JP2004307636A - Conductive polyurethane foam - Google Patents
Conductive polyurethane foam Download PDFInfo
- Publication number
- JP2004307636A JP2004307636A JP2003102944A JP2003102944A JP2004307636A JP 2004307636 A JP2004307636 A JP 2004307636A JP 2003102944 A JP2003102944 A JP 2003102944A JP 2003102944 A JP2003102944 A JP 2003102944A JP 2004307636 A JP2004307636 A JP 2004307636A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane foam
- aqueous dispersion
- polypyrrole
- conductive
- conductive polyurethane
- 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.)
- Granted
Links
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 79
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 79
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 62
- 239000006185 dispersion Substances 0.000 claims abstract description 46
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 229920005596 polymer binder Polymers 0.000 claims abstract description 9
- 239000002491 polymer binding agent Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- -1 acryl Chemical group 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Conductive Materials (AREA)
Abstract
【課題】内部まで均一に、使用環境温湿度で１０４Ω〜１０１０Ωの安定した表面固有抵抗値を有し、且つその耐久性に優れ、成形性、透明性、密着性、耐水性に優れた導電性ポリウレタンフォームを提供する。
【解決手段】ポリウレタンフォームの連通気孔表面にポリウレタンフォームに対して０．１〜１０重量％のポリピロールが付着されてなる導電性ポリウレタンフォーム。ポリウレタンフォームにポリピロールを含む水分散液を含浸してなる上記の導電性ポリウレタンフォーム。ポリピロールを含む水分散液が、高分子酸および酸化重合触媒を含む水溶液中でピロールを化学酸化重合することによって得られるポリピロールと高分子酸とを含有する水分散液である上記導電性ポリウレタンフォーム。上記ポリピロールを含む水分散液にさらに高分子バインダーを併用してなる導電性ポリウレタンフォーム。
【選択図】なし[Object] To provide a stable surface specific resistance value of 10 4 Ω to 10 10 Ω at a use environment temperature and humidity even inside, and to have excellent durability, moldability, transparency, adhesion, and water resistance. Provide excellent conductive polyurethane foam.
An electrically conductive polyurethane foam comprising 0.1 to 10% by weight of polypyrrole based on the polyurethane foam on the surface of continuous pores of the polyurethane foam. The above-mentioned conductive polyurethane foam obtained by impregnating a polyurethane foam with an aqueous dispersion containing polypyrrole. The above conductive polyurethane foam, wherein the aqueous dispersion containing polypyrrole is an aqueous dispersion containing polypyrrole and a polymer acid obtained by chemically oxidizing and polymerizing pyrrole in an aqueous solution containing a polymer acid and an oxidation polymerization catalyst. A conductive polyurethane foam obtained by further using a polymer binder in combination with the aqueous dispersion containing polypyrrole.
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、電子写真、静電記録等のプリンターにおける導電ローラー等に用いるに好適な導電性ポリウレタンフォームに関する。
【０００２】
【従来の技術】
近年広く普及し今日の社会活動にとっては不可欠のものとなっている電子写真は、一般にそのプロセスは１）帯電、２）露光、３）現像、４）転写、５）定着、６）除電 の各工程からなり、いずれの工程においても各種のローラーが使用されている。ローラーの素材は従来種々のゴムが使用されてきたが、感光ドラム等の精密部品と接触するためそれらの相手を傷つけないこと、あるいはローラーの接触面積を増してグリップ性を確実にする等の目的から柔軟性に優れたポリウレタンフォームが用いられるようになってきた。各工程で使用されるローラーには静電気を精密に制御することのできる素材が求められており、導電ローラー等は、環境が変化しても大きく変動しない導電性が要求される。
【０００３】
このような要求に応えるために導電性物質を添加したポリウレタンフォームが提案されている。使用されている導電性物質としては、カーボンや金属酸化物が主たるものである（特許文献１〜２参照）。特許文献１には、導電性カーボン、グラファイト、導電性金属粉、金属酸化物等の電子伝導機構による導電性付与物質と、ＮａＣｌＯ４その他の金属塩と多価アルコール等との錯体等のイオン伝導機構による導電性付与物質とをポリウレタンフォームを構成する材料中に混合分散させた後発泡させてなる導電性ポリウレタンフォームが開示されている。また、特許文献２には、アニリン、アニリン誘導体またはこれらの混合物の酸化重合物をポリウレタン中に分散させてなる半導電性材料が開示されている。
【０００４】
しかし、開示された方法はいずれも導電性付与物質をポリウレタンフォームの原料中に予め混合し、均一な原料混合物としてから重合および発泡して導電性ポリウレタンフォームを製造している。通常ポリウレタンフォームは生産性の向上のために大きな塊であるスラブとして製造しているが、スラブの上部と下部とでは発泡状態が異なり、比較的嵩密度の低い上部と気泡が細かく比較的嵩密度の高い下部とでは添加剤である導電性付与物質の単位体積当たりの存在量も異なってくる。そのため切り出されたフォームは切りだし部分によって電気特性も当然異なったものとなる。また特許文献２において使用されているような分子量の高い添加物をポリウレタン原料に混合すると原料の粘度が著しく増加して良好な発泡体を得ることは困難となる。
【０００５】
また、発泡させたポリウレタンフォームに導電性物質を付与する技術も開示されている（特許文献３）。特許文献３にはカーボン塗料のような導電性物質を後処理によってポリウレタンフォームに付与して得られる導電性ポリウレタンフォームが記載されている。しかし使用されているカーボン塗料では、カーボン粒子が比較的大きな粒子であるため、ウレタンフォームの内部まで均一に付着しない。このような導電性ポリウレタンフォームでは表面と内部で導電性が不均一であり、内部の導電性は十分に改良されない。
特許文献４には、ポリウレタンフォームの表面に酸化剤を塗布したのち、ピロールのような共役二重結合を持つ化合物を気相重合によって導電性重合体をポリウレタンフォームの表面に形成する技術が記載されている。しかしこの方法の場合も、ポリウレタンフォームの表面層だけに導電特性が付与されるに過ぎない。
しかし、例えば本発明の主たる用途である電子写真用導電ローラ等ではローラー内部の導電性が重要であって、導電性の大きさおよびその均一性が強く求められる。
さらに最近、ピロールと酸化剤をポリウレタンフォームに含浸させた状態でピロールを重合してポリウレタンフォームに導電性を付与する技術（特許文献５参照）、ポリピロールを含む水分散液をポリウレタンフォームに含浸してポリウレタンフォームに導電性を付与する技術（特許文献６参照）が開示されている。しかし、特許文献５及び６によって得られる導電性ポリウレタンフォームはともにポリピロールの基材への付着性を目的としたバインダーを使用していないため耐久性の点で問題がある。均一で且つ上記用途にとって適切な大きさの導電性を付与した導電性ポリウレタンフォームはこれまで得られていなかった。
【０００６】
【特許文献１】
特許第２６０１７８２号公報
【特許文献２】
特開平４−２９２６５４号公報
【特許文献３】
特開平５−２６２９０７号公報
【特許文献４】
特開平６−２９８９８９号公報
【特許文献５】
特開平９−２５３５７号公報
【特許文献６】
特開平９−６７５０６号公報
【０００７】
【発明が解決しようとする課題】
本発明は、上記の種々の課題を解決するためになされたものであり、湿度依存性がなく、内部まで均一に、使用環境温湿度で１０４Ω〜１０１０Ωの安定した表面抵抗値を発現し、表面抵抗値のバラツキが小さく、さらに導電性の耐久性に優れ、成形性、透明性、密着性、耐水性に優れた導電性ポリウレタンフォームを提供することにある。
【０００８】
【課題を解決するための手段】
本発明は、ポリウレタンフォームの連通気孔表面にポリウレタンフォームに対して０．１〜１０重量％のポリピロールが付着されてなる導電性ポリウレタンフォームに関する。
本発明は、詳しくは、ポリウレタンフォームにポリピロールを含む水分散液（以下、「ＰＰｙ含有水分散液」という。）を含浸してなる上記の導電性ポリウレタンフォームに関する。
特に、本発明は、上記において、ＰＰｙ含有水分散液が、高分子酸および酸化重合触媒を含む水溶液中でピロールを化学酸化重合することによって得られるポリピロールと高分子酸とを含有する水分散液である導電性ポリウレタンフォームに関する。
また、本発明では、上記のＰＰｙ含有水分散液は高分子バインダーを併用することができる。
さらにまた、本発明では、上記のＰＰｙ含有水分散液は界面活性剤および／または消泡剤をさらに含有していてもよい。
また、上記本発明の導電性ポリウレタンフォームは、１０４〜１０１０Ωの表面抵抗値を持ちうる。
【０００９】
【発明の実施の形態】
本発明の導電性ポリウレタンフォームは、ポリウレタンフォームの連通気孔表面にポリピロールが付着されたものである。このような導電性ポリウレタンフォームは、ポリウレタンフォームにＰＰｙ含有水分散液を含浸することによって得られる。
本発明の導電性ポリウレタンフォームの特徴は、ポリピロールが水分散液としてポリウレタンフォームに含浸されているため、ポリウレタンフォームの表面だけでなく、連通気孔の内部表面まで均一に導電性物質であるポリピロールが付着されているところにある。したがって、本発明の導電性ポリウレタンフォームはその表面だけでなく内部まで均一に導電性が付与されている。
【００１０】
本発明で使用する導電性ポリピロールは、、ピロールを高分子酸の存在下に化学酸化重合することによって、ポリピロールの水分散液として得られる。本発明の導電性ポリウレタンフォームは、そのようなポリピロール含有水分散液にポリウレタンフォームを含浸させ、乾燥させることにより得られる。
【００１１】
ポリウレタンフォームに含浸する、本発明で用いる上記のＰＰｙ含有水分散液は、例えば、特開平７−１６５８９２号公報の［０００７］〜［００１１］に記載された方法によって得ることができる。すなわち、高分子酸および酸化重合触媒を含む水溶液にピロールを添加するか、ピロールおよび高分子酸を含む水溶液に酸化重合触媒を添加することにより、ピロールを化学酸化重合させて、導電性のＰＰｙ含有水分散液を得ることができる。
このとき必要であれば、得られた水分散液を再沈法や透析法によって精製することができる。
【００１２】
高分子酸は、ポリピロールの分散安定剤として働くものであり、ポリピロールを反応媒体中に安定分散し得るものであれば特に制限はなく、具体的にはアルギン酸、ポリアクリル酸、ポリスチレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリビニル硫酸等が挙げられ、単独で使用しても２種以上を併用してもよい。これらの高分子酸は酸基の一部がナトリウム塩、カリウム塩、アンモニウム塩のような塩の形になっていてもよい。あるいは一部がエステル化していてもよい。
これらの高分子酸の量は、ピロール１モルに対して、フリーの酸基が好ましくは０．０１〜２０当量、より好ましくは０．１〜５当量となるように用いる。
【００１３】
酸化重合触媒としては、ピロールを重合し得るものであればよく、例えば、過硫酸アンモニウム、塩化第２鉄、重クロム酸カリウム、過マンガン酸カリウム等、または過酸化水素−第１鉄塩等のレドックス触媒等が好ましく用いられる。これらの酸化重合触媒は単独で使用しても２種以上を併用してもよい。
【００１４】
また、ＰＰｙ含有水分散液は、分散体の再凝集や沈殿に対する安定性を向上させるために、各種の界面活性剤、増粘剤等を、あるいは泡立ちを防ぐために消泡剤を併用することができる。
【００１５】
本発明のＰＰｙ含有水分散液には、ポリピロールをポリウレタンフォームの気孔表面に強固に付着させるために高分子バインダーを含有することが好ましい。このようなバインダーによってポリピロールをポリウレタンフォームに付着させることにより、ポリウレタンフォームの導電特性に耐久性を持たせることができる。高分子バインダーとしては、水溶性高分子化合物または水系でエマルジョンを形成する高分子化合物が用いられる。このような高分子化合物は水溶液または水性エマルジョンとしてＰＰｙ含有水分散液に混合することができる。
【００１６】
水溶性高分子化合物の具体例としては、ポリビニルアルコール、ポリビニルホルマール等のポリビニルアルコール類、ポリアクリルアミド、ポリアクリルアミドメチルプロパンスルホン酸等のポリアクリルアミド類、ポリビニルピロリドン類、水溶性アルキド樹脂、水溶性メラミン樹脂、水溶性尿素樹脂、水溶性フェノール樹脂、水溶性エポキシ樹脂、水溶性ポリブタジエン樹脂、水溶性アクリル樹脂、水溶性ウレタン樹脂、水溶性アクリル／スチレン樹脂、水溶性酢酸ビニル／アクリル共重合樹脂、水溶性ポリエステル樹脂、水溶性スチレン／マレイン酸共重合樹脂、水溶性フッ素樹脂およびこれらの共重合体等が挙げられる。
【００１７】
水系でエマルジョンを形成する高分子化合物の具体例としては、水系アルキド樹脂、水系メラミン樹脂、水系尿素樹脂、水系フェノール樹脂、水系エポキシ樹脂、水系ポリブタジエン樹脂、水系アクリル樹脂、水系ウレタン樹脂、水系アクリル／スチレン樹脂、水系酢酸ビニル樹脂、水系酢酸ビニル／アクリル共重合樹脂、水系ポリエステル樹脂、水系スチレン／マレイン酸共重合樹脂、水系フッ素樹脂、水系塩素化ポリオレフィン樹脂およびこれらの共重合体等が挙げられる。
特に好ましい高分子バインダーは、水系アクリル樹脂、水系ウレタン樹脂及び水系ポリエステル樹脂である。これらのバインダーは水溶液としてポリピロール水分散液に混合すると、水分散液の粘度を上げ、その結果ポリウレタンフォームへの含浸性が低下するため、エマルジョンまたはサスペジョンのような分散液として用いることが好ましい。
【００１８】
ＰＰｙ含有水分散液中と併用する高分子バインダーの量は、ＰＰｙ含有水分散液固形分：高分子バインダー固形分として、１０：９０〜９０：１０、好ましくは３０：７０〜７０：３０（重量比）である。
【００１９】
本発明の導電性ポリウレタンフォームにおけるポリピロールの付着量は、ポリウレタンフォームに対して、好ましくは０．１〜１０重量％である。０．１重量％未満では安定した表面抵抗値が得られず、１０重量％以上では得られる表面抵抗値が一定に近づくため、付着量を多くしてもコストが上昇し、かつ生産性が低下する傾向になる。好ましい範囲は１．０〜５重量％、より好ましくは１．０〜４．０重量％である。
これにより、表面抵抗値が１０４〜１０１０Ωの導電性ポリウレタンフォームが安定して得られる。
【００２０】
なお、本発明で特定する表面抵抗値は、抵抗測定器（三菱化学社製Ｈｉｒｅｓｔａ ＩＰ ＭＣＰ−ＨＴ２６０ ＨＡ型プローブ）を用いて１０Ｖの電圧下、１０秒で測定した。
【００２１】
本発明で使用するポリウレタンフォームは、２個以上の活性水素を含有する化合物と２個以上のイソシアネート基を有する化合物と、触媒、発泡剤、整泡剤等の添加剤と共に撹拌混合して発泡硬化させてなるポリウレタンフォームであり、２個以上の活性水素を含有する化合物としては、一般のポリウレタンフォームに用いられるポリオール、即ち末端にＯＨ基を有するポリエーテルポリオール、ポリエステルポリオール、ポリエーテルエステルポリオールなどが挙げられる他、ポリマーポリオール等も使用できる。２個以上のイソシアネート基を含有する化合物としては、同様に一般的なポリウレタンフォームで使用されるポリイソシアネートが使用できる。例えば、トリレンジイソシアネート（ＴＤＩ）、４，４−ジフェニルメタンジイソシアネート（ＭＤＩ）およびこれらのポリイソシアネートの混合物や変性物などである。なお、密度および硬度はその用途によって任意に選ぶことができる。
【００２２】
本発明の導電性ポリウレタンフォームは、上記のポリウレタンフォームに、ポリピロールを含む上記の水分散液を含浸し、乾燥することによって製造することができる。乾燥は必ずしも加熱を必要としないが、付着をより確実にするためには、高分子バインダーの軟化点以上の温度で加熱することが好ましい。
【００２３】
【実施例】
以下、実施例によって本発明をより詳細に且つ具体的に説明する。
ＰＰｙ含有水分散液（Ａ）の調製
水１００ｍｌにポリアクリル酸２ｇ、硫酸第１鉄（７水和物）０．５ｇ、ピロール２ｍｌを溶解した。これを室温で攪拌しながら、過酸化水素（３１％水溶液）３．８ｇを水で１００ｍｌとしてものを１時間かけてゆっくり滴下し、さらに３時間反応させてポリピロー水分散液を得た。得られた水分散液を２５％アンモニア水でｐＨを１０．０に調整したのち、メタノールで沈殿させ、濾過し、濾過物に全量が５０ｇとなる量の水を加えて再分散して、固形分濃度が８重量％の精製ポリピロールを含有する水分散液を得た。また、未反応モノマーの定量の結果により、ポリピロール濃度は３．２重量％であった。
【００２４】
実施例 １〜４
上記で調製した固形分濃度が８重量％のＰＰｙ含有水分散液（Ａ）にアクリルエマルジョン「マルサーブ７６０」〔丸菱油化工業社製、商品名；アクリル樹脂含量５０重量％〕及び水を混合して全固形分中のＰＰｙ含有水分散液（Ａ）の固形分の割合が４０重量％一定で総固形分濃度がそれぞれ１０（実施例１）、１２（実施例２）、１４（実施例３）、１５（実施例４）重量％の処理液を調製し、この中に、見かけ密度３５ｋｇ／ｍ３の軟質ポリウレタンフォーム（寸法：２．５ｃｍ（ａ）×７．５ｃｍ（ｂ）×１５ｃｍ（ｃ））を３分間浸漬後、マングル（ロール径：１２．５ｃｍ、絞り圧：５．０ｋｇ／ｃｍ２）で絞った。マングルで絞った後、オーブン中で８０℃×２時間乾燥した。
放冷後、試料内部から（ａ）×（ｂ）面に平行に試料の先端から、５ｃｍ、１０ｃｍの所で切断し、（イ）先端（ａ）×（ｂ）面、（ロ）５ｃｍ切断面、（ハ）１０ｃｍ切断面の表面抵抗値を測定した。
なお、未処理の軟質ポリウレタンフォームの表面抵抗値は３．０×１０１４Ωであった。
ポリピロール（ＰＰｙ）固形分の付着率と表面固有抵抗値のデータを表１に記載した。
ここでポリピロール付着率とは処理前の乾燥ポリウレタンフォームの重量に対する付着処理液ポリピロールの百分率をいう。
【００２５】
実施例 ５〜８
ＰＰｙ含有水分散液（Ａ）にアクリルエマルジョン「マルサーブ７６０」〔丸菱油化工業社製、商品名；アクリル樹脂含量５０重量％〕及び水を混合して全固形分中のＰＰｙ含有水分散液（Ａ）の固形分の割合が５０重量％一定で総固形分濃度がそれぞれ１０（実施例５）、１１（実施例６）、１２（実施例７）、１３（実施例８）重量％の処理液を調製した。この原液に実施例１〜４と同様に軟質ポリウレタンフォームを浸漬して、フォームにポリピロールを付着した。
ポリピロール（ＰＰｙ）付着率と表面固有抵抗値のデータを表２に記載した。
【００２６】
実施例 ９〜１２
ＰＰｙ含有水分散液（Ａ）にアクリルエマルジョン「マルサーブ７６０」〔丸菱油化工業社製、商品名；アクリル樹脂含量５０重量％〕及び水を混合して全固形分中のＰＰｙ含有水分散液（Ａ）の固形分の割合が６０重量％一定で総固形分濃度がそれぞれ１０（実施例９）、１０．５（実施例１０）、１１（実施例１１）重量％の処理液を調製した。この原液に実施例１〜４と同様に軟質ポリウレタンフォームを浸漬して、フォームにポリピロールを付着した。さらに、実施例１２として、ＰＰｙ含有水分散液（Ａ）にアクリルエマルジョン「マルサーブ７６０」〔丸菱油化工業社製、商品名；アクリル樹脂含量５０重量％〕及び水を混合して全固形分中のＰＰｙ含有水分散液（Ａ）の固形分の割合が６５重量％一定で総固形分濃度が１１重量％の処理液を調製した。この原液に実施例１〜４と同様に軟質ポリウレタンフォームを浸漬して、フォームにポリピロールを付着した。実施例９〜１２のポリピロール（ＰＰｙ）付着率と表面固有抵抗値のデータを表３に記載した。
なお、得られた実施例１〜１２のポリピロール付着フォームを、１０万回繰返し圧縮試験後、抵抗値を測定したところ、繰返し試験前の抵抗値と比較して、ほとんど変化は見られなかった。
【００２７】
【表１】
【表２】
【表３】
【発明の効果】
本発明は、内部まで均一に優れた導電性を有するポリウレタンフォームを提供することができ、電子写真、静電記録等のプリンターにおける導電ローラー等として有用である。この導電性ポリウレタンフォームは１０４Ωのオーダーの高い導電性をもち、その耐久性にも優れている。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a conductive polyurethane foam suitable for use as a conductive roller in a printer for electrophotography, electrostatic recording, and the like.
[0002]
[Prior art]
Electrophotography, which has become widespread in recent years and has become indispensable for today's social activities, generally involves the following processes: 1) electrification, 2) exposure, 3) development, 4) transfer, 5) fixing, and 6) static elimination. It consists of steps, and in each step, various rollers are used. Various types of rubber have been used as the material of the roller in the past, but they do not damage the opponent because they are in contact with precision parts such as the photosensitive drum, or to increase the contact area of the roller to ensure grip Therefore, polyurethane foams having excellent flexibility have been used. Rollers used in each step are required to be made of a material capable of precisely controlling static electricity, and conductive rollers and the like are required to have conductivity that does not greatly change even when the environment changes.
[0003]
In order to meet such a demand, a polyurethane foam to which a conductive substance is added has been proposed. The conductive materials used are mainly carbon and metal oxides (see Patent Documents 1 and 2). Patent Literature 1 discloses a conductive material such as conductive carbon, graphite, conductive metal powder, and metal oxide which imparts conductivity by an electron conduction mechanism, and ion conduction such as a complex of NaClO 4 or another metal salt with a polyhydric alcohol or the like. A conductive polyurethane foam obtained by mixing and dispersing a conductivity-imparting substance by a mechanism in a material constituting the polyurethane foam and then foaming the mixture is disclosed. Patent Document 2 discloses a semiconductive material in which an oxidized polymer of aniline, an aniline derivative, or a mixture thereof is dispersed in polyurethane.
[0004]
However, in each of the disclosed methods, a conductive polyurethane foam is produced by previously mixing a conductivity-imparting substance in a raw material of a polyurethane foam, forming a uniform raw material mixture, and polymerizing and foaming the mixture. Normally, polyurethane foam is manufactured as a large slab to improve productivity.However, the foamed state is different between the upper and lower parts of the slab. The amount of the conductive material, which is an additive, per unit volume is different between the lower part and the higher part. Therefore, the cut-out foam naturally has different electrical characteristics depending on the cut-out portion. Further, when an additive having a high molecular weight as used in Patent Document 2 is mixed with a polyurethane raw material, the viscosity of the raw material is significantly increased, and it is difficult to obtain a good foam.
[0005]
In addition, a technique for imparting a conductive substance to a foamed polyurethane foam is also disclosed (Patent Document 3). Patent Document 3 describes a conductive polyurethane foam obtained by applying a conductive substance such as a carbon paint to a polyurethane foam by post-treatment. However, in the carbon coating used, since carbon particles are relatively large particles, they do not uniformly adhere to the inside of the urethane foam. In such a conductive polyurethane foam, the conductivity is not uniform between the surface and the inside, and the inside conductivity is not sufficiently improved.
Patent Literature 4 describes a technique in which an oxidizing agent is applied to the surface of a polyurethane foam, and then a compound having a conjugated double bond such as pyrrole is subjected to gas phase polymerization to form a conductive polymer on the surface of the polyurethane foam. ing. However, also in this method, only the surface layer of the polyurethane foam is provided with conductive properties.
However, for example, in a conductive roller for electrophotography which is a main application of the present invention, the conductivity inside the roller is important, and the magnitude and uniformity of the conductivity are strongly required.
More recently, a technique of imparting conductivity to a polyurethane foam by polymerizing pyrrole in a state in which the polyurethane foam is impregnated with pyrrole and an oxidizing agent (see Patent Document 5), and impregnating a polyurethane foam with an aqueous dispersion containing polypyrrole. A technique for imparting conductivity to a polyurethane foam (see Patent Document 6) is disclosed. However, the conductive polyurethane foams obtained in Patent Literatures 5 and 6 both have a problem in durability because they do not use a binder for the purpose of adhering polypyrrole to a substrate. Until now, conductive polyurethane foams which have been imparted with conductivity of a uniform size suitable for the above-mentioned applications have not been obtained.
[0006]
[Patent Document 1]
Japanese Patent No. 2601782 [Patent Document 2]
Japanese Patent Application Laid-Open No. 4-292654 [Patent Document 3]
Japanese Patent Application Laid-Open No. 5-262907 [Patent Document 4]
Japanese Patent Application Laid-Open No. 6-298889 [Patent Document 5]
Japanese Patent Application Laid-Open No. 9-25357 [Patent Document 6]
JP-A-9-67506
[Problems to be solved by the invention]
The present invention has been made in order to solve the above-described various problems, has no humidity dependency, and has a stable surface resistance value of 10 4 Ω to 10 10 Ω at a use environment temperature and humidity evenly to the inside. It is an object of the present invention to provide a conductive polyurethane foam which exhibits a small variation in surface resistance value, has excellent conductivity durability, and is excellent in moldability, transparency, adhesion and water resistance.
[0008]
[Means for Solving the Problems]
The present invention relates to a conductive polyurethane foam comprising 0.1 to 10% by weight of polypyrrole based on the polyurethane foam on the surface of continuous pores of the polyurethane foam.
More specifically, the present invention relates to the above-mentioned conductive polyurethane foam obtained by impregnating a polyurethane foam with an aqueous dispersion containing polypyrrole (hereinafter, referred to as a “PPy-containing aqueous dispersion”).
In particular, the present invention relates to the above-mentioned, wherein the PPy-containing aqueous dispersion contains polypyrrole obtained by chemically oxidatively polymerizing pyrrole in an aqueous solution containing a polymeric acid and an oxidative polymerization catalyst, and an aqueous dispersion containing a polymeric acid. And a conductive polyurethane foam.
Further, in the present invention, the PPy-containing aqueous dispersion may be used in combination with a polymer binder.
Furthermore, in the present invention, the PPy-containing aqueous dispersion described above may further contain a surfactant and / or an antifoaming agent.
In addition, the conductive polyurethane foam of the present invention may have a surface resistance of 10 4 to 10 10 Ω.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
The conductive polyurethane foam of the present invention is obtained by attaching polypyrrole to the surface of continuous pores of a polyurethane foam. Such a conductive polyurethane foam is obtained by impregnating a polyurethane foam with an aqueous dispersion containing PPy.
The feature of the conductive polyurethane foam of the present invention is that polypyrrole is impregnated into the polyurethane foam as an aqueous dispersion, so that not only the surface of the polyurethane foam but also the inner surface of the communicating pores, polypyrrole, which is a conductive substance, adheres uniformly. Where they are. Therefore, the conductive polyurethane foam of the present invention is uniformly provided with conductivity not only on the surface but also on the inside.
[0010]
The conductive polypyrrole used in the present invention can be obtained as an aqueous dispersion of polypyrrole by subjecting pyrrole to chemical oxidative polymerization in the presence of a polymeric acid. The conductive polyurethane foam of the present invention can be obtained by impregnating such a polypyrrole-containing aqueous dispersion with a polyurethane foam and drying.
[0011]
The above-mentioned PPy-containing aqueous dispersion used in the present invention to be impregnated into a polyurethane foam can be obtained, for example, by a method described in JP-A-7-165892 [0007] to [0011]. That is, by adding pyrrole to an aqueous solution containing a polymeric acid and an oxidative polymerization catalyst, or by adding an oxidative polymerization catalyst to an aqueous solution containing a pyrrole and a polymeric acid, the pyrrole is chemically oxidized and polymerized, and the conductive PPy-containing An aqueous dispersion can be obtained.
At this time, if necessary, the obtained aqueous dispersion can be purified by a reprecipitation method or a dialysis method.
[0012]
The polymer acid serves as a dispersion stabilizer for polypyrrole, and is not particularly limited as long as polypyrrole can be stably dispersed in the reaction medium.Specifically, alginic acid, polyacrylic acid, polystyrenesulfonic acid, polyvinyl Sulfonic acid, polyallylsulfonic acid, polyvinyl sulfuric acid and the like are mentioned, and they may be used alone or in combination of two or more. These polymeric acids may have some of the acid groups in the form of salts such as sodium salts, potassium salts, and ammonium salts. Alternatively, some may be esterified.
The amount of these polymeric acids is such that the amount of free acid groups is preferably 0.01 to 20 equivalents, more preferably 0.1 to 5 equivalents, per 1 mol of pyrrole.
[0013]
As the oxidative polymerization catalyst, any catalyst capable of polymerizing pyrrole may be used. For example, redox such as ammonium persulfate, ferric chloride, potassium dichromate, potassium permanganate, or hydrogen peroxide-ferrous salt is used. Catalysts and the like are preferably used. These oxidation polymerization catalysts may be used alone or in combination of two or more.
[0014]
Further, the PPy-containing aqueous dispersion may be used in combination with various surfactants, thickeners and the like in order to improve the stability of the dispersion against re-aggregation and precipitation, or with an antifoaming agent in order to prevent foaming. it can.
[0015]
The PPy-containing aqueous dispersion of the present invention preferably contains a polymer binder for firmly attaching polypyrrole to the pore surface of the polyurethane foam. By attaching polypyrrole to the polyurethane foam with such a binder, durability can be imparted to the conductive properties of the polyurethane foam. As the polymer binder, a water-soluble polymer compound or a polymer compound that forms an emulsion in an aqueous system is used. Such a polymer compound can be mixed with the PPy-containing aqueous dispersion as an aqueous solution or an aqueous emulsion.
[0016]
Specific examples of the water-soluble polymer compound include polyvinyl alcohols, polyvinyl alcohols such as polyvinyl formal, polyacrylamides, polyacrylamides such as polyacrylamide methylpropanesulfonic acid, polyvinylpyrrolidones, water-soluble alkyd resins, and water-soluble melamine resins. , Water-soluble urea resin, water-soluble phenol resin, water-soluble epoxy resin, water-soluble polybutadiene resin, water-soluble acrylic resin, water-soluble urethane resin, water-soluble acryl / styrene resin, water-soluble vinyl acetate / acryl copolymer resin, water-soluble Examples include polyester resins, water-soluble styrene / maleic acid copolymer resins, water-soluble fluororesins, and copolymers thereof.
[0017]
Specific examples of the polymer compound that forms an emulsion in an aqueous system include an aqueous alkyd resin, an aqueous melamine resin, an aqueous urea resin, an aqueous phenol resin, an aqueous epoxy resin, an aqueous polybutadiene resin, an aqueous acrylic resin, an aqueous urethane resin, and an aqueous acrylic resin. Examples include styrene resin, aqueous vinyl acetate resin, aqueous vinyl acetate / acrylic copolymer resin, aqueous polyester resin, aqueous styrene / maleic acid copolymer resin, aqueous fluororesin, aqueous chlorinated polyolefin resin, and copolymers thereof.
Particularly preferred polymer binders are aqueous acrylic resins, aqueous urethane resins and aqueous polyester resins. When these binders are mixed with an aqueous polypyrrole dispersion as an aqueous solution, the viscosity of the aqueous dispersion is increased, and as a result, the impregnation property of the polyurethane foam is reduced. Therefore, it is preferable to use the binder as a dispersion such as an emulsion or a suspension.
[0018]
The amount of the polymer binder used in combination with the PPy-containing aqueous dispersion is 10:90 to 90:10, preferably 30:70 to 70:30 (weight: PPy-containing aqueous dispersion solid: polymer binder solid). Ratio).
[0019]
The attached amount of polypyrrole in the conductive polyurethane foam of the present invention is preferably 0.1 to 10% by weight based on the polyurethane foam. If the amount is less than 0.1% by weight, a stable surface resistance cannot be obtained. If the amount is more than 10% by weight, the obtained surface resistance approaches a constant value. Tend to. A preferred range is 1.0 to 5% by weight, more preferably 1.0 to 4.0% by weight.
Thereby, a conductive polyurethane foam having a surface resistance value of 10 4 to 10 10 Ω can be stably obtained.
[0020]
The surface resistance value specified in the present invention was measured in 10 seconds under a voltage of 10 V using a resistance measuring device (Hiresta IP MCP-HT260 HA type probe manufactured by Mitsubishi Chemical Corporation).
[0021]
The polyurethane foam used in the present invention is foam-hardened by stirring and mixing with a compound containing two or more active hydrogens, a compound having two or more isocyanate groups, and additives such as a catalyst, a foaming agent, and a foam stabilizer. Polyurethane foam obtained by the above, as a compound containing two or more active hydrogen, polyols used in general polyurethane foam, that is, polyether polyol having a terminal OH group, polyester polyol, polyether ester polyol and the like In addition, polymer polyols and the like can also be used. As the compound containing two or more isocyanate groups, polyisocyanate which is also used in a general polyurethane foam can be used. For example, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), and mixtures or modified products of these polyisocyanates. The density and hardness can be arbitrarily selected depending on the application.
[0022]
The conductive polyurethane foam of the present invention can be produced by impregnating the above polyurethane foam with the above aqueous dispersion containing polypyrrole and drying. Drying does not necessarily require heating, but it is preferable to heat at a temperature higher than the softening point of the polymer binder in order to ensure adhesion.
[0023]
【Example】
Hereinafter, the present invention will be described in more detail and specifically with reference to examples.
Preparation of PPy-Containing Aqueous Dispersion (A) 2 g of polyacrylic acid, 0.5 g of ferrous sulfate (heptahydrate) and 2 ml of pyrrole were dissolved in 100 ml of water. While stirring the mixture at room temperature, 3.8 g of hydrogen peroxide (31% aqueous solution) was adjusted to 100 ml with water and slowly added dropwise over 1 hour. The mixture was further reacted for 3 hours to obtain an aqueous polypillow dispersion. The resulting aqueous dispersion is adjusted to pH 10.0 with 25% aqueous ammonia, precipitated with methanol, filtered, and redispersed by adding 50 g of water to the filtrate to obtain a solid. An aqueous dispersion containing purified polypyrrole having a concentration of 8% by weight was obtained. In addition, according to the result of quantification of the unreacted monomer, the polypyrrole concentration was 3.2% by weight.
[0024]
Example 1-4
Acrylic emulsion "Mulserve 760" (trade name, manufactured by Marubishi Yuka Kogyo Co., Ltd .; acrylic resin content: 50% by weight) and water are mixed with the aqueous dispersion (A) containing PPy having a solid concentration of 8% by weight prepared above. Then, the proportion of the solid content of the PPy-containing aqueous dispersion (A) in the total solid content was constant at 40% by weight, and the total solid content concentration was 10 (Example 1), 12 (Example 2), and 14 (Example), respectively. 3) and 15 (Example 4) were prepared by weight of a treatment liquid, into which a flexible polyurethane foam having an apparent density of 35 kg / m 3 (dimensions: 2.5 cm (a) × 7.5 cm (b) × 15 cm) (C)) was immersed for 3 minutes, and then squeezed with a mangle (roll diameter: 12.5 cm, drawing pressure: 5.0 kg / cm 2 ). After squeezing with a mangle, it was dried in an oven at 80 ° C. × 2 hours.
After allowing to cool, cut from the inside of the sample at 5 cm and 10 cm from the tip of the sample in parallel to the (a) × (b) plane, and cut (a) the tip (a) × (b) plane and (b) 5 cm The surface resistance value of the 10 cm section was measured.
The untreated flexible polyurethane foam had a surface resistance of 3.0 × 10 14 Ω.
Table 1 shows data of the adhesion ratio of polypyrrole (PPy) solids and the surface resistivity.
Here, the adhesion ratio of polypyrrole means the percentage of the adhesion treatment liquid polypyrrole to the weight of the dried polyurethane foam before the treatment.
[0025]
Example 5-8
The PPy-containing aqueous dispersion (A) is mixed with an acrylic emulsion "Mulserve 760" (manufactured by Marubishi Yuka Kogyo Co., Ltd., trade name; acrylic resin content 50% by weight) and water, and the PPy-containing aqueous dispersion in the total solid content is mixed. The solid content ratio of (A) is 50% by weight and the total solid concentration is 10 (Example 5), 11 (Example 6), 12 (Example 7), and 13 (Example 8)% by weight. A treatment liquid was prepared. A soft polyurethane foam was immersed in this stock solution in the same manner as in Examples 1 to 4, and polypyrrole was attached to the foam.
Table 2 shows data of the adhesion ratio of polypyrrole (PPy) and the specific surface resistance.
[0026]
Example 9-12
The PPy-containing aqueous dispersion (A) is mixed with an acrylic emulsion “Mulserve 760” (trade name, manufactured by Marubishi Yuka Kogyo Co., Ltd .; acrylic resin content 50% by weight) and water, and the PPy-containing aqueous dispersion in the total solid content is mixed. A treatment solution was prepared in which the solid content ratio of (A) was constant at 60% by weight and the total solid content concentration was 10 (Example 9), 10.5 (Example 10), and 11 (Example 11)% by weight, respectively. . A flexible polyurethane foam was immersed in this stock solution in the same manner as in Examples 1 to 4, and polypyrrole was attached to the foam. Further, as Example 12, the PPy-containing aqueous dispersion (A) was mixed with an acrylic emulsion “Mulserve 760” (trade name, manufactured by Marubishi Yuka Kogyo Co., Ltd .; acrylic resin content: 50% by weight) and water to obtain a total solid content. A treatment liquid was prepared in which the PPy-containing aqueous dispersion (A) had a solid content of 65% by weight and a total solid content of 11% by weight. A flexible polyurethane foam was immersed in this stock solution in the same manner as in Examples 1 to 4, and polypyrrole was attached to the foam. Table 3 shows the data of the adhesion ratio of polypyrrole (PPy) and the surface resistivity of Examples 9 to 12.
In addition, when the resistance value of the obtained polypyrrole-adhered foams of Examples 1 to 12 was measured after repeating the compression test 100,000 times, almost no change was observed as compared with the resistance value before the repeated test.
[0027]
[Table 1]
[Table 2]
[Table 3]
【The invention's effect】
INDUSTRIAL APPLICABILITY The present invention can provide a polyurethane foam having excellent conductivity even inside, and is useful as a conductive roller in a printer for electrophotography, electrostatic recording, or the like. This conductive polyurethane foam has a high conductivity of the order of 10 4 Ω and is excellent in durability.
Claims (6)
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| JP2003102944A JP4250010B2 (en) | 2003-04-07 | 2003-04-07 | Conductive polyurethane foam |
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| JP2003102944A JP4250010B2 (en) | 2003-04-07 | 2003-04-07 | Conductive polyurethane foam |
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| JP4250010B2 JP4250010B2 (en) | 2009-04-08 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012113871A (en) * | 2010-11-22 | 2012-06-14 | Tayca Corp | Planar heating element and manufacturing method thereof |
| CN103172900A (en) * | 2013-02-20 | 2013-06-26 | 深圳创怡兴实业有限公司 | Preparation method of conductive sponge |
| CN108795014A (en) * | 2018-05-11 | 2018-11-13 | 重庆工商大学 | A kind of easy construction, instant polyurathamc conductive foam and preparation method thereof |
-
2003
- 2003-04-07 JP JP2003102944A patent/JP4250010B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012113871A (en) * | 2010-11-22 | 2012-06-14 | Tayca Corp | Planar heating element and manufacturing method thereof |
| CN103172900A (en) * | 2013-02-20 | 2013-06-26 | 深圳创怡兴实业有限公司 | Preparation method of conductive sponge |
| CN108795014A (en) * | 2018-05-11 | 2018-11-13 | 重庆工商大学 | A kind of easy construction, instant polyurathamc conductive foam and preparation method thereof |
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| JP4250010B2 (en) | 2009-04-08 |
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