JP2008163062A - Method for producing polyaniline composition, polyaniline composition and covered material with the same - Google Patents
Method for producing polyaniline composition, polyaniline composition and covered material with the same Download PDFInfo
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- JP2008163062A JP2008163062A JP2006350784A JP2006350784A JP2008163062A JP 2008163062 A JP2008163062 A JP 2008163062A JP 2006350784 A JP2006350784 A JP 2006350784A JP 2006350784 A JP2006350784 A JP 2006350784A JP 2008163062 A JP2008163062 A JP 2008163062A
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- Prior art keywords
- polyaniline composition
- polyaniline
- aniline
- acrylate
- sulfonic acid
- Prior art date
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Links
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000463 material Substances 0.000 title 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000002019 doping agent Substances 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 15
- 150000001448 anilines Chemical class 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 7
- 238000010894 electron beam technology Methods 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 238000012423 maintenance Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 229920000775 emeraldine polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 2-ethylhexyl Chemical group 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 2
- BOKRKKCPFKUCIZ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;2-methyloxirane Chemical compound CC1CO1.OCC(CO)(CO)CO BOKRKKCPFKUCIZ-UHFFFAOYSA-N 0.000 description 2
- VFFFESPCCPXZOQ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.OCC(CO)(CO)CO VFFFESPCCPXZOQ-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- SNZYOYGFWBZAQY-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methyloxirane Chemical compound CC1CO1.CCC(CO)(CO)CO SNZYOYGFWBZAQY-UHFFFAOYSA-N 0.000 description 1
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 1
- BJUPZVQSAAGZJL-UHFFFAOYSA-N 2-methyloxirane;propane-1,2,3-triol Chemical compound CC1CO1.OCC(O)CO BJUPZVQSAAGZJL-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005973 Carvone Substances 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005011 alkyl ether group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QUANRIQJNFHVEU-UHFFFAOYSA-N oxirane;propane-1,2,3-triol Chemical compound C1CO1.OCC(O)CO QUANRIQJNFHVEU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229960004838 phosphoric acid Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、新規な導電性有機重合体の製造方法、組成物およびその被覆物に関するものである。さらに詳しくは、本発明は、（ａ）活性エネルギー線硬化性化合物、（ｂ）リン酸および／またはスルホン酸基含有化合物、および（ｃ）ドーピング剤の存在下で、（ｄ）アニリンまたはアニリン誘導体を酸化重合させることを特徴とするポリアニリン組成物の製造方法、ポリアニリン組成物およびその被覆物に関するものである。 The present invention relates to a method for producing a novel conductive organic polymer, a composition and a coating thereof. More specifically, the present invention relates to (d) aniline or an aniline derivative in the presence of (a) an active energy ray-curable compound, (b) a phosphoric acid and / or sulfonic acid group-containing compound, and (c) a doping agent. The present invention relates to a method for producing a polyaniline composition characterized by oxidative polymerization of polyaniline, a polyaniline composition, and a coating thereof.
ポリアニリン、ポリチオフェン、ポリピロール等の導電性高分子は電解コンデンサ、リチウム電池電極等に応用されている。一般的に導電性高分子は不溶、不融であるため、溶媒やバインダー樹脂中に溶解あるいは分散させることが困難であり、加工性を向上させることが実用化への課題となっていた。 Conductive polymers such as polyaniline, polythiophene, and polypyrrole are applied to electrolytic capacitors, lithium battery electrodes, and the like. In general, since conductive polymers are insoluble and infusible, it is difficult to dissolve or disperse them in a solvent or binder resin, and improving workability has been a problem for practical use.
ポリアニリンのとり得る形態の一部として、絶縁性である非ドープ状態のエメラルジンベースと導電性であるドープ状態のエメラルジンソルトがあり、ドーピング剤の添加、脱離によりその性状を可逆的に変化させることができる。 Some of the possible forms of polyaniline are the undoped emeraldine base that is insulating and the conductive emeraldine salt that is electrically conductive, and its properties are reversibly changed by adding and removing dopants. be able to.
ポリアニリンは他の導電性高分子とは異なり、ピリジン、ジメチルホルムアミド、Ｎ−メチルピロリドン等の一部の非プロトン性極性溶媒に溶解することが知られている。特に、絶縁性であるエメラルジンベース状態のポリアニリンはＮ−メチルピロリドンへの溶解性が高い。このことを利用してＮ−メチルピロリドン溶液から成形体に加工した後に、ドーピング剤を添加し導電性のポリアニリンを得る方法が特許文献１に開示されている。しかし、この方法によれば、エメラルジンベースからＮ−メチルピロリドンを揮発させ成形体を得る工程と、得られた成形体にドーピング剤を添加させる工程の２つの工程が必要であり、工程が煩雑であるとともに、Ｎ−メチルピロリドンという揮発性有機溶剤を含有するため労働衛生上および環境上の問題が生じている。 Unlike other conductive polymers, polyaniline is known to dissolve in some aprotic polar solvents such as pyridine, dimethylformamide, N-methylpyrrolidone and the like. In particular, the insulating emeraldine-based polyaniline has high solubility in N-methylpyrrolidone. Patent Document 1 discloses a method for obtaining a conductive polyaniline by adding a doping agent after processing an N-methylpyrrolidone solution into a molded body by utilizing this fact. However, according to this method, two steps are required, that is, a step of volatilizing N-methylpyrrolidone from emeraldine base to obtain a molded product and a step of adding a doping agent to the obtained molded product. In addition, since it contains a volatile organic solvent called N-methylpyrrolidone, there are problems in terms of occupational health and environment.
一方で、導電性のエメラルジンソルト状態のポリアニリン粉末を放射線硬化性樹脂に分散させた導電性組成物が特許文献２に開示されている。しかしながら、導電性のエメラルジンソルト状態のポリアニリンにおいては、ポリアニリンの環構造に由来する強い分子間相互作用により放射線硬化性樹脂への分散性が十分ではなく、アクリル系樹脂を分散剤として併用しなければならない。さらに記載されている実施例は何れも揮発性有機溶剤を使用しており、上記と同様の問題が生じている。 On the other hand, Patent Document 2 discloses a conductive composition in which a conductive polyaniline powder in an emeraldine salt state is dispersed in a radiation curable resin. However, polyaniline in the conductive emeraldine salt state is not sufficiently dispersible in the radiation curable resin due to the strong intermolecular interaction derived from the polyaniline ring structure, and an acrylic resin must be used as a dispersant. I must. Further, all of the examples described use volatile organic solvents, which cause the same problems as described above.
また、特許文献３には重合性二重結合を有するスルホン酸系ドーピング剤を用いた紫外線硬化性のポリアニリン組成物について開示されているが、記載されている実施例は何れも有機溶剤を併用するものであり、上記と同様の問題が生じている。 Further, Patent Document 3 discloses an ultraviolet curable polyaniline composition using a sulfonic acid-based doping agent having a polymerizable double bond, but all the examples described together use an organic solvent. However, the same problem as described above occurs.
さらに、特許文献４には重合性二重結合を有する化合物中で、アニオン性界面活性剤をドーピング剤として用いてポリアニリン組成物を合成することにより、重合性化合物中で凝集することなく良好な分散状態を得る方法が提案されている。しかしながら、塩酸、硫酸または硝酸という腐食性の酸を併用する必要があり、合成後の洗浄を十分にしなければならないという煩雑さに加え、洗浄中にドーピング剤も系から除去され、分散不安定となり凝集物が生じやすいという問題が生じている。
本発明は上記問題を解決するために、揮発性有機溶剤や腐食性の酸を使用することなく、容易かつ優れた導電性を有するポリアニリン組成物の製造方法を提供することを課題としている。 In order to solve the above-described problems, an object of the present invention is to provide a method for producing a polyaniline composition having an easy and excellent conductivity without using a volatile organic solvent or a corrosive acid.
（ａ）活性エネルギー線硬化性化合物、（ｂ）リン酸および／またはスルホン酸基含有化合物、および（ｃ）ドーピング剤の存在下で、（ｄ）アニリンまたはアニリン誘導体を酸化重合させることにより製造されるポリアニリン組成物は、揮発性有機溶剤を含有せず、活性エネルギー線で硬化させることにより容易に導電性の優れた塗膜を提供することを見出し、本発明を完成するに至った。 It is produced by oxidative polymerization of (d) aniline or an aniline derivative in the presence of (a) an active energy ray-curable compound, (b) a phosphoric acid and / or sulfonic acid group-containing compound, and (c) a doping agent. The polyaniline composition does not contain a volatile organic solvent and has been found to easily provide a coating film having excellent conductivity by curing with active energy rays, and has completed the present invention.
すなわち、本発明は（ａ）活性エネルギー線硬化性化合物、（ｂ）リン酸および／またはスルホン酸基含有化合物、および（ｃ）ドーピング剤の存在下で、（ｄ）アニリンまたはアニリン誘導体を酸化重合させることを特徴とするポリアニリン組成物の製造方法に関するものである。 That is, the present invention provides (a) an active energy ray-curable compound, (b) a phosphoric acid and / or sulfonic acid group-containing compound, and (c) oxidative polymerization of aniline or an aniline derivative in the presence of a doping agent. The present invention relates to a method for producing a polyaniline composition.
また本発明は、（ｃ）ドーピング剤が、スルホン酸基を分子内に有する化合物であることを特徴とする上記記載のポリアニリン組成物の製造方法に関するものである。 The present invention also relates to the method for producing a polyaniline composition as described above, wherein (c) the doping agent is a compound having a sulfonic acid group in the molecule.
また本発明は、酸化重合後に水を除去してなることを特徴とするポリアニリン組成物の製造方法に関するものである。 The present invention also relates to a method for producing a polyaniline composition, wherein water is removed after oxidative polymerization.
また本発明は、上記記載の製造方法により得られるポリアニリン組成物である。 The present invention also provides a polyaniline composition obtained by the production method described above.
また本発明は、上記記載のポリアニリン組成物を基材に塗工後、活性エネルギー線により硬化してなることを特徴とする被覆物である。 Moreover, this invention is a coating characterized by being hardened | cured with an active energy ray after applying the polyaniline composition described above to a substrate.
本発明に係わるポリアニリン組成物は、分散安定性に優れ、紫外線および電子線等の活性エネルギー線の照射により導電性と被膜耐性に優れた硬化被膜を提供することができる。また、揮発性有機溶剤を含有しないため作業環境および地球環境保全上も優れるものである。 The polyaniline composition according to the present invention is excellent in dispersion stability and can provide a cured film excellent in conductivity and film resistance by irradiation with active energy rays such as ultraviolet rays and electron beams. Moreover, since it does not contain a volatile organic solvent, it is excellent in terms of work environment and global environmental conservation.
本発明は（ａ）活性エネルギー線硬化性化合物、（ｂ）リン酸および／またはスルホン酸基含有化合物、および（ｃ）ドーピング剤の存在下で、（ｄ）アニリンまたはアニリン誘導体を酸化重合させることにより得られるポリアニリン組成物、その製造方法およびその被覆物に関するものである。 In the present invention, (d) aniline or an aniline derivative is oxidatively polymerized in the presence of (a) an active energy ray-curable compound, (b) a phosphoric acid and / or sulfonic acid group-containing compound, and (c) a doping agent. Relates to a polyaniline composition obtained by the above method, a production method thereof and a coating thereof.
本発明における（ａ）活性エネルギー線硬化性化合物とは、特に限定されるものではなく、紫外線および電子線等の活性エネルギー線の照射により硬化する化合物であればよく、分子内に不飽和二重結合を有する化合物が挙げられる。活性エネルギー線硬化性化合物としては、例えば、スチレン、２−エチルヘキシル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、Ｎ−メチルピロリドン、アクリロイルモルホリン等の単官能ビニル化合物、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート（ｎ＝２〜２０）、プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート（ｎ＝２〜２０）、アルカン（炭素数４〜１２）グリコールジ（メタ）アクリレート、アルカン（炭素数４〜１２）グリコールエチレンオキサイド付加物（２〜２０モル）ジ（メタ）アクリレート、アルカン（炭素数４〜１２）グリコールプロピレンオキサイド付加物（２〜２０モル）ジ（メタ）アクリレート、ビスフェノールＡエチレンオキサイド付加物（２〜２０モル）ジ（メタ）アクリレート等の２官能ビニル化合物、グリセリントリ（メタ）アクリレート、グリセリンエチレンオキサイド付加物（３〜３０モル）トリ（メタ）アクリレート、グリセリンプロピレンオキサイド付加物（３〜３０モル）トリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイド付加物（３〜３０モル）トリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキサイド付加物（３〜３０モル）トリ（メタ）アクリレート等の３官能ビニル化合物、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールエチレンオキサイド付加物（４〜４０モル）テトラ（メタ）アクリレート、ペンタエリスリトールプロピレンオキサイド付加物（４〜４０モル）テトラ（メタ）アクリレート、ジグリセリンテトラ（メタ）アクリレート、ペンタエリスリトールエチレンオキサイド付加物（４〜４０モル）テトラ（メタ）アクリレート、ペンタエリスリトールプロピレンオキサイド付加物（４〜４０モル）テトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジトリメチロールプロパンエチレンオキサイド付加物（４〜４０モル）テトラ（メタ）アクリレート、ジトリメチロールプロパンプロピレンオキサイド付加物（３〜３０モル）テトラ（メタ）アクリレート等の４官能ビニル化合物、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールエチレンオキサイド付加物（６〜６０モル）ヘキサ（メタ）アクリレート、ジペンタエリスリトールプロピレンオキサイド付加物（６〜６０モル）ヘキサ（メタ）アクリレート等の多官能ビニル化合物およびそれらの混合物が挙げられる。（ａ）活性エネルギー線硬化性化合物は、要求される硬化被膜物性に応じて適宜選択することが可能であり、必要に応じて、ポリエステルアクリレート、ポリウレタンアクリレート、エポキシアクリレート等の活性エネルギー線硬化性オリゴマーを併用することも可能である。 The (a) active energy ray-curable compound in the present invention is not particularly limited as long as it is a compound that is cured by irradiation with active energy rays such as ultraviolet rays and electron beams. Examples include compounds having a bond. Examples of the active energy ray-curable compound include monofunctional vinyl compounds such as styrene, 2-ethylhexyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, N-methylpyrrolidone, and acryloylmorpholine, ethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate (n = 2 to 20), propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate (n = 2 to 20), alkane (carbon number 4 to 12) glycol di (meta) ) Acrylate, alkane (4 to 12 carbon atoms) glycol ethylene oxide adduct (2 to 20 mol) di (meth) acrylate, alkane (4 to 12 carbon atoms) glycol propylene oxide adduct (2 to 20 mol) di Bifunctional vinyl compounds such as (meth) acrylate, bisphenol A ethylene oxide adduct (2-20 mol) di (meth) acrylate, glycerin tri (meth) acrylate, glycerin ethylene oxide adduct (3-30 mol) tri (meth) Acrylate, glycerin propylene oxide adduct (3-30 mol) tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide adduct (3-30 mol) tri (meth) acrylate, trimethylolpropane Propylene oxide adduct (3 to 30 mol) Trifunctional vinyl compound such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide adduct (4 to 40 mol) ) Tetra (meth) acrylate, pentaerythritol propylene oxide adduct (4-40 mol) tetra (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol ethylene oxide adduct (4-40 mol) tetra (meth) acrylate , Pentaerythritol propylene oxide adduct (4 to 40 mol) tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane ethylene oxide adduct (4 to 40 mol) tetra (meth) acrylate, ditrimethylolpropane Propylene oxide adduct (3 to 30 mol) Tetrafunctional vinyl compounds such as tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol And polyfunctional vinyl compounds such as ethylene oxide adduct (6 to 60 mol) hexa (meth) acrylate, dipentaerythritol propylene oxide adduct (6 to 60 mol) hexa (meth) acrylate, and mixtures thereof. (A) The active energy ray-curable compound can be appropriately selected according to the required cured film properties, and an active energy ray-curable oligomer such as polyester acrylate, polyurethane acrylate, or epoxy acrylate, if necessary. It is also possible to use together.
（ｂ）リン酸および／またはスルホン酸基含有化合物としては、リン酸、メタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、キシレンスルホン酸、スチレンスルホン酸、１０−カンファースルホン酸等およびそれらの混合物が挙げられる。特に、水溶液を形成し得るものであれば、より好ましい。リン酸を使用した場合には、高導電性の硬化塗膜が得られ、好適である。また、これらの酸は水溶液として使用することが取り扱い上好ましく、その際の濃度は１〜２０規定が好ましい。この範囲以外では、アニリンまたはアニリン組成物の酸化重合後、水の分離が困難になり易く好ましくない。 (B) Examples of phosphoric acid and / or sulfonic acid group-containing compounds include phosphoric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, styrenesulfonic acid, 10-camphorsulfonic acid, and the like. A mixture is mentioned. In particular, it is more preferable if it can form an aqueous solution. When phosphoric acid is used, a highly conductive cured coating film is obtained, which is preferable. Moreover, it is preferable on handling that these acids are used as aqueous solution, and the density | concentration in that case has preferable 1-20N. Outside this range, it is difficult to separate water after oxidative polymerization of aniline or an aniline composition.
（ｃ）ドーピング剤としては、アニリンの窒素原子をイオン化できるものであれば特に限定されるものではなく、塩酸、硫酸、硝酸、リン酸等の無機酸、およびスルホン酸基、リン酸基、カルボン酸基、硫酸エステル基、リン酸エステル基等の含有化合物である有機酸が挙げられる。スルホン酸基含有化合物が分散安定性とイオン化能力、すなわち最終的に得られる塗膜の導電性の点で好ましい。スルホン酸基含有化合物の例としては、メタンスルホン酸等のアルキルスルホン酸、ビニルスルホン酸、アリルスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、キシレンスルホン酸、ドデシルベンゼンスルホン酸等のアルキルベンゼンスルホン酸、スチレンスルホン酸、ナフタレンスルホン酸、カンファースルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸等を挙げることができる。これらは単独で使用してもよく２種類以上を併用してもよい。また、上記（ｂ）リン酸、スルホン酸基含有化合物およびカルボン酸基含有化合物のうち１種類あるいは２種類以上の化合物に用いられる酸化合物と同一であっても差し支えない。 (C) The doping agent is not particularly limited as long as it can ionize the nitrogen atom of aniline, and includes inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfonic acid groups, phosphoric acid groups, and carvone. An organic acid which is a compound containing an acid group, a sulfate ester group, a phosphate ester group or the like can be used. A sulfonic acid group-containing compound is preferable from the viewpoint of dispersion stability and ionization ability, that is, conductivity of a finally obtained coating film. Examples of sulfonic acid group-containing compounds include alkyl sulfonic acids such as methane sulfonic acid, alkyl sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, xylene sulfonic acid, and dodecyl benzene sulfonic acid. Styrene sulfonic acid, naphthalene sulfonic acid, camphor sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid and the like. These may be used alone or in combination of two or more. Further, the acid compound may be the same as the acid compound used in one or more of the above-mentioned (b) phosphoric acid, sulfonic acid group-containing compound and carboxylic acid group-containing compound.
（ｄ）アニリンまたはアニリン誘導体とは、アニリン骨格を有するものであれば特に限定されるものではなく、アニリン、またはアニリンのアミノ基またはベンゼン環上の水素を、アルキル基、アリール基、アルキルエーテル基、カルボキシルエステル基、シアノ基、ハロゲン基等で置換した化合物が例示できる。導電性の点では、アニリンが好ましい。 (D) The aniline or aniline derivative is not particularly limited as long as it has an aniline skeleton, and aniline or an amino group of aniline or a hydrogen on a benzene ring is substituted with an alkyl group, an aryl group, or an alkyl ether group. And a compound substituted with a carboxyl ester group, a cyano group, a halogen group or the like. From the viewpoint of conductivity, aniline is preferable.
本発明は上記（ａ）活性エネルギー線硬化性化合物、（ｂ）リン酸および／またはスルホン酸基含有化合物、および（ｃ）ドーピング剤の存在下で、（ｄ）アニリンまたはアニリン誘導体を酸化重合させるものである。 The present invention oxidizes and polymerizes (d) aniline or an aniline derivative in the presence of (a) an active energy ray-curable compound, (b) a phosphoric acid and / or sulfonic acid group-containing compound, and (c) a doping agent. Is.
各組成比としては、（ａ）活性エネルギー線硬化性化合物１００重量部に対して（ｄ）アニリンまたはアニリン誘導体１〜１０重量部、酸化重合させる際の化合物の総重量１００重量部に対して（ｂ）リン酸および／またはスルホン酸基含有化合物としては、０．１〜１０モル、（ｄ）アニリンまたはアニリン誘導体１００重量部に対して、（ｃ）ドーピング剤３０〜１０００重量部の範囲が好ましい。この範囲以外では、得られる（ｄ）ポリアニリン組成物の良好な分散安定性、および硬化被膜の良好な導電性が得られ難く好ましくない。 As each composition ratio, (d) 1 to 10 parts by weight of aniline or an aniline derivative with respect to 100 parts by weight of the active energy ray-curable compound, b) The phosphoric acid and / or sulfonic acid group-containing compound is preferably in the range of 0.1 to 10 moles, (d) 100 to parts by weight of aniline or aniline derivative, and (c) 30 to 1000 parts by weight of the doping agent. . Outside this range, it is not preferable because it is difficult to obtain good dispersion stability of the obtained (d) polyaniline composition and good conductivity of the cured film.
酸化重合は従来公知の一般的な方法で行うことができる。−４０℃〜８０℃、より好ましくは−５℃〜３０℃の反応温度で酸化剤の存在下で行われる。酸化剤としては、過硫酸アンモニウム、過硫酸カリウム、過塩素酸カリウム、塩化カリウム、ヨウ化カリウム、塩化鉄(II)などが挙げられ、特に過硫酸アンモニウムに代表される過硫酸類が好ましい。 The oxidation polymerization can be performed by a conventionally known general method. It is carried out in the presence of an oxidizing agent at a reaction temperature of −40 ° C. to 80 ° C., more preferably −5 ° C. to 30 ° C. Examples of the oxidizing agent include ammonium persulfate, potassium persulfate, potassium perchlorate, potassium chloride, potassium iodide, iron (II) chloride and the like, and persulfates represented by ammonium persulfate are particularly preferable.
酸化重合で得られるポリアニリンの重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定のポリスチレン換算で、１，０００〜５００，０００の範囲内にあることが好ましい。重量平均分子量が１，０００未満では、ドーピング剤をドープした状態での導電性が低くなりやすく好ましくない。一方、重量平均分子量が５００，０００を超えると、ポリアニリン組成物の分散安定性が悪くなりやすく好ましくない。重量平均分子量は２，０００〜２００,０００の範囲内がさらに好ましく、最も好ましくは５，０００〜１００，０００の範囲内である。 The weight average molecular weight of polyaniline obtained by oxidative polymerization is preferably in the range of 1,000 to 500,000 in terms of polystyrene measured by gel permeation chromatography (GPC). If the weight average molecular weight is less than 1,000, the conductivity in a state where the dopant is doped is likely to be low, which is not preferable. On the other hand, when the weight average molecular weight exceeds 500,000, the dispersion stability of the polyaniline composition tends to deteriorate, which is not preferable. The weight average molecular weight is more preferably in the range of 2,000 to 200,000, and most preferably in the range of 5,000 to 100,000.
本発明のポリアニリン組成物には、必要に応じて、光重合開始剤、紫外線安定剤、紫外線吸収剤、酸化防止剤、可塑剤、レベリング剤、ハジキ防止剤等の化合物を任意に混合することが出来る。 The polyaniline composition of the present invention may be optionally mixed with a compound such as a photopolymerization initiator, an ultraviolet stabilizer, an ultraviolet absorber, an antioxidant, a plasticizer, a leveling agent, an anti-repellent agent, if necessary. I can do it.
以下に、実施例により、本発明をさらに詳細に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。なお、実施例における「部」は、「重量部」を表す。
〔実施例１〕
撹拌器、温度計及び滴下ロートを備えた４つ口フラスコに、３規定リン酸水溶液を１００部、アニリン３部、ドデシルベンゼンスルホン酸６部、トリプロピレングリコールトリエトキシトリアクリレート１００部を仕込み、室温で３０分攪拌後、０℃に冷却し、さらに２時間攪拌した。過硫酸アンモニウム６ｇを５規定リン酸２４ｇに溶解させた水溶液を滴下ロートから、系を０℃に保持しながら１時間で滴下した。さらに０℃で撹拌を２４時間行った。反応終了後、反応溶液を静置し、水層を分離除去し、ポリアニリン組成物（Ａ１）を得た。
〔実施例２〕
３規定リン酸水溶液を１規定メタンスルホン酸水溶液に変えた以外は、実施例１と同様の方法で、ポリアニリン組成物（Ａ２）を得た。
〔実施例３〕
アニリンをｏ−トルイジンに変えた以外は、実施例１と同様の方法で、ポリアニリン組成物（Ａ３）を得た。
〔実施例４〕
ドデシルベンゼンスルホン酸をラウリル硫酸ナトリウムに変えた以外は、実施例１と同様の方法で、ポリアニリン組成物（Ａ４）を得た。
〔比較例１〕
３規定リン酸水溶液を１規定塩酸水溶液に変えた以外は、実施例１と同様の方法で、ポリアニリン組成物（Ａ５）を得た。
EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.
[Example 1]
A four-necked flask equipped with a stirrer, a thermometer and a dropping funnel is charged with 100 parts of a 3N aqueous phosphoric acid solution, 3 parts of aniline, 6 parts of dodecylbenzenesulfonic acid, and 100 parts of tripropylene glycol triethoxytriacrylate at room temperature. For 30 minutes, cooled to 0 ° C., and further stirred for 2 hours. An aqueous solution in which 6 g of ammonium persulfate was dissolved in 24 g of 5N phosphoric acid was dropped from an addition funnel over 1 hour while maintaining the system at 0 ° C. Further, stirring was performed at 0 ° C. for 24 hours. After completion of the reaction, the reaction solution was allowed to stand, and the aqueous layer was separated and removed to obtain a polyaniline composition (A1).
[Example 2]
A polyaniline composition (A2) was obtained in the same manner as in Example 1 except that the 3N phosphoric acid aqueous solution was changed to the 1N methanesulfonic acid aqueous solution.
Example 3
A polyaniline composition (A3) was obtained in the same manner as in Example 1 except that aniline was changed to o-toluidine.
Example 4
A polyaniline composition (A4) was obtained in the same manner as in Example 1 except that dodecylbenzenesulfonic acid was changed to sodium lauryl sulfate.
[Comparative Example 1]
A polyaniline composition (A5) was obtained in the same manner as in Example 1 except that the 3N phosphoric acid aqueous solution was changed to the 1N hydrochloric acid aqueous solution.
（電子線硬化性試験）
実施例１〜４、比較例１で得られたポリアニリン組成物（Ａ１〜Ａ５）を、ワイヤバーコータにより乾燥被膜厚が約５μｍとなるようにＰＥＴフィルム（東洋紡績社製コスモシャインＡ４１００）上に塗工し、Ｍｉｎ−ＥＢ Ｌａｂｏ電子線照射装置（ウシオ電機社製）を用い、加速電圧５０ｋＶ、照射線量１００ｋＧｙ、酸素濃度５００ｐｐｍの窒素置換した雰囲気で電子線を照射した。電子線硬化後の塗膜の表面抵抗率を測定した。評価結果を表１に示す。
(Electron beam curability test)
The polyaniline compositions (A1 to A5) obtained in Examples 1 to 4 and Comparative Example 1 were placed on a PET film (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) so that the dry film thickness was about 5 μm using a wire bar coater. Coating was performed, and an electron beam was irradiated in a nitrogen-substituted atmosphere with an acceleration voltage of 50 kV, an irradiation dose of 100 kGy, and an oxygen concentration of 500 ppm using a Min-EB Labo electron beam irradiation apparatus (manufactured by Ushio Inc.). The surface resistivity of the coating film after electron beam curing was measured. The evaluation results are shown in Table 1.
（紫外線硬化性試験）
実施例１〜４、比較例１で得られたポリアニリン組成物（Ａ１〜Ａ５）１００部にイルガキュア１８４（チバ・スペシャリティーケミカルズ社製光重合開始剤）５部を添加し、ワイヤバーコータにより乾燥被膜厚が約５μｍとなるようにＰＥＴフィルム（東洋紡績社製コスモシャインＡ４１００）上に塗工し、紫外線硬化装置（アイグラフィックス社製）を用いて、メタルハライドランプ１１２Ｗ／ｃｍ、コンベアスピード３０ｍ／ｍｉｎで紫外線を照射した。紫外線照射後の塗膜の表面抵抗率を測定した。評価結果を表１に示す。
(UV curing test)
5 parts of Irgacure 184 (Ciba Specialty Chemicals photopolymerization initiator) was added to 100 parts of the polyaniline composition (A1 to A5) obtained in Examples 1 to 4 and Comparative Example 1, and dried with a wire bar coater. The film was coated on a PET film (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) so that the film thickness was about 5 μm, and a metal halide lamp 112 W / cm, conveyor speed 30 m / Ultraviolet rays were irradiated for min. The surface resistivity of the coating film after ultraviolet irradiation was measured. The evaluation results are shown in Table 1.
（金属腐食試験）
実施例１〜４、比較例１で得られたポリアニリン組成物（Ａ１〜Ａ５）を、冷間圧延鋼板（ＳＰＣＣ−ＳＢ）上に０．１ｍｌ液滴状に置いた。室温で２４時間放置後、ポリアニリン組成物を拭き取った後の状態を目視で評価した。評価結果を表１に示す。
(Metal corrosion test)
The polyaniline compositions (A1 to A5) obtained in Examples 1 to 4 and Comparative Example 1 were placed in the form of 0.1 ml droplets on a cold rolled steel sheet (SPCC-SB). After standing at room temperature for 24 hours, the state after wiping off the polyaniline composition was visually evaluated. The evaluation results are shown in Table 1.
値を測定した。
The value was measured.
表１に示すように、実施例１〜５の本発明のポリアニリン組成物は、電子線または紫外線の照射により容易に硬化し、導電性に優れた塗膜を得ることができる。また、比較例１のように腐食性の酸を用いていないため、金属腐食性にも優れるものであった。 As shown in Table 1, the polyaniline composition of the present invention of Examples 1 to 5 can be easily cured by irradiation with an electron beam or ultraviolet rays, and a coating film excellent in conductivity can be obtained. Moreover, since the corrosive acid was not used like the comparative example 1, it was excellent also in metal corrosivity.
Claims (5)
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