JP4196489B2 - Semiconductive vulcanized rubber composition and semiconductive vulcanized rubber material - Google Patents
Semiconductive vulcanized rubber composition and semiconductive vulcanized rubber material Download PDFInfo
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- JP4196489B2 JP4196489B2 JP19683599A JP19683599A JP4196489B2 JP 4196489 B2 JP4196489 B2 JP 4196489B2 JP 19683599 A JP19683599 A JP 19683599A JP 19683599 A JP19683599 A JP 19683599A JP 4196489 B2 JP4196489 B2 JP 4196489B2
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- 239000004636 vulcanized rubber Substances 0.000 title claims description 31
- 239000000463 material Substances 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 title claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 9
- 229920001897 terpolymer Polymers 0.000 claims description 9
- 230000007613 environmental effect Effects 0.000 claims description 8
- YFBUDXNMBTUSOC-UHFFFAOYSA-N 1,4-dihydroquinoxaline-2,3-dithione Chemical class C1=CC=C2NC(=S)C(=S)NC2=C1 YFBUDXNMBTUSOC-UHFFFAOYSA-N 0.000 claims description 7
- 238000011156 evaluation Methods 0.000 claims description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 5
- 229960001545 hydrotalcite Drugs 0.000 claims description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- -1 quaternary ammonium salt compound Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、含ハロゲンポリエーテル系ポリマーをベースとする半導電性加硫ゴム用組成物、および同組成物を加硫してなる半導電性加硫ゴム材料に関する。本発明による半導電性加硫ゴム材料は、コピー機、プリンター等における電子写真用プロセスの現像ロールまたはベルト、帯電ロールまたはベルト、転写ロールまたはベルト等の半導電性ゴムロールまたはベルトを構成する材料として有用である。
【０００２】
【従来の技術】
近年、コピー機、プリンター等では非接触型帯電方式であるコロナ放電に代わって接触型帯電方式のものが採用されて来ている。接触型帯電方式では、一般に、帯電ロール、現像ロール等の半導電性ゴムロールは感光体と接触するため、ロール表面のゴム層の物性が画像の高画質化に大きな影響を及ぼす。
【０００３】
また、帯電ロール、現像ロール等は、適度の電気抵抗値、すなわち１０5 〜１０9 Ωｃｍ程度の電気抵抗値を持っていないと、感光体上に均一な帯電を付与することができない。しかも、この電気抵抗値は、複写機の高画質化の要求から、高温高湿下でも低温低湿下でも変動幅が小さいこと、すなわち、周囲の環境条件の変化によっても安定した値を示すことが要求されている。
【０００４】
従って、前記ゴム層の材料としては、通常、電気抵抗値が１０5 〜１０9 Ωｃｍ程度で、かつ、周囲の環境条件の変化によっても安定した電気抵抗値を示す耐環境性に優れたものであることが要求されている。
【０００５】
また、帯電ロール、現像ロールは、通常、トナーをロールから離し易くするように、ゴム層の表面にコーティング層が設けられている。そのため、ロール全体の抵抗値が高くなってしまうので、これを防ぐにはゴム層自身の抵抗値をできるだけ低くすることが望まれている。さらに、帯電ロール、現像ロール等は、ロールの両端部に荷重が掛かって、長期に渡り荷重変形が繰り返されることが多く、ゴムのへたりが問題となる。そのため、これらロールは圧縮永久歪性に優れたものであることも要求されている。
【０００６】
これらの要求を満たすため、従来から導電性を有する物質をポリマーに添加する等の方法が知られている。
【０００７】
しかしながら、従来の方法では、得られる半導電性ゴムの電気抵抗値は、添加物の添加量、分散によって大きく左右されるといった欠点がある。例えば、カーボンブラックを添加する方法では、わずかな添加量の差異や分散不良等により電気抵抗値の再現性が確保されなかったり、得られる半導電性ゴムの硬度上昇が起こるといった問題が生じる。また、Ｌｉ塩等のイオン導電剤を添加する方法では、半導電性ゴムとしての抵抗値は低下するものの、環境依存性が大きくなるといった問題がある。
【０００８】
特開平７−１４０７６０号、特開平７−７７８５９号、特開平６−２６４９１９号、特開平６−２６４９１８号の各公報には、ゴムロールの抵抗調整層に導電剤として第四級アンモニウム塩を添加する方法が提案されている。しかしながら、これらは、半導電性加硫ゴム材料に対する上記のような要求をすべて満たしたものではない。
【０００９】
【発明が解決しようとする課題】
本発明は、上記実状に鑑み、コピー機、プリンター等の現像ロールまたはベルト、帯電ロールまたはベルト、転写ロールまたはベルト等の半導電性ゴムロールまたはベルトを構成する材料として好適に使用可能なように、１０5 〜１０9 Ωｃｍ程度で、かつ、周囲の環境条件の変化によっても安定した電気抵抗値を示す半導電性加硫ゴム材料を提供することを目的をする。
【００１０】
【課題を解決するための手段】
本発明者等は、種々研究を重ねた結果、含ハロゲンポリエーテルポリマーに特定の第四級アンモニウム塩を添加することにより、上記要求をすべて満たす半導電性加硫ゴム用組成物および半導電性加硫ゴム材料が得られることを見いだし、本発明を完成した。
【００１１】
すなわち、本発明は、
ａ）エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体 １００重量部と、
ｂ）下記一般式[Ｉ]で表される第四級アンモニウム塩 ０．１〜１０重量部と、
ｃ）２，３−ジメルカプトキノキサリン誘導体 ０．１〜１０重量部と
ｄ）合成ハイドロタルサイト ０．５〜２０重量部
とを含んでなる、半導電性加硫ゴム用組成物ある。
【００１２】
【化２】
【００１３】
また、本発明においては、加硫剤として２，３−ジメルカプトキノキサリン誘導体を使用することにより、圧縮永久歪率の小さい半導電性ゴム材料が得られる。
【００１６】
エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体の分子量は、ムーニー粘度表示でＭＬ1+4 （１００℃）＝３０〜１５０程度であることが好ましい。
【００１７】
本発明による加硫ゴム用組成物のもう１つの構成成分である第四級アンモニウム塩化合物において、一般式[Ｉ]中のＲ1 、Ｒ2 、Ｒ3 、Ｒ4 およびＲ5 として定義されている炭素原子数１〜１８のアルキル基は、例えば、メチル基、エチル基、プロピル基、ｎ−ブチル基、第二ブチル基、ペンチル基、ヘキシル基、ヘプチル基、ｎ−オクチル基、イソオクチル基、２−エチルヘキシル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等である。Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 としての炭素原子数１〜１８のアルケニル基は、例えば、ビニル基、アリル基、オレイル基等である。Ｒ6 としての炭素原子数１〜６のアルキレン基は、例えば、メチレン基、１，２−エチレン基、１，２−プロピレン基、１，３−ブロピレン基、１，４−ブチレン基、１，６−へキシレン基である。
【００１８】
また、一般式[Ｉ]中のＸ−としての１価のアニオンは、例えば、ハロゲン化物イオン、無機酸イオン、有機酸イオン等である。ハロゲン化物イオンは、フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオン等であり、無機酸イオンとしては、過塩素酸イオン、炭酸イオン、硝酸イオン、硫化物イオン等が例示される。Ｘ−としては過塩素酸イオンが好ましい。
【００１９】
ｎは２〜１５の整数を意味する。
【００２０】
第四級アンモニウム塩[Ｉ]はその１種を単独で用いても２種以上を組み合わせて用いてもよい。
【００２１】
第四級アンモニウム塩[Ｉ]の添加量は、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体１００重量部に対して０．１〜１０重量部、好ましくは０．２〜５重量部である。第四級アンモニウム塩[Ｉ]の添加量が０．１重量部未満であると、電気抵抗値の低下が不十分であり、また１０重量部を超えても、特に効果が増大することはない。
【００２６】
２，３−ジメルカプトキノキサリン誘導体の例としては、キノキサリン−２，３−ジチオカーボネート、６−メチルキノキサリン−２，３−ジチオカーボネート、６−イソプロピルキノキサリン−２，３−ジチオカーボネート、５，８−ジメチルキノキサリン−２，３−ジチオカーボネート等が挙げられる。２，３−ジメルカプトキノキサリン誘導体の添加量は、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体１００重量部に対して通常０．１〜１０重量部、好ましくは０．５〜５重量部である。この範囲未満の添加量では、優れた圧縮永久歪性を得ることが困難になり、一方この範囲を超えると得られた加硫物が剛直になりすぎて、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体加硫物に通常期待される物性が得られなくなることがある。２，３−ジメルカプトキノキサリン誘導体以外の加硫剤の添加量も上記と同じ範囲であってよい。
【００２７】
加硫剤はその１種を単独で用いても２種以上を組み合わせて用いてもよい。
【００２８】
また、加硫剤と共に公知の促進剤（加硫促進剤）、遅延剤などをエピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体に添加することもできる。加硫促進剤の例としては、アミン類、アミンの弱酸塩類、塩基性シリカ、第四級アンモニウム塩類、第四級ホスホニウム塩類、多官能ビニル化合物、メルカプトベンゾチアゾール類、スルフェンアミド類、ジメチオカーバメート類、チウラムポリスルフィド類等を挙げることができる。また、遅延剤としてはＮ−シクロヘキシルチオフタルイミド等を挙げることができる。
【００２９】
これらは単独で用いても２種以上を組み合わせて用いてもよい。
【００３０】
促進剤または遅延剤の添加量は、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体１００重量部に対して０〜１０重量部、好ましくは０．１〜５重量部である。
【００３１】
本発明による半導電性加硫ゴム用組成物は受酸剤としては、下記一般式[II]
Ｍｇx Ｚｎy Ａｌz （ＯＨ）2(x+y)+3z-2 ＣＯ3 ・ｗＨ2 Ｏ ……[II]
（式中、ｘとｙは０〜１０、ただしｘ＋ｙ＝１〜１０、ｚは１〜５、ｗは０〜１０の実数をそれぞれ示す）
で表される合成ハイドロタルサイト類等を含む。
【００３２】
合成ハイドロタルサイト類としては、Ｍｇ4.5 Ａｌ2 （ＯＨ）13ＣＯ3 ・３．５Ｈ2 Ｏ、Ｍｇ4.5 Ａｌ2 （ＯＨ）13ＣＯ3 、Ｍｇ4 Ａｌ2 （ＯＨ）12ＣＯ3 ・３．５Ｈ2 Ｏ、Ｍｇ6 Ａｌ2 （ＯＨ）16ＣＯ3 ・４Ｈ2 Ｏ、Ｍｇ3 Ａｌ2 （ＯＨ）10ＣＯ3 ・１．７Ｈ2 Ｏ、Ｍｇ3 ＺｎＡｌ2 （ＯＨ）12ＣＯ3 ・ｗＨ2 Ｏ、Ｍｇ3ＺｎＡｌ2 （ＯＨ）12ＣＯ3 等を挙げることができる。
【００３３】
受酸剤はその１種を単独で用いても２種以上を組み合わせて用いてもよい。
【００３４】
受酸剤の量は、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体１００重量部に対して０〜５０重量部、好ましくは０．５〜２０重量部である。
【００３５】
また、本発明による半導電性加硫ゴム用組成物は、他の添加剤、例えば滑剤、老化防止剤、充填剤、補強剤、可塑剤、加工助剤、難燃剤、顔料等を適宜含むことができる。さらに本発明の技術的特徴が失われない範囲で、当該技術分野で通常行われているゴム、樹脂等のブレンドを行うことも可能である。
【００３６】
本発明による組成物の構成成分の配合手段としては、従来ポリマー加工の分野において利用されている任意の手段、例えばミキシングロール、バンバリーミキサー、各種ニーダー類等を利用することができる。
【００３７】
本発明による半導電性加硫ゴム用組成物は、これを通常１００〜２５０℃の温度に加熱することで加硫物とすることができる。加硫時間は温度によっても異なるが、通常は０．５〜３００分の間である。加硫成型の方法としては、金型による圧縮成型、射出成型、スチーム缶、エアーバス、赤外線あるいはマイクロウェーブによる加熱等、任意の方法を用いることができる。
【００３８】
本発明による半導電性加硫ゴム材料は、温度２３℃で相対湿度５０％における体積固有電気抵抗値が１０5 Ωｃｍ以上１０9 Ωｃｍ未満の範囲、好ましくは１０6 Ωｃｍ以上１０7 Ωｃｍ未満の範囲にあるものである。
【００３９】
また、本発明による半導電性加硫ゴム材料は、温度１０℃で相対湿度１５％における体積固有電気抵抗値（Ａ）および温度３０℃で相対湿度８０％における体積固有電気抵抗値（Ｂ）の対数の差
ｌｏｇ10（Ａ）−ｌｏｇ10（Ｂ）
で定義される環境依存性の評価値が１．０〜１．８の範囲にあるものである。
【００４０】
本発明による半導電性加硫ゴム材料は、コピー機、プリンター等における電子写真用プロセスの現像ロールまたはベルト、帯電ロールまたはベルト、転写ロールまたはベルト等の半導電性ゴムロールまたはベルトを構成する材料として有用である。
【００４１】
【発明の実施の形態】
つぎに本発明の実施例を幾つか挙げるが、これらは本発明を限定するものではない。なお、実施例４〜７は本発明の範囲に属する実施例である。実施例１〜３は本発明の範囲に属さないものであって、参考例として示したものである。
【００４２】
［実施例１］
表１に示す成分を配合して、加硫ゴム用組成物を得た。
【００４３】
この組成物を、温度７０℃に調整したオープンロールで混練りし、得られた混練物を温度１７０℃で１５分間プレス加硫し、２ｍｍ厚の加硫ゴムシートを得た。
【００４４】
［実施例２〜４］［比較例１〜５］
成分および配合量を表１および表２に示すように変更した点を除いて、実施例１と同様の操作を行い、加硫ゴムシートを得た。
【００４５】
性能評価試験
実施例および比較例で得られた加硫ゴムシートに対し、体積固有電気抵抗および環境依存性について、下記の方法で性能評価試験を行った。
【００４６】
・体積固有電気抵抗
加硫ゴムシートおよび絶縁抵抗計（三菱油化（株）製「ハイレスタＨＰ」）を、温度１０℃で相対湿度（ＲＨ）１５％、温度２３℃で５０％ＲＨ（この条件が標準的な条件である）、および温度３０℃で８０％ＲＨの各環境条件下に設定した恒温恒湿槽内に入れ、２４時間以上放置した。その後、電圧を１０Ｖ印加し、１分後のシートの抵抗値を測定した。
【００４７】
・環境依存性
体積固有電気抵抗の環境依存性を、温度１０℃で相対湿度１５％における体積固有電気抵抗値（Ａ）および温度３０℃で相対湿度８０％における体積固有電気抵抗値（Ｂ）の対数の差と定義する。
【００４８】
すなわち、環境依存性の評価値は、上記測定によって得られた抵抗値から、
式：
ｌｏｇ10（Ａ）−ｌｏｇ10（Ｂ）
で算出した値である。
【００４９】
得られた体積固有電気抵抗値および環境依存性の評価値を表３および表４に、またＪＩＳＫ６３０１に従って測定した、温度７０℃で２２時間圧縮の条件における圧縮永久歪率を表５および表６にそれぞれ示す。
【００５０】
【表１】
【表２】
１）ＥＰ／ＥＯ／ＡＧＥ共重合ゴム：「エピクロマーＣＧ−１０２」（ダイソー（株）製、エピクロルヒドリン（ＥＰ）／エチレンオキサイド（ＥＯ）／アリルグリシジルエーテル（ＡＧＥ）三元共重合体、モノマー比：ＥＰ／ＥＯ／ＡＧＥ＝４０／５６／４ｍｏｌ％）
２）「ＤＨＴ−４Ａ」（協和化学工業（株）製ハイドロタルサイト）
３）ＤＢＵ：１，８−ジアザビシクロ（５，４，０）ウンデセン−７
４）ｎ＝１および＝２の混合物（ｎ＝１ ４５重量％、ｎ＝２ ５５重量％）
【表３】
【発明の効果】
本発明による半導電性加硫ゴム材料は、体積固有電気抵抗値が１０5 Ωｃｍ以上１０9 Ωｃｍ未満の範囲にあり、かつ、周囲の環境条件の変化によっても安定した電気抵抗値を示す耐環境性に優れたものである。
【００５４】
また、加硫剤として２，３−ジメルカプトキノキサリン誘導体を使用することにより、圧縮永久歪率の小さい半導電性ゴム材料を得ることができる。
【００５５】
よって、本発明より得られた半導電性加硫ゴム材料は、このような特性の故に、コピー機、プリンター等における電子写真用プロセスの現像ロールまたはベルト、帯電ロールまたはベルト、転写ロールまたはベルト等の半導電性ゴムロールまたはベルトを構成する材料として好適に用いることができるものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composition for semiconductive vulcanized rubber based on a halogen-containing polyether-based polymer, and a semiconductive vulcanized rubber material obtained by vulcanizing the composition. The semiconductive vulcanized rubber material according to the present invention is a material constituting a semiconductive rubber roll or belt such as a developing roll or belt, a charging roll or belt, a transfer roll or belt in an electrophotographic process in a copying machine, a printer or the like. Useful.
[0002]
[Prior art]
2. Description of the Related Art In recent years, a contact-type charging system has been adopted in a copy machine, a printer, and the like instead of a corona discharge that is a non-contact type charging system. In the contact-type charging method, generally, a semiconductive rubber roll such as a charging roll or a developing roll comes into contact with the photosensitive member, so that the physical properties of the rubber layer on the roll surface have a great influence on improving the image quality.
[0003]
Further, if the charging roll, the developing roll, etc. do not have an appropriate electrical resistance value, that is, an electrical resistance value of about 10 5 to 10 9 Ωcm, uniform charging cannot be imparted to the photoreceptor. In addition, this electrical resistance value has a small fluctuation range under high temperature and high humidity and low temperature and low humidity due to the demand for high image quality of the copying machine, that is, it can show a stable value even when the surrounding environmental conditions change. It is requested.
[0004]
Therefore, the material of the rubber layer is generally excellent in environmental resistance having an electric resistance value of about 10 5 to 10 9 Ωcm and a stable electric resistance value even when the surrounding environmental conditions change. It is required to be.
[0005]
The charging roll and the developing roll are usually provided with a coating layer on the surface of the rubber layer so that the toner can be easily separated from the roll. Therefore, since the resistance value of the whole roll will become high, in order to prevent this, it is desired to make the resistance value of the rubber layer itself as low as possible. Furthermore, a charging roll, a developing roll, and the like are subjected to a load on both ends of the roll, and the load deformation is often repeated over a long period of time, and rubber sag becomes a problem. Therefore, these rolls are also required to be excellent in compression set.
[0006]
In order to satisfy these requirements, conventionally, a method of adding a conductive material to a polymer is known.
[0007]
However, the conventional method has a drawback in that the electric resistance value of the obtained semiconductive rubber is greatly influenced by the amount and dispersion of the additive. For example, in the method of adding carbon black, there is a problem that the reproducibility of the electric resistance value is not ensured due to a slight difference in addition amount or poor dispersion, or the hardness of the obtained semiconductive rubber is increased. In addition, the method of adding an ionic conductive agent such as a Li salt has a problem that although the resistance value as a semiconductive rubber is lowered, the environmental dependency is increased.
[0008]
In JP-A-7-140760, JP-A-7-77859, JP-A-6-264919, and JP-A-6-264918, a quaternary ammonium salt is added as a conductive agent to the resistance adjustment layer of the rubber roll. A method has been proposed. However, these do not satisfy all the above-mentioned requirements for the semiconductive vulcanized rubber material.
[0009]
[Problems to be solved by the invention]
In view of the above, the present invention can be suitably used as a material constituting a semiconductive rubber roll or belt such as a developing roll or belt of a copying machine, a printer, a charging roll or belt, a transfer roll or a belt, An object of the present invention is to provide a semiconductive vulcanized rubber material having an electric resistance value of about 10 5 to 10 9 Ωcm and stable even when the surrounding environmental conditions are changed.
[0010]
[Means for Solving the Problems]
As a result of various studies, the present inventors have added a specific quaternary ammonium salt to the halogen-containing polyether polymer, thereby satisfying all of the above requirements and a semiconductive vulcanized rubber composition. The inventors found that a vulcanized rubber material can be obtained and completed the present invention.
[0011]
That is, the present invention
a) 100 parts by weight of an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer ,
b) 0.1 to 10 parts by weight of a quaternary ammonium salt represented by the following general formula [I];
c) 2,3-dimercaptoquinoxaline derivative 0.1 to 10 parts by weight
d) Synthetic hydrotalcite 0.5-20 parts by weight
And a composition for semiconductive vulcanized rubber.
[0012]
[Chemical 2]
[0013]
In the present invention, a semiconductive rubber material having a small compression set can be obtained by using a 2,3-dimercaptoquinoxaline derivative as a vulcanizing agent.
[0016]
The molecular weight of the epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer is preferably about ML 1 + 4 (100 ° C.) = 30 to 150 in terms of Mooney viscosity.
[0017]
In the quaternary ammonium salt compound which is another component of the composition for vulcanized rubber according to the present invention, it is defined as R 1 , R 2 , R 3 , R 4 and R 5 in the general formula [I]. Examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, pentyl group, hexyl group, heptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like. Examples of the alkenyl group having 1 to 18 carbon atoms as R 1 , R 2 , R 3 , R 4 , and R 5 include a vinyl group, an allyl group, and an oleyl group. Examples of the alkylene group having 1 to 6 carbon atoms as R 6 include a methylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1, 6-hexylene group.
[0018]
In addition, the monovalent anion as X − in the general formula [I] is, for example, a halide ion, an inorganic acid ion, an organic acid ion, or the like. Halide ions are fluoride ions, chloride ions, bromide ions, iodide ions and the like, and inorganic acid ions include perchlorate ions, carbonate ions, nitrate ions, sulfide ions and the like. X − is preferably a perchlorate ion.
[0019]
n means an integer of 2 to 15.
[0020]
The quaternary ammonium salt [I] may be used alone or in combination of two or more.
[0021]
The addition amount of the quaternary ammonium salt [I] is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. is there. When the addition amount of the quaternary ammonium salt [I] is less than 0.1 parts by weight, the electric resistance value is not sufficiently lowered, and even when the amount exceeds 10 parts by weight, the effect is not particularly increased. .
[0026]
Examples of 2,3-dimercaptoquinoxaline derivatives include quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 6-isopropylquinoxaline-2,3-dithiocarbonate, 5,8- Examples thereof include dimethylquinoxaline-2,3-dithiocarbonate. The amount of 2,3-dimercaptoquinoxaline derivative added is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. It is. If the addition amount is less than this range, it becomes difficult to obtain excellent compression set, while if it exceeds this range, the resulting vulcanizate becomes too rigid and epichlorohydrin-ethylene oxide-allyl glycidyl ether In some cases, the physical properties normally expected of the original copolymer vulcanizate may not be obtained. The amount of vulcanizing agent other than the 2,3-dimercaptoquinoxaline derivative may also be in the same range as described above.
[0027]
One vulcanizing agent may be used alone, or two or more vulcanizing agents may be used in combination.
[0028]
Moreover, a well-known accelerator (vulcanization accelerator), a retarder, etc. can also be added to an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer with a vulcanizing agent. Examples of vulcanization accelerators include amines, weak acid salts of amines, basic silica, quaternary ammonium salts, quaternary phosphonium salts, polyfunctional vinyl compounds, mercaptobenzothiazoles, sulfenamides, dimethio. Carbamates, thiuram polysulfides and the like can be mentioned. Examples of the retarder include N-cyclohexylthiophthalimide.
[0029]
These may be used alone or in combination of two or more.
[0030]
The addition amount of the accelerator or retarder is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer .
[0031]
Semiconductive vulcanized rubber composition of the present invention as the acid acceptor, under following general formula [II]
Mg x Zn y Al z (OH) 2 (x + y) + 3z-2 CO 3 · wH 2 O ...... [II]
(Wherein x and y are 0 to 10, where x + y = 1 to 10, z is 1 to 5, and w is a real number of 0 to 10, respectively)
In comprising represented by synthetic hydrotalcite like.
[0032]
The synthetic hydrotalcite, Mg 4.5 Al 2 (OH) 13 CO 3 · 3.5H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3, Mg 4 Al 2 (OH) 12 CO 3 · 3. 5H 2 O, Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, Mg 3 Al 2 (OH) 10 CO 3 .1.7H 2 O, Mg 3 ZnAl 2 (OH) 12 CO 3 .wH 2 O Mg 3 ZnAl 2 (OH) 12 CO 3 and the like.
[0033]
The acid acceptor may be used alone or in combination of two or more.
[0034]
The amount of the acid acceptor is 0 to 50 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer .
[0035]
Moreover, the composition for semiconductive vulcanized rubber according to the present invention appropriately contains other additives such as lubricants, anti-aging agents, fillers, reinforcing agents, plasticizers, processing aids, flame retardants, pigments and the like. Can do. Furthermore, it is possible to carry out blending of rubber, resin, etc., which is usually performed in the technical field, as long as the technical features of the present invention are not lost.
[0036]
As a means for blending the constituent components of the composition according to the present invention, any means conventionally used in the field of polymer processing, for example, a mixing roll, a Banbury mixer, various kneaders, and the like can be used.
[0037]
The semiconductive vulcanized rubber composition according to the present invention can be made into a vulcanized product by heating it to a temperature of usually 100 to 250 ° C. The vulcanization time varies depending on the temperature, but is usually between 0.5 and 300 minutes. As a method of vulcanization molding, any method such as compression molding using a mold, injection molding, steam can, air bath, infrared ray or heating by microwave can be used.
[0038]
The semiconductive vulcanized rubber material according to the present invention has a volume specific electrical resistance value in the range of 10 5 Ωcm or more and less than 10 9 Ωcm, preferably 10 6 Ωcm or more and less than 10 7 Ωcm, at a temperature of 23 ° C. and a relative humidity of 50%. It is what.
[0039]
The semiconductive vulcanized rubber material according to the present invention has a volume specific electric resistance value (A) at a temperature of 10 ° C. and a relative humidity of 15% and a volume specific electric resistance value (B) at a temperature of 30 ° C. and a relative humidity of 80%. Logarithmic difference log 10 (A) −log 10 (B)
The evaluation value of the environment dependency defined by is in the range of 1.0 to 1.8.
[0040]
The semiconductive vulcanized rubber material according to the present invention is a material constituting a semiconductive rubber roll or belt such as a developing roll or belt, a charging roll or belt, a transfer roll or belt in an electrophotographic process in a copying machine, a printer or the like. Useful.
[0041]
DETAILED DESCRIPTION OF THE INVENTION
Next, several examples of the present invention will be given, but these do not limit the present invention. Examples 4 to 7 are examples belonging to the scope of the present invention. Examples 1 to 3 do not belong to the scope of the present invention and are shown as reference examples .
[0042]
[Example 1]
The components shown in Table 1 were blended to obtain a vulcanized rubber composition.
[0043]
This composition was kneaded with an open roll adjusted to a temperature of 70 ° C., and the obtained kneaded product was press-vulcanized at a temperature of 170 ° C. for 15 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm.
[0044]
[Examples 2 to 4] [Comparative Examples 1 to 5]
A vulcanized rubber sheet was obtained by performing the same operation as in Example 1 except that the components and blending amounts were changed as shown in Tables 1 and 2.
[0045]
Performance Evaluation Tests The vulcanized rubber sheets obtained in Examples and Comparative Examples were subjected to performance evaluation tests by the following methods for volume specific electrical resistance and environment dependency.
[0046]
・ Volume specific electric resistance vulcanized rubber sheet and insulation resistance meter (“HIRESTA HP” manufactured by Mitsubishi Yuka Co., Ltd.) at a relative humidity (RH) of 15% at a temperature of 10 ° C. and 50% RH at a temperature of 23 ° C. (this condition Is a standard condition) and in a thermo-hygrostat set at 80 ° C. and at a temperature of 30 ° C., and left for 24 hours or more. Thereafter, a voltage of 10 V was applied, and the resistance value of the sheet after 1 minute was measured.
[0047]
Environment dependency The volume dependency of the volume specific electric resistance is expressed as follows: volume specific electric resistance value (A) at a relative humidity of 15% at a temperature of 10 ° C. and volume specific electric resistance value (B) at a relative humidity of 80% at a temperature of 30 ° C. Defined as logarithmic difference.
[0048]
That is, the evaluation value of the environment dependency is from the resistance value obtained by the above measurement,
formula:
log 10 (A) -log 10 (B)
This is the value calculated in.
[0049]
Tables 3 and 4 show the volume specific electrical resistance values and environmental evaluation values obtained, and Tables 5 and 6 show the compression set ratios measured at a temperature of 70 ° C. for 22 hours under the conditions of compression for 22 hours. Each is shown.
[0050]
[Table 1]
[Table 2]
1) EP / EO / AGE copolymer rubber: “Epichromer CG-102” (manufactured by Daiso Corporation, epichlorohydrin (EP) / ethylene oxide (EO) / allyl glycidyl ether (AGE) terpolymer, monomer ratio) EP / EO / AGE = 40/56/4 mol%)
2) "DHT-4A" (Kyowa Chemical Industry Co., Ltd. hydrotalcite)
3) DBU: 1,8-diazabicyclo (5,4,0) undecene-7
4) Mixture of n = 1 and = 2 (n = 1 45% by weight, n = 2 55% by weight)
[Table 3]
【The invention's effect】
The semiconductive vulcanized rubber material according to the present invention has a volume specific electrical resistance value in the range of 10 5 Ωcm or more and less than 10 9 Ωcm, and also exhibits an environment resistance value that exhibits a stable electrical resistance value due to changes in ambient environmental conditions. It has excellent properties.
[0054]
Further, by using a 2,3-dimercaptoquinoxaline derivative as a vulcanizing agent, a semiconductive rubber material having a small compression set can be obtained.
[0055]
Therefore, the semiconductive vulcanized rubber material obtained from the present invention has such characteristics, and therefore, a development roll or belt, a charging roll or belt, a transfer roll or belt, etc. for an electrophotographic process in a copying machine, a printer, etc. The semiconductive rubber roll or belt can be suitably used as a material constituting the belt.
Claims (7)
ｂ）下記一般式[Ｉ]で表される第四級アンモニウム塩 ０．１〜１０重量部と、
ｃ）２，３−ジメルカプトキノキサリン誘導体 ０．１〜１０重量部と
ｄ）合成ハイドロタルサイト ０．５〜２０重量部
とを含んでなる、半導電性加硫ゴム用組成物。
b) 0.1 to 10 parts by weight of a quaternary ammonium salt represented by the following general formula [I] ;
c) 2,3-dimercaptoquinoxaline derivative 0.1 to 10 parts by weight
d) Synthetic hydrotalcite 0.5-20 parts by weight
A composition for semiconductive vulcanized rubber, comprising:
で定義される環境依存性の評価値が１．０〜１．８の範囲にある請求項４〜６のいずれかに記載の半導電性加硫ゴム材料。Log 10 (A) -log 10 (B) logarithmic difference between volume specific electric resistance value (A) at a relative humidity of 15% at a temperature of 10 ° C. and volume specific electric resistance value (B) at a relative humidity of 80% at a temperature of 30 ° C.
The semiconductive vulcanized rubber material according to any one of claims 4 to 6 , wherein the evaluation value of the environmental dependency defined by the formula is in the range of 1.0 to 1.8.
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| JP19683599A JP4196489B2 (en) | 1999-07-12 | 1999-07-12 | Semiconductive vulcanized rubber composition and semiconductive vulcanized rubber material |
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| JP19683599A JP4196489B2 (en) | 1999-07-12 | 1999-07-12 | Semiconductive vulcanized rubber composition and semiconductive vulcanized rubber material |
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| Publication Number | Publication Date |
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| JP2001019843A JP2001019843A (en) | 2001-01-23 |
| JP4196489B2 true JP4196489B2 (en) | 2008-12-17 |
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| JP19683599A Expired - Lifetime JP4196489B2 (en) | 1999-07-12 | 1999-07-12 | Semiconductive vulcanized rubber composition and semiconductive vulcanized rubber material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8357942B2 (en) | 2006-10-02 | 2013-01-22 | Kabushiki Kaisha Toshiba | Semiconductor device with a peripheral circuit formed therein |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4565425B2 (en) * | 2004-08-17 | 2010-10-20 | ダイソー株式会社 | Composition for semiconductive vulcanized rubber excellent in flame retardancy and vulcanized rubber member thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8357942B2 (en) | 2006-10-02 | 2013-01-22 | Kabushiki Kaisha Toshiba | Semiconductor device with a peripheral circuit formed therein |
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| JP2001019843A (en) | 2001-01-23 |
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