction, the pH decreased, but at that time, the pH was maintained at 10 by adding a 0.5N sodium hydroxide aqueous solution.
When the consumption of sodium hydroxide is 2.5 mmol per 1 g of cellulose, it is determined that a desired amount of carboxy group is introduced (based on a calibration curve prepared in advance), and a sufficient amount of ethanol is added. The reaction was stopped by addition. Thereafter, hydrochloric acid was added until the pH reached 3, and then washing with distilled water was repeated to obtain modified cellulose.
In addition, 0.1 g of the modified cellulose as a solid content mass was weighed and dispersed in water so that the concentration became 1% by mass, and hydrochloric acid was added to adjust the pH to 3. Subsequently, when the amount of carboxy groups was determined for this solution by the conductivity titration method using a 0.5N aqueous sodium hydroxide solution, it was 1 per 1 g of modified cellulose (cellulose whose surface was modified with carboxy groups). 0.6 mmol, ie 1.6 mmol / g.
(2) Refinement step 4 g of the modified cellulose obtained in (1) above was dispersed in 396 g of distilled water, and an aqueous sodium hydroxide solution was added to adjust the pH to 10. Subsequently, this liquid was refined with a mixer for 60 minutes to obtain a modified CSNF dispersion (A) (modified CSNF concentration of 1% by mass).
この分散液(A)中の修飾CSNFのカルボキシ基は、塩型(ナトリウム)である。
分散液(A)に含まれる修飾CSNFの繊維幅(平均値)は3.5nm、繊維長(平均値)は800nmであった(原子間力顕微鏡(AFM)観察による。測定サンプル数は20)。
The carboxy group of the modified CSNF in this dispersion (A) is a salt form (sodium).
The fiber width (average value) of the modified CSNF contained in the dispersion (A) was 3.5 nm, and the fiber length (average value) was 800 nm (according to atomic force microscope (AFM) observation. The number of measurement samples was 20). .
[実施例1]
上記分散液(A)を蒸留水で希釈して、カルボキシ基で修飾されたセルロースナノファイバーの分散液(A−1)(濃度0.1質量%)を得た。
この分散液(A−1)10mLに対して、修飾CNTが分散した分散液(B−1)(濃度0.003質量%)を20mL混合し、複合分散液(1)を調製した。
なお、修飾CNTとしては、上述の「Single−walled carbon nanotubes,carboxylic acid functionalized(652490−250MG,1G)」(シグマアルドリッチジャパン社)を用いた。
また、この複合分散液は、30分間の超音波分散後、9000rpmの条件で40分間遠心分離しても、良好な分散性を維持していた。
この複合分散液(1)をテフロン(登録商標)シャーレ上にキャストし、40℃で3日間乾燥した後にシャーレから剥離し、修飾CNTを6質量%含有する厚み6μmの自立フィルム(導電性フィルム)を得た。
得られた自立フィルムについて、下記評価を行った。結果を表1に示す。
[Example 1]
The dispersion liquid (A) was diluted with distilled water to obtain a dispersion liquid (A-1) (concentration of 0.1% by mass) of cellulose nanofibers modified with a carboxy group.
20 mL of dispersion (B-1) (concentration 0.003 mass%) in which modified CNT was dispersed was mixed with 10 mL of this dispersion (A-1) to prepare a composite dispersion (1).
As the modified CNT, the above-described “Single-walled carbon nanotubes, carboxylic acid acid functionalized (65490-250MG, 1G)” (Sigma Aldrich Japan) was used.
In addition, this composite dispersion maintained good dispersibility even after centrifugation for 30 minutes at 9000 rpm after ultrasonic dispersion for 30 minutes.
This composite dispersion (1) was cast on a Teflon (registered trademark) petri dish, dried at 40 ° C. for 3 days, then peeled off from the petri dish, and a 6 μm thick self-supporting film (conductive film) containing 6% by mass of modified CNT Got.
The following evaluation was performed about the obtained self-supporting film. The results are shown in Table 1.
<評価>
(1)電気抵抗値
JIS R3256に基づき、得られた自立フィルムの電気抵抗値を測定した。5回測定し、その平均値RAを求めた。
また、測定された最大値と最小値のうち、平均値RAとの差の絶対値が大きい方の電気抵抗値とRAとの差(絶対値)をRとし、下記式により、電気抵抗値の振れ幅を求めた。
振れ幅(%)=R/RA×100
(2)透明性
分光光度計により、得られた自立フィルムの可視光透過率を測定した(波長λ=600nm)。
(3)湿度センサーとしての使用可能性
(a)得られた自立フィルムを50、60、70、80、90、98%RHの各湿度環境下に置き、上記(1)と同様の方法にて電気抵抗値を測定し、湿度センサーとしての使用可能性を評価した。温度はいずれも30℃とした。
(b)得られた自立フィルムの電気抵抗値を上記(1)と同様の方法にて測定しながら、自立フィルムの置かれた環境の湿度を変化させた。具体的には、60%RHと90RH%とを繰り返した。温度はいずれも30℃とした。
<Evaluation>
(1) Electric resistance value Based on JIS R3256, the electric resistance value of the obtained self-supporting film was measured. The measurement was made 5 times, and the average value RA was determined.
Further, of the measured maximum value and minimum value, R is the difference (absolute value) between R A and the electric resistance value having the larger absolute value of the difference from the average value R A , The amplitude of the value was obtained.
Swing width (%) = R / R A × 100
(2) Transparency The visible light transmittance of the obtained self-supporting film was measured with a spectrophotometer (wavelength λ = 600 nm).
(3) Possibility of use as a humidity sensor (a) The obtained self-supporting film is placed in each humidity environment of 50, 60, 70, 80, 90, and 98% RH, and the same method as in (1) above. The electrical resistance value was measured, and the applicability as a humidity sensor was evaluated. The temperature was 30 ° C. for all.
(B) While measuring the electrical resistance value of the obtained self-supporting film by the same method as in the above (1), the humidity of the environment where the self-supporting film was placed was changed. Specifically, 60% RH and 90RH% were repeated. The temperature was 30 ° C. for all.
[比較例1]
修飾CNTのみが分散した分散液(B−1)(濃度0.003質量%)をテフロン(登録商標)シャーレ上にキャストし、40℃で3日間乾燥したが、フィルム化できなかった。
[Comparative Example 1]
A dispersion (B-1) (concentration: 0.003 mass%) in which only modified CNTs were dispersed was cast on a Teflon (registered trademark) petri dish and dried at 40 ° C. for 3 days, but could not be formed into a film.
[比較例2]
実施例1で調製した修飾CSNFの分散液(A−1)(濃度0.1質量%)をテフロン(登録商標)シャーレ上にキャストし、40℃で3日間乾燥し、修飾CSNFからなる厚み6μmの自立フィルム(2)を得た。そして、実施例1と同様の評価(1)(2)を実施した。
[Comparative Example 2]
The modified CSNF dispersion (A-1) (concentration: 0.1% by mass) prepared in Example 1 was cast on a Teflon (registered trademark) petri dish, dried at 40 ° C. for 3 days, and a thickness of 6 μm comprising the modified CSNF. A self-supporting film (2) was obtained. And evaluation (1) (2) similar to Example 1 was implemented.
[比較例3]
修飾CNTが分散した分散液(B−1)(濃度0.003質量%)の代わりに、未修飾のCNTが分散した分散液(濃度0.003質量%)を用いた以外は、実施例1と同様にして、厚み6μmの自立フィルム(3)を得た。そして、実施例1と同様の評価(1)を実施した。
なお、この複合分散液中のCNTは、30分間の超音波分散後、9000rpmの条件で40分間遠心分離すると、良好な分散性を維持できず凝集した。
[Comparative Example 3]
Example 1 except that the dispersion liquid (concentration 0.003% by mass) in which unmodified CNTs were dispersed was used instead of the dispersion liquid (B-1) (concentration 0.003% by mass) in which the modified CNTs were dispersed. In the same manner as above, a self-supporting film (3) having a thickness of 6 μm was obtained. And evaluation (1) similar to Example 1 was implemented.
The CNTs in this composite dispersion liquid were aggregated because they could not maintain good dispersibility when centrifuged for 40 minutes at 9000 rpm after ultrasonic dispersion for 30 minutes.
<結果および考察>
(1)電気抵抗値、(2)透明性
修飾CNTを用いた実施例1の自立フィルムは、電気抵抗値の振れ幅が非常に小さかった。このことから、実施例1の自立フィルム中では修飾CNTが均一に分散し、そのために安定した電気抵抗値を示すことがわかった。また、実施例1の自立フィルムは、フィルム全体にわたって透明性が優れ、可視光透過率が高かった。これに対して、未修飾のCNTを用いた比較例3の自立フィルム中では未修飾のCNTの分散にムラがあり、そのために、透明な部分と不透明な部分とがあり、外観が不良であるとともに、電気の流れる部分と流れない部分が生じ、電気抵抗値の振れ幅も大きかった。
(3)湿度センサーとしての使用可能性
実施例1のみ行った。評価(a)にて、湿度環境を50、60、70、80、90、98%RHとすると、電気抵抗値も1.5、1.7、1.8、2.1、3.1、4.2kΩと変化し、湿度を大きくすると抵抗値も大きくなった。また、2日かけてこの測定を2回繰り返し、再現性が確認された。
評価(b)にて、60%RHと90RH%とを繰り返し、電気抵抗値を測定した場合、いずれの場合でも、電気測定値が10分以内に安定し、良好な応答性が認められた。
これらの結果から、実施例1の自立フィルムは、湿度センサーとして利用できることが示された。
<Results and discussion>
(1) Electric resistance value, (2) Transparency The self-standing film of Example 1 using modified CNTs had a very small fluctuation width of the electric resistance value. From this, it was found that the modified CNTs were uniformly dispersed in the self-supporting film of Example 1 and exhibited a stable electric resistance value. Moreover, the self-supporting film of Example 1 was excellent in transparency over the entire film and had high visible light transmittance. On the other hand, in the self-supporting film of Comparative Example 3 using unmodified CNT, the dispersion of unmodified CNT is uneven, and therefore there are transparent portions and opaque portions, and the appearance is poor. At the same time, a portion where electricity flows and a portion where electricity does not flow are generated, and the fluctuation range of the electric resistance value is large.
(3) Possibility of use as a humidity sensor Only Example 1 was performed. In the evaluation (a), when the humidity environment is 50, 60, 70, 80, 90, 98% RH, the electric resistance value is 1.5, 1.7, 1.8, 2.1, 3.1, The resistance value increased as the humidity was increased. Moreover, this measurement was repeated twice over 2 days, and reproducibility was confirmed.
In the evaluation (b), when 60% RH and 90 RH% were repeated and the electrical resistance value was measured, the electrical measurement value was stable within 10 minutes and good responsiveness was observed in any case.
From these results, it was shown that the self-supporting film of Example 1 can be used as a humidity sensor.
[実施例2]
上記分散液(A)を蒸留水で希釈して、カルボキシ基で修飾されたセルロースナノファイバーの分散液(A−2)(濃度0.2質量%)を得た。
この分散液(A−2)20mLに対して、カルボキシ基で修飾されたCNTが分散した分散液(B−1)(濃度0.003質量%)を10mL混合して混合液を得た。
この混合液2mLに対して、0.2mM−HCl水溶液を1mL添加し、室温で1時間放置することにより、CNT/セルロースナノファイバーハイドロゲル(水分99質量%)を得た。
このゲルを複合分散液(1)の代わりに用いた以外は、実施例1と同様にして、自立フィルムを得た。
[Example 2]
The dispersion liquid (A) was diluted with distilled water to obtain a dispersion liquid (A-2) (concentration 0.2% by mass) of cellulose nanofibers modified with a carboxy group.
10 mL of dispersion liquid (B-1) (concentration 0.003 mass%) in which CNTs modified with carboxy groups were dispersed was mixed with 20 mL of this dispersion liquid (A-2) to obtain a mixed liquid.
1 mL of 0.2 mM HCl aqueous solution was added to 2 mL of this mixed solution, and left at room temperature for 1 hour to obtain a CNT / cellulose nanofiber hydrogel (water content 99 mass%).
A self-supporting film was obtained in the same manner as in Example 1 except that this gel was used in place of the composite dispersion (1).
[実施例3]
実施例1で調製された複合分散液(1)を厚み100μmのPETフィルム上に塗工し、40℃で3日間乾燥し、膜厚0.5μmの導電層が形成されたPETフィルム積層体を得た。
このPETフィルム積層体について、実施例1と同様にして可視光透過率を測定したところ、70%であり、透明性に優れていた。
また、導電層表面の平均表面粗さ(JIS B0651)は2.66nmであり、平滑性にも優れていた。これは、導電層中において、修飾CSNFおよび修飾CNTが高分散していることを裏付けるものと理解できる。
[Example 3]
The composite dispersion (1) prepared in Example 1 was coated on a PET film having a thickness of 100 μm, dried at 40 ° C. for 3 days, and a PET film laminate having a 0.5 μm-thick conductive layer formed thereon. Obtained.
When the visible light transmittance of this PET film laminate was measured in the same manner as in Example 1, it was 70% and was excellent in transparency.
Moreover, the average surface roughness (JIS B0651) of the surface of the conductive layer was 2.66 nm, and the smoothness was excellent. This can be understood to support the high dispersion of the modified CSNF and the modified CNT in the conductive layer.
[実施例4〜7]
実施例1と同様にして、各例の自立フィルム(厚み6μm)を得た。ただし、各例では、得られた自立フィルム中における、修飾CSNF100質量部に対する修飾CNTの質量比率が表2に示す値となるようにした。
実施例4〜6で得られた自立フィルムの導電率をJIS H0505により測定した。また、実施例5の自立フィルムの表面抵抗値をJIS C2139により測定した。また、実施例4〜7の自立フィルムの弾性率および引張強度をJIS K6400により測定した。これらの結果を表2に示す。
[Examples 4 to 7]
In the same manner as in Example 1, a self-supporting film (thickness 6 μm) of each example was obtained. However, in each example, the mass ratio of the modified CNT with respect to 100 parts by mass of the modified CSNF in the obtained self-supporting film was set to the value shown in Table 2.
The electric conductivity of the self-supporting films obtained in Examples 4 to 6 was measured according to JIS H0505. Moreover, the surface resistance value of the self-supporting film of Example 5 was measured according to JIS C2139. Moreover, the elastic modulus and tensile strength of the self-supporting films of Examples 4 to 7 were measured according to JIS K6400. These results are shown in Table 2.
<考察>
(導電率)
実施例4〜6の各自立フィルムは、表2に示す導電率を示した。
これに対して、マトリックス成分として、カルボキシル基を導入していないセルロースナノファイバー(バクテリアセルロース)を用いたフィルムの導電率は0.1S/cm(Biomacromolecules 2006,7,1280-1284参照。参考例1とする。)、マトリックス成分として、ポリエチレンを用いたフィルムの導電率は0.8S/cm(CARBON47(2009)1983-1988参照。参考例2とする。)、マトリックス成分として、再生セルロースを用いたフィルムの導電率は0.03S/cm(Journal of AppliedPolymer Science,Vol. 117, 3588-3594(2010)参照。参考例3とする。)である。なお、これら参考例1〜3のフィルムにおけるマトリックス成分と修飾CNTとの比率は、実施例5における修飾CSNFと修飾CNTとの比率と同程度である。
このように実施例5と同程度に修飾CNTを含有する参考例1〜3のフィルムの導電率は、いずれも実施例5の導電率を大幅に下回った。
この結果から、マトリックス成分として修飾CSNFを使用することが、導電率の向上に大きく寄与していることが理解できる。
<Discussion>
(conductivity)
Each self-supporting film of Examples 4 to 6 exhibited the electrical conductivity shown in Table 2.
On the other hand, the conductivity of a film using cellulose nanofibers (bacterial cellulose) into which carboxyl groups are not introduced as a matrix component is 0.1 S / cm (see Biomacromolecules 2006, 7, 1280-1284. Reference Example 1 The conductivity of a film using polyethylene as a matrix component is 0.8 S / cm (see CARBON 47 (2009) 1983-1988. Reference example 2), and regenerated cellulose is used as a matrix component. The electrical conductivity of the film is 0.03 S / cm (see Journal of Applied Polymer Science, Vol. 117, 3588-3594 (2010), referred to as Reference Example 3). The ratio of the matrix component and the modified CNT in the films of Reference Examples 1 to 3 is approximately the same as the ratio of the modified CSNF and the modified CNT in Example 5.
Thus, the electrical conductivity of the films of Reference Examples 1 to 3 containing modified CNT to the same extent as in Example 5 was significantly lower than that in Example 5.
From this result, it can be understood that the use of modified CSNF as a matrix component greatly contributes to the improvement of conductivity.
(表面抵抗値)
実施例5の自立フィルムの表面抵抗値は、表2に示すように300Ω/□であった。
これに対して、マトリックス成分として、PEDOT/PSS(ポリスチレンスルホン酸をドープしたポリ(3,4−エチレンジオキシチオフェン))を用いたフィルム(参考例4とする。)の表面抵抗値は1200Ω/□、マトリックス成分として、ポリエチレンを用いたフィルム(参考例5とする。)の表面抵抗値は8.1MΩ/□、マトリックス成分として、ポリアミドを用いたフィルム(参考例6とする。)の表面抵抗値は0.5MΩ/□(いずれもAdv. Mater. 2010, 22, 1672-1688参照。)である。なお、これら参考例4〜6のフィルムにおけるマトリックス成分と修飾CNTとの比率は、実施例5における修飾CSNFと修飾CNTとの比率と同程度である。
このように実施例5と同程度に修飾CNTを含有する参考例4〜6のフィルムの表面抵抗値は、いずれも実施例5の表面抵抗値を大幅に上回った。
この結果から、マトリックス成分として修飾CSNFを使用することが、表面抵抗値の低下に大きく寄与していることが理解できる。
(Surface resistance value)
The surface resistance value of the self-supporting film of Example 5 was 300Ω / □ as shown in Table 2.
On the other hand, the surface resistance value of a film using PEDOT / PSS (poly (3,4-ethylenedioxythiophene doped with polystyrene sulfonic acid)) as a matrix component (referred to as Reference Example 4) is 1200Ω / The surface resistance of a film using polyethylene as a matrix component (referred to as Reference Example 5) is 8.1 MΩ / □, and the surface resistance of a film using polyamide as a matrix component (referred to as Reference Example 6). The value is 0.5 MΩ / □ (all refer to Adv. Mater. 2010, 22, 1672-1688). In addition, the ratio of the matrix component and modified CNT in the films of these Reference Examples 4 to 6 is approximately the same as the ratio of modified CSNF and modified CNT in Example 5.
Thus, the surface resistance values of the films of Reference Examples 4 to 6 containing modified CNT to the same extent as in Example 5 were significantly higher than those in Example 5.
From this result, it can be understood that the use of modified CSNF as a matrix component greatly contributes to the reduction of the surface resistance value.
(弾性率および引張強度)
実施例4〜7の自立フィルムは、表2に示す弾性率、引張強度を示した。
これに対して、マトリックス成分として、PMMA(ポリメタクリル酸メチル)を用いたフィルム(参考例7とする。)の弾性率は3〜6GPa、引張強度は70〜110MPa(ただし、参考例7のフィルムにおけるマトリックス成分100質量部に対する修飾CNTの比率は0.5〜7質量部の範囲。文献Chemical Physics Letters 330 (2000) 219-225参照。)であり、マトリックス成分として、再生セルロースを用いたフィルム(参考例8とする。)の弾性率は1〜5GPa、引張強度は40〜80MPa(ただし、参考例8のフィルムにおけるマトリックス成分100質量部に対する修飾CNTの比率は0または0.2〜7質量部の範囲。Journal of AppliedPolymer Science,Vol. 117, 3588-3594(2010)参照。)である。なお、修飾CNT単体の弾性率は、8.0GPaである(Chem. Mater. 2003, 15, 175-178参照。)。
このように実施例4〜7と参考例7および8との比較から、マトリックス成分として修飾CSNFを使用することが、高い弾性率、高い引張強度に寄与しているものと理解できる。
(Elastic modulus and tensile strength)
The self-supporting films of Examples 4 to 7 exhibited the elastic modulus and tensile strength shown in Table 2.
On the other hand, a film using PMMA (polymethyl methacrylate) as a matrix component (referred to as Reference Example 7) has an elastic modulus of 3 to 6 GPa and a tensile strength of 70 to 110 MPa (However, the film of Reference Example 7) The ratio of the modified CNT to 100 parts by mass of the matrix component in the range of 0.5 to 7 parts by mass (see the document Chemical Physics Letters 330 (2000) 219-225)), and a film using regenerated cellulose as the matrix component ( The elastic modulus of Reference Example 8 is 1 to 5 GPa, and the tensile strength is 40 to 80 MPa (however, the ratio of the modified CNT to 100 parts by mass of the matrix component in the film of Reference Example 8 is 0 or 0.2 to 7 parts by mass) (Journal of Applied Polymer Science, Vol. 117, 3588-3594 (2010)). The elastic modulus of the modified CNT alone is 8.0 GPa (see Chem. Mater. 2003, 15, 175-178).
Thus, it can be understood from the comparison between Examples 4 to 7 and Reference Examples 7 and 8 that the use of modified CSNF as the matrix component contributes to high elastic modulus and high tensile strength.
[実施例8]
上記分散液(A)(修飾CSNF:1質量%)に、オキサゾリン(WS−500)を添加した。この際、オキサゾリンの添加量(固形分)は、修飾CSNF100質量部に対し3質量部とした。添加後の分散液に対して、修飾CSNFと修飾CNTの比率が実施例1と同じになるように修飾CNTの分散液を加え、以降、実施例1と同様にして自立フィルムを作製した。
そして、この自立フィルムを120℃で15分間加熱した後、水または0.1NNaOH水溶液それぞれの中に1日間浸漬し、浸漬後の自立フィルムを観察し、耐水性を評価した。
[Example 8]
Oxazoline (WS-500) was added to the dispersion (A) (modified CSNF: 1% by mass). At this time, the amount of oxazoline added (solid content) was 3 parts by mass with respect to 100 parts by mass of the modified CSNF. The dispersion of modified CNT was added to the dispersion after addition so that the ratio of modified CSNF and modified CNT was the same as in Example 1, and then a self-supporting film was produced in the same manner as in Example 1.
And after heating this self-supporting film at 120 degreeC for 15 minute (s), it immersed for 1 day in each of water or 0.1N NaOH aqueous solution, the self-supporting film after immersion was observed, and water resistance was evaluated.
[比較例4]
修飾CSNFの代わりに、カルボキシメチルセルロース(DS(エーテル化度)=1.2)を用いた以外は、実施例1と同様にして自立フィルムを作製した。
そして、この自立フィルムを120℃で15分間加熱した後、水または0.1NNaOH水溶液それぞれの中に1日間浸漬し、浸漬後の自立フィルムを観察し、耐水性を評価した。
[Comparative Example 4]
A self-supporting film was produced in the same manner as in Example 1 except that carboxymethylcellulose (DS (degree of etherification) = 1.2) was used instead of the modified CSNF.
And after heating this self-supporting film at 120 degreeC for 15 minute (s), it immersed for 1 day in each of water or 0.1N NaOH aqueous solution, the self-supporting film after immersion was observed, and water resistance was evaluated.
<考察>
(耐水性)
実施例8の自立フィルムは、水、0.1NNaOH水溶液それぞれの中に1日間浸漬しても、外観上変化は認められなかった。これに対して、実施例1の自立フィルムについても、同様に水、0.1NNaOH水溶液への浸漬を実施したところ、水に浸漬後の自立フィルムには変化が認められなかったものの、0.1NNaOH水溶液に浸漬後の自立フィルムには膨潤が認められた。この結果から、実施例8ではオキサゾリン(架橋剤)を添加しているため、自立フィルムの耐水性が向上し、0.1NNaOH水溶液への浸漬後にも何ら変化が認められなかったものと理解できる。
また、比較例4のように、表面がカルボキシ基で修飾されているのではなく、化合物自体が(−COO−)を有するカルボキシメチルセルロースを用いた場合には、水に浸漬後の自立フィルムには膨潤が認められ、また、0.1NNaOH水溶液に浸漬後の自立フィルムには溶解が認められ、耐水性が劣っていることがわかった。
<Discussion>
(water resistant)
When the self-supporting film of Example 8 was immersed in water and 0.1N NaOH aqueous solution for 1 day, no change in appearance was observed. In contrast, the self-supporting film of Example 1 was similarly immersed in water and a 0.1N NaOH aqueous solution, but no change was observed in the self-supporting film after being immersed in water, but 0.1N NaOH. Swelling was observed in the free-standing film immersed in the aqueous solution. From this result, since oxazoline (crosslinking agent) was added in Example 8, it can be understood that the water resistance of the self-supporting film was improved and no change was observed after immersion in a 0.1 N NaOH aqueous solution.
In addition, as in Comparative Example 4, when the surface of the film itself is not modified with a carboxy group and carboxymethyl cellulose having (—COO − ) is used, the self-supporting film after being immersed in water Swelling was observed, and dissolution was observed in the self-supporting film immersed in 0.1N NaOH aqueous solution, indicating that the water resistance was poor.
Claims (4)
前記カルボキシ基で修飾されたカーボンナノチューブのカルボキシ基量が0.1〜2.0mmol/gであることを特徴とする導電性複合体。 Containing cellulose nanofibers modified with carboxy groups and carbon nanotubes modified with carboxy groups ,
The conductive composite, wherein the carbon nanotube modified with the carboxy group has a carboxy group content of 0.1 to 2.0 mmol / g .
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