JP4186445B2 - Urethane urea material for office automation equipment - Google Patents

Description

【００２０】
上記ジアミノ化合物（Ｃ）の配合割合は、上記ポリオール（Ｂ）１００重量部（以下「部」と略す）に対して、０．１〜７５部の範囲が好ましく、特に好ましくは０．５〜３５部である。すなわち、上記ジアミノ化合物（Ｃ）が０．１部未満であると、高強度が得られず、逆に７５部を超えると、可撓性が得られないおそれがあるからである。
【００２１】
なお、上記ウレタンウレアイミド組成物には、上記イソシアネート系化合物およびイミド変性イソシアネート系化合物の混合物（Ａ）、ポリオール（Ｂ）、ジアミノ化合物（Ｃ）に加え、必要に応じて、鎖延長剤、触媒、界面活性剤、難燃剤、着色剤、充填剤、可塑剤、安定剤、離型剤、電気抵抗調整剤等を適宜配合して用いることも可能である。
【００２２】
上記鎖延長剤としては、例えば、１，４−ブタンジオール（１，４−ＢＤ）、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ヘキサンジオール、１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメタノール、キシレングリコール、トリエチレングリコール、トリメチロールプロパン（ＴＭＰ）、グリセリン、ペンタエリスリトール、ソルビトール、１，２，６−ヘキサントリオール等の、分子量３００以下のポリオール等があげられる。これらは単独でもしくは２種以上併せて用いられる。
【００２３】
上記触媒としては、第三級アミン等のアミン系化合物、有機錫化合物等の有機金属化合物等があげられる。なかでも、アミン系化合物が好適に用いられる。
【００２４】
上記第三級アミンとしては、例えば、トリエチルアミン等のトリアルキルアミン；Ｎ，Ｎ，Ｎ′，Ｎ′−テトラメチル−１，３−ブタンジアミン等のテトラアルキルジアミン；ジメチルエタノールアミン等のアミノアルコール；エトキシル化アミン；エトキシル化ジアミン；ビス（ジエチルエタノールアミン）アジペート等のエステルアミン；トリエチレンジアミン；Ｎ，Ｎ−ジメチルシクロヘキシルアミン等のシクロヘキシルアミン誘導体；Ｎ−メチルモルホリン、Ｎ−（２−ヒドロキシプロピル）−ジメチルモルホリン等のモルホリン誘導体；Ｎ，Ｎ′−ジエチル−２−メチルピペラジン、Ｎ，Ｎ′−ビス−（２−ヒドロキシプロピル）−２−メチルピペラジン等のピペラジン誘導体等があげられる。
【００２５】
上記有機錫化合物としては、例えば、ジブチル錫ジラウレート、ジブチル錫ジ（２−エチルヘキソエート）等のジアルキル錫化合物や、２−エチルカプロン酸第１錫、オレイン酸第１錫等があげられる。
【００２６】
上記ウレタンウレアイミド組成物は、上記各材料を用い、例えばつぎのように調製して各種ＯＡ機器用部材の成形材料として用いられる。すなわち、まず、無溶媒下、イソシアネート系化合物と酸無水物とを上記所定の割合となるイソシアネート系化合物過剰の状態で反応させることによりイソシアネート系化合物およびイミド変性イソシアネート系化合物の混合物（Ａ）を調製する。一方、ポリオール（Ｂ）、ジアミノ化合物（Ｃ）および必要に応じて他の添加剤を配合して減圧下で攪拌しながら脱泡脱水し硬化剤液を調製する。つぎに、予め上記イソシアネート系化合物およびイミド変性イソシアネート系化合物の混合物（Ａ）を減圧脱泡し、これを上記硬化剤液に添加し、減圧下で攪拌混合してウレタンウレアイミド組成物を調製する。ついで、このウレタンウレアイミド組成物を予め加熱された所定の成形用金型に注型して硬化させた後、上記成形用金型から成形物を脱型し、さらに、２次硬化として１００〜１２０℃の温度で硬化反応を行うことによりウレタンウレアイミド組成物を用いてなるＯＡ機器用の各種部材を製造することができる。
【００２７】
例えば、クリーニングブレードを作製する場合は、予め加熱され、取付用板金が設置された成形用金型にウレタンウレアイミド組成物を注型して硬化させた後、上記成形用金型から成形物を脱型する。さらに、上記と同様、加熱して２次硬化させることによりクリーニングブレードを作製する。または、遠心成形によっても作製することができる。
【００２８】
そして、ＯＡ機器用ウレタンウレア部材として上記クリーニングブレード以外の他の部材、例えば、給紙搬送ロール等の各種ロールや中間転写ベルト等の製造に関しても、上記ウレタンウレアイミド組成物を用い、それぞれの成形用金型を準備し、先に述べたと同様、注型成形や遠心成形により作製することができる。
【００２９】
上記イソシアネート系化合物およびイミド変性イソシアネート系化合物の混合物（Ａ）の反応は、無溶媒下はもちろん、窒素等の不活性雰囲気下にて１３０〜１７０℃の高温条件下で行われることが好ましい。
【００３０】
さらに、上記イソシアネート系化合物およびイミド変性イソシアネート系化合物の混合物（Ａ）の製造工程では、上記イソシアネート系化合物、酸無水物以外に、必要に応じて、他の添加剤を適宜配合することもできる。
【００３１】
上記他の添加剤としては、先に述べた、鎖延長剤、触媒、界面活性剤、難燃剤、着色剤、充填剤、可塑剤、安定剤、離型剤、電気抵抗調整剤等が用いられる。
【００３２】
上記イソシアネート系化合物およびイミド変性イソシアネート系化合物の混合物（Ａ）を予め減圧脱泡する際の減圧条件としては、１３３．３２〜２６６６．４Ｐａの範囲に設定することが好ましい。
【００３３】
上記ポリオール（Ｂ）、ジアミノ化合物（Ｃ）および必要に応じて他の添加剤を配合して減圧下で攪拌しながら脱泡脱水し硬化剤液を調製する際の減圧条件としては、１３３．３２〜２６６６．４Ｐａの範囲に設定することが好ましい。
【００３４】
上記混合物（Ａ）を硬化剤液に添加し混合攪拌する際の減圧条件としては、１３３．３２〜２６６６．４Ｐａの範囲に設定することが好ましい。
【００３５】
なお、上記ウレタンウレアイミド組成物は、上記混合物（Ａ）、ポリオール（Ｂ）およびジアミノ化合物（Ｃ）を予め減圧脱泡した後、ジメチルホルムアミド（ＤＭＦ）等の溶剤にそれぞれ溶解させて、これらを常圧下で混合攪拌することにより調製しても差し支えない。
【００３６】
もしくは、本発明のＯＡ機器用ウレタンウレア部材は、イソシアネート系化合物とポリオールとを用いてなるプレポリマー（Ｄ）と、酸無水物（Ｅ）と、ジアミノ化合物（Ｆ）とを備えたウレタンウレアイミド組成物を用いて所定の各種形状に成形されてなるものである。
【００３７】
上記プレポリマー（Ｄ）に用いられるイソシアネート系化合物としては、特に限定はないが、前記混合物（Ａ）に用いられるイソシアネート系化合物と同様のものがあげられる。
【００３８】
また、上記プレポリマー（Ｄ）に用いられるポリオールとしては、特に限定はないが、前記ポリオール（Ｂ）と同様のものがあげられる。なかでも、耐摩耗性に優れる点で、ポリエステル系ポリオール、ポリカーボネート系ポリオールが好適に用いられる。
【００３９】
上記プレポリマー（Ｄ）に用いられるイソシアネート系化合物とポリオールとの混合モル比は、通常、イソシアネート系化合物／ポリオール＝１．２／１〜１１／１の範囲である。
【００４０】
上記プレポリマー（Ｄ）とともに用いられる酸無水物（Ｅ）としては、特に限定はないが、前記混合物（Ａ）の作製に用いられるものと同様のものがあげられる。なかでも、機械的強度に優れる点で、無水ピロメリット酸（ＡＰＡ）が好適に用いられる。
【００４１】
上記プレポリマー（Ｄ）と酸無水物（Ｅ）との重量混合比は、Ｄ／Ｅ＝１００／０．８〜１００／３０の範囲が好ましく、特に好ましくはＤ／Ｅ＝１００／９〜１００／２５である。すなわち、酸無水物（Ｅ）の重量混合比が０．８未満であると、イミド変性が不充分でウレタンの充分な耐熱性が得られ難く、逆に酸無水物（Ｅ）の重量混合比が３０を超えると、イミド含有量が多くなりすぎて硬度が高くなり、ゴム弾性が得られにくくなるからである。
【００４２】
上記プレポリマー（Ｄ）および酸無水物（Ｅ）とともに用いられるジアミノ化合物（Ｆ）としては、特に限定はないが、前記ジアミノ化合物（Ｃ）と同様のものがあげられる。
【００４３】
上記プレポリマー（Ｄ）は、ジメチルホルムアミド（ＤＭＦ）等の溶剤に溶解させて、プレポリマー溶液として使用することが好ましい。また、上記酸無水物（Ｅ）も、ＤＭＦ等の溶剤に溶解させて、酸無水物溶液として使用することが好ましい。さらに、上記ジアミノ化合物（Ｆ）も、ＤＭＦ等の溶剤に溶解させて、ジアミン溶液として使用することが好ましい。
【００４４】
そして、上記ＯＡ機器用ウレタンウレア部材は、例えば、つぎのようにして作製することができる。すなわち、まず、所定の条件（好ましくは、８０℃で１時間）にて真空脱泡脱水したポリオールに対し、イソシアネート系化合物を添加し、窒素雰囲気下で所定の条件（好ましくは、８０℃で３時間）にて反応させ、ＮＣＯ末端のプレポリマー（Ｄ）を得る。ついで、このプレポリマー（Ｄ）をＤＭＦ等の溶剤に溶解させ、プレポリマー溶液を調製する。一方、無水ピロメリット酸（ＡＰＡ）等の酸無水物（Ｅ）をＤＭＦ等の溶剤に溶解させ、酸無水物溶液を調製する。また、上記ジアミノ化合物（Ｆ）をＤＭＦ等の溶剤に溶解させ、ジアミン溶液を調製する。そして、上記プレポリマー溶液と、上記酸無水物溶液と、上記ジアミン溶液とを、窒素雰囲気下で所定の条件（好ましくは、１１０℃で２．５時間）にて混合攪拌しながら反応させ、その後、必要に応じて、電気抵抗調整剤を添加し、ウレタンウレアイミド溶液を調製する。ついで、このウレタンウレアイミド溶液を用いて、前記と同様にして、ＯＡ機器用の各種ウレタンウレア部材を製造することができる。
【００４５】
例えば、中間転写ベルト等の無端ベルトを作製する場合は、上記ウレタンウレアイミド溶液を円筒金型内に注入し、所定の条件にて遠心成形した後、蓋を取り外して脱型することにより作製することができる。
【００４６】
本発明のＯＡ機器用部材としては、例えば、電子写真複写機のクリーニングブレードや層形成ブレード、給紙搬送ロール等の各種ロールや中間転写ベルト等の無端ベルト等があげられる。
【００４７】
つぎに、実施例について比較例と併せて説明する。
【００４８】
まず、実施例および比較例に先立ち、下記に示す、イソシアネート系化合物とイミド変性イソシアネート系化合物の混合物を調製した。
【００４９】
〔混合物Ａの調製〕
イソホロンジイソシアネート（ＩＰＤＩ）８８．８部と無水ピロメリット酸（ＡＰＡ）２１．８部とを、窒素雰囲気下、１５０℃で５時間攪拌しながら反応させることにより、イソシアネート系化合物とイミド変性イソシアネート系化合物の混合物Ａを調製した。なお、イソシアネート成分（ＩＰＤＩ）と酸無水物（ＡＰＡ）の配合割合はモル比で１００／２５であった。
【００５０】
〔混合物Ｂの調製〕
ＩＰＤＩ４４．４部と４，４′−ジフェニルメタンジイソシアネート（ＭＤＩ）５０部と無水ピロメリット酸（ＡＰＡ）２１．８部とを、窒素雰囲気下、１５０℃で５時間攪拌しながら反応させることにより、イソシアネート系化合物とイミド変性イソシアネート系化合物の混合物Ｂを調製した。なお、イソシアネート成分（ＩＰＤＩ＋ＭＤＩ）と酸無水物（ＡＰＡ）の配合割合はモル比で１００／２５であった。
【００５１】
〔混合物Ｃの調製〕
ＭＤＩ１００部と、ＡＰＡ５．２部とを、窒素雰囲気下、１５０℃で５時間攪拌しながら反応させることにより、イソシアネート系化合物とイミド変性イソシアネート系化合物の混合物Ｃを調製した。なお、ＭＤＩとＡＰＡの配合割合はモル比で１００／６であった。
【００５２】
〔混合物Ｄの調製〕
ＩＰＤＩ８８．８部とＡＰＡ４３．６部とを、窒素雰囲気下、１５０℃で５時間攪拌しながら反応させることにより、イソシアネート系化合物とイミド変性イソシアネート系化合物の混合物Ｄを調製した。なお、ＩＰＤＩとＡＰＡの配合割合はモル比で１００／５０であった。
【００５３】
〔混合物Ｅの調製〕
ＭＤＩ１００部とＡＰＡ０．０９部とを、窒素雰囲気下、１５０℃で５時間攪拌しながら反応させることにより、イソシアネート系化合物とイミド変性イソシアネート系化合物の混合物Ｅを調製した。なお、ＭＤＩとＡＰＡの配合割合はモル比で１００／０．１であった。
【００５４】
【実施例１】
ポリブチレンアジペート（ＰＢＡ）（日本ポリウレタン工業社製のニッポラン４０１０）１００部と、無水ピロメリット酸（ＡＰＡ）１１部と、４，４′−ジフェニルメタンジイソシアネート（ＭＤＩ）３０部とを配合し、ＤＭＦ２００部中で窒素雰囲気下１１０℃で２．５時間混合攪拌しながら反応させた後、２，２′，３，３′−テトラクロロ−４，４′−ジアミノジフェニルメタン６部を添加し、窒素雰囲気下１１０℃で２．５時間混合攪拌しながら反応させることにより、ウレタンウレアイミド組成物を調製した。
【００５５】
そして、このウレタンウレアイミド組成物を１４０℃に予熱された金型で遠心成形した後、続いて２次硬化（１１０℃×１２時間）を行うことにより、ウレタンウレアイミドシートを作製した。また、板金に上記ウレタンウレアイミドシートを貼り付ける後接着法にてクリーニングブレードを作製した。
【００５６】
【実施例２】
ポリブチレンアジペート（ＰＢＡ）（日本ポリウレタン工業社製のニッポラン４０１０、Ｍｎ：２０００）１００部と、２，２′，３，３′−テトラクロロ−４，４′−ジアミノジフェニルメタン７．５部とを配合し、１５０℃で１時間加熱して、ジアミノ化合物（２，２′，３，３′−テトラクロロ−４，４′−ジアミノジフェニルメタン）をポリオールに溶解させた。ついで、トリメチロールプロパン（ＴＭＰ）４部を添加し、減圧下（６６６．６Ｐａ）で攪拌しながら、８０℃で２０分間脱泡脱水した後、予め８０℃で２０分間減圧脱泡（６６６．６Ｐａ）した上記混合物Ａ４７部を添加し、６０秒間攪拌混合してウレタンウレアイミド組成物Ａを調製した。
【００５７】
そして、このウレタンウレアイミド組成物Ａを、１４０℃に予熱されたシート成形用金型に注型して成形した後、脱型し、続いて２次硬化（１１０℃×１２時間）を行うことにより、ウレタンウレアイミドシートを作製した。
【００５８】
また、上記ウレタンウレアイミド組成物Ａを、１４０℃に予熱されたクリーニングブレード成形用金型に注型して成形した後、脱型し、続いて２次硬化（１１０℃×１２時間）を行うことにより、板金との一体成形体であるクリーニングブレードを作製した。
【００５９】
【実施例３】
上記混合物Ａに代えて上記混合物Ｂを用いる以外は、実施例２と同様にしてウレタンウレアイミド組成物Ｂを調製した。そして、このウレタンウレアイミド組成物Ｂを用いて、実施例２と同様にしてウレタンウレアイミドシートおよびクリーニングブレードを作製した。
【００６０】
【実施例４】
２，２′，３，３′−テトラクロロ−４，４′−ジアミノジフェニルメタンを２２．４部に増量するとともに、上記混合物Ａ４７部に代えて上記混合物Ｃ４５部を用いる以外は、実施例２と同様にしてウレタンウレアイミド組成物Ｃを調製した。そして、このウレタンウレアイミド組成物Ｃを用いて、実施例２と同様にしてウレタンウレアイミドシートおよびクリーニングブレードを作製した。
【００６１】
【実施例５】
変性シリコーンオイル（東レダウコーニングシリコーン社製のカルビノール変性シリコーンオイルＳＦ８４２７、Ｍｎ：２４００）１００部と、２，２′，３，３′−テトラクロロ−４，４′−ジアミノジフェニルメタン１．９部とを配合し、１５０℃で１時間加熱して、ジアミノ化合物（２，２′，３，３′−テトラクロロ−４，４′−ジアミノジフェニルメタン）をポリオールに溶解させた。ついで、トリメチロールプロパン（ＴＭＰ）２部を添加し、減圧下（６６６．６Ｐａ）で攪拌しながら、８０℃で２０分間脱泡脱水した後、予め８０℃で２０分間減圧脱泡（６６６．６Ｐａ）した上記混合物Ｄ４７部を添加し、６０秒間攪拌混合してウレタンウレアイミド組成物Ｄを調製した。そして、このウレタンウレアイミド組成物Ｄを用いて、実施例２と同様にしてウレタンウレアイミドシートおよびクリーニングブレードを作製した。
【００６２】
【実施例６】
ポリブチレンアジペート（ＰＢＡ）（日本ポリウレタン工業社製のニッポラン４０１０、Ｍｎ：２０００）１００部と、２，２′，３，３′−テトラクロロ−４，４′−ジアミノジフェニルメタン３３．６部とを配合し、１５０℃で１時間加熱して、ジアミノ化合物（２，２′，３，３′−テトラクロロ−４，４′−ジアミノジフェニルメタン）をポリオールに溶解させた。ついで、トリメチロールプロパン（ＴＭＰ）２部を添加し、減圧下（６６６．６Ｐａ）で攪拌しながら、８０℃で２０分間脱泡脱水した後、予め８０℃で２０分間減圧脱泡（６６６．６Ｐａ）した上記混合物Ｅ４７部を添加し、６０秒間攪拌混合してウレタンウレアイミド組成物Ｅを調製した。そして、このウレタンウレアイミド組成物Ｅを用いて、実施例２と同様にしてウレタンウレアイミドシートおよびクリーニングブレードを作製した。
【００６３】
【比較例１】
ポリブチレンアジペート（ＰＢＡ）（日本ポリウレタン工業社製のニッポラン４０１０）１００部と、１，４−ＢＤ６部と、ＴＭＰ４部とを配合し、減圧下（６６６．６Ｐａ）で攪拌しながら、８０℃で２０分間脱泡脱水した後、これにＩＰＤＩ３８部を添加し、６０秒間攪拌混合してウレタン組成物ａを調製した。そして、このウレタン組成物ａを用いて、実施例２と同様にしてウレタンシートおよびクリーニングブレードを作製した。
【００６４】
【比較例２】
ＩＰＤＩ３８部に代えて、ＭＤＩ４４部を用いる以外は、比較例１と同様にしてウレタン組成物ｂを調製した。そして、このウレタン組成物ｂを用いて、実施例２と同様にしてウレタンシートおよびクリーニングブレードを作製した。
【００６５】
このようにして得られた実施例のウレタンウレアイミドシート，クリーニングブレード、および比較例のウレタンシート，クリーニングブレードを用いて、下記の基準に従い、各特性の評価を行った。これらの結果を、後記の表１に併せて示した。
【００６６】
〔引張強さ（Ｔ_B ）〕
ＪＩＳ Ｋ ６２５１に準じて、各ウレタンウレアイミドシート（ウレタンシート）の引張強さ（Ｔ_B ）を、２５℃および５０℃の各温度にて測定した。
【００６７】
〔耐摩耗性〕
各クリーニングブレードを市販のレーザープリンター（ＬＢＰ）に組み込み、常温常湿環境下（２５℃×６０％ＲＨ）にて、Ａ４サイズで３万枚画出ししたのち、走査型電子顕微鏡にてクリーニングブレードのエッジ部の摩耗量を観察し、摩耗した部分の断面積（Ｕμｍ² ）と、先端部の単位長さ（Ｘμｍ）を測定し、数式：Ｗ＝Ｕ×Ｘにより、摩耗量（Ｗμｍ³ ）を算出した。なお、この摩耗量が小さいほど、耐摩耗性に優れているといえる。そして、この摩耗量が５０μｍ³ 未満のものを○、５０μｍ³ 以上のものを×として評価した。
【００６８】
〔耐エッジ欠け性〕
各クリーニングブレードを市販のレーザープリンター（ＬＢＰ）に組み込み、低温低湿環境下（１５℃×１０％ＲＨ）にて、Ａ３サイズで３万枚画出しを行った。そして、上記３万枚画出し後のクリーニングブレードのエッジ部の欠けの有無を、走査型電子顕微鏡を用いて倍率５００倍で観察した。そして、欠けがないものを○、欠けがあるものを×として評価した。
【００６９】
【表１】

【００７０】
上記結果から、実施例品は、いずれも耐摩耗性および耐エッジ欠け性に優れたものであった。また、２５℃はもちろん５０℃の高温下でも引張強さが高く摩擦熱等においても強度的に優れていることがわかる。
【００７１】
これに対して比較例品は、いずれも耐摩耗性および耐エッジ欠け性に劣るものであった。そして、引張強さに関して２５℃では良好な値が得られたが、５０℃の高温ではその値が著しく低下した。
【００７２】
【実施例７】
まず、前記と同様にして、ウレタンウレアイミド組成物Ａを調製した。そして、このウレタンウレアイミド組成物Ａを、層形成用ブレート成形用金型に注型して上記クリーニングブレードと同様の条件にて層形成ブレードを作製した。
【００７３】
【実施例８〜１１、比較例３，４】
ウレタンウレアイミド組成物Ａに代えて、後記の表２に示す、ウレタンウレアイミド組成物もしくはウレタン組成物を用いる以外は、実施例７と同様にして、層形成ブレードを作製した。
【００７４】
このようにして得られた実施例および比較例の層形成ブレードを用いて、下記の基準に従い耐摩耗性の評価を行った。その結果を後記の表２に示した。
【００７５】
〔耐摩耗性〕
各層形成ブレードをヒューレットパッカード社製のレーザービームプリンターＬＪ４０００の現像機に組み込み、文字画像を１枚（Ａ４印字部分５％原稿使用）画出し毎に、数秒間停止させる方法で６０００枚耐久試験を行った後、層形成ブレード表面に生じた摩耗深さを、表面粗さ計サーフコム（東京精密社製）で測定した。その結果、摩耗深さが２０μｍ以下であったものに○、２０μｍを超えていたものに×をつけた。
【００７６】
【表２】

【００７７】
上記結果から、実施例品の層形成ブレードは、耐摩耗性に優れたものであり良好なＯＡ機器用ウレタンウレア部材が得られたことがわかる。これに対して、比較例品は、耐摩耗性に劣っていた。
【００７８】
【実施例１２】
まず、前記と同様にして、ウレタンウレアイミド組成物Ａを調製した。そして、このウレタンウレアイミド組成物Ａを、円筒状軸体が配設されたロール成形用金型に注型して上記クリーニングブレードと同様の条件にて給紙ロールを作製した。
【００７９】
【実施例１３〜１６、比較例５，６】
ウレタンウレアイミド組成物Ａに代えて、後記の表３に示す、ウレタンウレアイミド組成物もしくはウレタン組成物を用いる以外は、実施例１２と同様にして、給紙ロールを作製した。
【００８０】
このようにして得られた実施例および比較例の給紙ロールを用いて、下記の基準に従い耐摩耗性の評価を行った。その結果を後記の表３に示した。
【００８１】
〔耐摩耗性〕
各給紙ロールを市販の複写機に装着して、常温常湿環境下で６万枚の実機耐久評価を行った。評価前後の外径を測定し、外径変化が６０μｍ未満のものを○、６０μｍ以上のものを×とした。
【００８２】
【表３】

【００８３】
上記結果から、実施例品の給紙ロールは、耐摩耗性に優れたものであり良好なＯＡ機器用ウレタンウレア部材が得られたことがわかる。これに対して、比較例品は、耐摩耗性に劣っていた。
【００８４】
〔ウレタンウレアイミド組成物Ａ′の調製〕
ウレタンウレアイミド組成物Ａに電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１部を添加して、ウレタンウレアイミド組成物Ａ′を調製した。
【００８５】
〔ウレタンウレアイミド組成物Ｂ′の調製〕
ウレタンウレアイミド組成物Ｂに電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１部を添加して、ウレタンウレアイミド組成物Ｂ′を調製した。
【００８６】
〔ウレタンウレアイミド組成物Ｃ′の調製〕
ウレタンウレアイミド組成物Ｃに電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１部を添加して、ウレタンウレアイミド組成物Ｃ′を調製した。
【００８７】
〔ウレタンウレアイミド組成物Ｄ′の調製〕
ウレタンウレアイミド組成物Ｄに電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１部を添加して、ウレタンウレアイミド組成物Ｄ′を調製した。
【００８８】
〔ウレタンウレアイミド組成物Ｅ′の調製〕
ウレタンウレアイミド組成物Ｅに電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１部を添加して、ウレタンウレアイミド組成物Ｅ′を調製した。
【００８９】
〔ウレタン組成物ａ′の調製〕
ウレタン組成物ａに電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１部を添加して、ウレタン組成物ａ′を調製した。
【００９０】
〔ウレタン組成物ｂ′の調製〕
ウレタン組成物ｂに電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１部を添加して、ウレタン組成物ｂ′を調製した。
【００９１】
【実施例１７】
上記ウレタンウレアイミド組成物Ａ′を、１４０℃に予熱した遠心成形機に注型して中間転写ベルトを成形し、上記クリーニングブレードと同様の条件にて２次硬化を行い中間転写ベルトを作製した。
【００９２】
【実施例１８〜２１、比較例７，８】
ウレタンウレアイミド組成物Ａ′に代えて、後記の表４に示す、ウレタンウレアイミド組成物もしくはウレタン組成物を用いる以外は、実施例１７と同様にして、中間転写ベルトを作製した。
【００９３】
このようにして得られた実施例および比較例の中間転写ベルトを用いて、下記の基準に従い耐久性の評価を行った。その結果を後記の表４に示した。
【００９４】
〔耐久性〕
市販のカラー複写機の中間転写ユニットを取り出し、回転試験を７２０時間行った。その間、安定して正常に回転したものを○、ベルト内面が摩擦しその摩擦粉によるベルトの滑りが発生したものを×とした。
【００９５】
【表４】

【００９６】
上記結果から、実施例品の中間転写ベルトは、耐久性に優れたものであり良好なＯＡ機器用ウレタンウレア部材が得られたことがわかる。これに対して、比較例品は、耐久性に劣っていた。
【００９７】
〔プレポリマー溶液Ａの調製〕
８０℃にて１時間真空脱泡脱水したポリブチレンアジペート（ＰＢＡ）（日本ポリウレタン工業社製のニッポラン４００９、Ｍｎ：１０００）１００部に対し、４，４′−ジフェニルメタンジイソシアネート（ＭＤＩ）５８部を添加し、窒素雰囲気下で８０℃にて３時間反応させ、ＮＣＯ末端のプレポリマーを得た。ついで、これをジメチルホルムアミド（ＤＭＦ）３００部に溶解させ、プレポリマー溶液（ＮＣＯ％：７重量％）を調製した。
【００９８】
〔プレポリマー溶液Ｂの調製〕
ポリブチレンアジペート（ＰＢＡ）（日本ポリウレタン工業社製のニッポラン４００９、Ｍｎ：１０００）に代えて、ポリカーボネートジオール（ＰＣＤ）（日本ポリウレタン工業社製のニッポラン９８１、Ｍｎ：１０００）を用いた。それ以外は、上記プレポリマー溶液Ａと同様にして、プレポリマー溶液（ＮＣＯ％：７重量％）を調製した。
【００９９】
〔酸無水物溶液の調製〕
酸無水物である無水ピロメリット酸（ＡＰＡ）１０部を、ＤＭＦ９０部に溶解させ、酸無水物溶液を調製した。
【０１００】
〔ジアミン溶液の調製〕
２，２′，３，３′−テトラクロロ−４，４′−ジアミノジフェニルメタン１０部を、ＤＭＦ９０部に溶解させ、ジアミン溶液を調製した。
【０１０１】
〔鎖延長剤溶液の調製〕
鎖延長剤である１，４−ブタンジオール（１，４−ＢＤ）１０部を、ＤＭＦ９０部に溶解させ、鎖延長剤溶液（酸無水物不含）を調製した。
【０１０２】
【実施例２２】
上記プレポリマー溶液Ａ４３５部と上記酸無水物溶液１８２部とを窒素雰囲気下で１１０℃にて２．５時間混合攪拌しながら反応させた後、上記ジアミン溶液１４０部を添加し、窒素雰囲気下で１１０℃にて２．５時間混合攪拌しながら反応させた。その後、電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１．４部を添加し、ウレタンウレアイミド溶液を調製した。そして、このウレタンウレアイミド溶液を円筒金型内に注入し、遠心成形した後、蓋を取り外して脱型することにより、単層構造（厚み１５０μｍ）の無端ベルトである中間転写ベルトを作製した。
【０１０３】
【実施例２３】
プレポリマー溶液Ａに代えて、プレポリマー溶液Ｂを用いる以外は、実施例２２と同様にして、ウレタンウレアイミド溶液を調製した。そして、このウレタンウレアイミド溶液を用いて、実施例２２と同様にして、中間転写ベルトを作製した。
【０１０４】
【比較例９】
上記プレポリマー溶液Ａ２９０部と、上記鎖延長剤溶液（酸無水物不含）７５部とを、窒素雰囲気下で１１０℃にて２．５時間混合攪拌しながら反応させ、その後、電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１．１部を添加し、ウレタン溶液を調製した。そして、このウレタン溶液を用いて、実施例２２と同様にして、中間転写ベルトを作製した。
【０１０５】
【比較例１０】
プレポリマー溶液Ａに代えて、プレポリマー溶液Ｂを用いる以外は、比較例９と同様にして、ウレタン溶液を調製した。そして、このウレタン溶液を用いて、実施例２２と同様にして、中間転写ベルトを作製した。
【０１０６】
【比較例１１】
ポリイミド樹脂（新日本理化社製のリカコートＰＮ−２０）１００部と、電気抵抗調整剤（日本カーリット社製のＬＲ−１４７）１部とを、ＤＭＦ２５０部に溶解混合させ、ポリイミド溶液を調製した。そして、このポリイミド溶液を用いて、実施例２２と同様にして、中間転写ベルトを作製した。
【０１０７】
このようにして得られた実施例品および比較例品の中間転写ベルトを用いて、下記の基準に従い、耐久性の評価を行った。その結果を、後記の表５に示した。
【０１０８】
〔耐久性〕
各中間転写ベルトについて、市販のカラー複写機の中間転写ユニットを取り出し、回転試験を７２０時間行い、耐久性の評価を行った。評価は、回転試験の間、安定して正常に回転したものを○、ベルト内面が摩耗し、その摩耗粉によるベルトの滑りが発生したもの、またはベルト表面に割れやひびが発生したものを×とした。
【０１０９】
【表５】

【０１１０】
上記結果から、実施例品の中間転写ベルトは、比較例品に比べて、耐久性に優れることがわかる。また、比較例１１品の中間転写ベルトは、ポリイミド樹脂を用いて形成されているため、屈曲性がなく、ベルト走行中に割れやひび等が発生した。
【０１１１】
【発明の効果】
以上のように、本発明のＯＡ機器用ウレタンウレア部材は、イソシアネート系化合物およびイミド変性イソシアネート系化合物の混合物（Ａ）と、ポリオール（Ｂ）と、ジアミノ化合物（Ｃ）とを備えたウレタンウレアイミド組成物、もしくはイソシアネート系化合物とポリオールとを用いてなるプレポリマー（Ｄ）と、酸無水物（Ｅ）と、ジアミノ化合物（Ｆ）とを備えたウレタンウレアイミド組成物によって形成されたものである。このため、上記混合物（Ａ）とポリオール（Ｂ）とジアミノ化合物（Ｃ）との反応過程において二酸化炭素が発生しないために、もしくは上記プレポリマー（Ｄ）と酸無水物（Ｅ）とジアミノ化合物（Ｆ）との反応過程において二酸化炭素を前もって発生させるために、それぞれ得られる硬化物は無発泡で強度的に優れ、結果、耐摩耗性および耐欠け性に優れた、特に摩擦熱のような高温においても高い強度を備えたＯＡ機器用ウレタンウレア部材が得られる。
【０１１２】
また、上記ポリオール（Ｂ）として、変性シリコーンオイルおよび変性パーフルオロエーテルの少なくとも一方を用いると、摩擦係数の低下が図れる。
【０１１３】
そして、本発明のＯＡ機器用ウレタンウレア部材としては、例えば、電子写真複写機のクリーニングブレードをはじめ、層形成用ブレード、給紙搬送ロール等の各種ロールや中間転写ベルト等の無端ベルト等に有用に用いられる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a urethane urea member for OA equipment used as various members of OA (Office Automation) equipment, and more specifically, a cleaning blade, a layer forming blade, and a sheet feeding / conveying roll of an electrophotographic copying machine. The present invention relates to a urethane urea member for office automation equipment used as an endless belt such as various rolls such as a charging roll, a developing roll, a transfer roll, and a fixing roll, and an intermediate transfer belt.
[0002]
[Prior art]
Conventionally, polyurethane elastomer has been used as a material for forming various members for OA equipment, for example, a cleaning blade because of its excellent wear resistance. Various proposals have been made to further improve wear resistance and chipping resistance. For example, (1) the above characteristics are improved by disturbing the regularity (crystallinity) of the soft segment of the polymer (JP-A-8-44264), and (2) the friction is reduced on the urethane surface. Examples of the method include improving the characteristics. As the above (2), specifically, a lubricant is added to the cleaning blade forming material (JP-A-7-306616, JP-A-5-158389, JP-A-5-173464, etc.), and cleaning. Examples include coating the blade surface (JP-A-4-260084, JP-A-4-212190, etc.) and the like.
[0003]
[Problems to be solved by the invention]
However, the above method (1) raises the problem that the viscosity of the forming material increases and the workability decreases. Further, the above method (2) has a problem that the number of forming steps of the cleaning blade increases and becomes complicated. As described above, the conventional proposals for improving the wear resistance and chipping resistance of the cleaning blade cause the problems as described above. Therefore, the characteristics can be improved without causing such problems. Was requested.
[0004]
The present invention has been made in view of such circumstances, and uses urethane materials for office automation equipment having excellent wear resistance and chipping resistance without using complicated processes using a forming material having excellent workability. The purpose is to provide a member.
[0005]
[Means for Solving the Problems]
In order to achieve the above object, the present invention ,under Urethane ureaimide composition comprising the following (A) to (C) Where To a fixed shape Cure The Set Or a urethane ureaimide composition comprising the following (D) to (F) Where To a fixed shape Cure The Set It takes the composition of becoming.
(A) A mixture of an isocyanate compound and an imide-modified isocyanate compound.
(B) Polyol.
(C) Diamino compound.
(D) A prepolymer comprising an isocyanate compound and a polyol.
(E) Acid anhydride.
(F) Diamino compound.
[0006]
That is, the present inventors have made extensive studies in order to obtain a urethane urea member for office automation equipment having excellent wear resistance and chipping resistance without going through complicated processes. As a result, when a urethane urea imide composition having the above (A), (B) and (C) is used as a material for forming a urethane urea member, carbon dioxide is not generated in the reaction process, or (D ), (E), and (F), a urethane urea imide composition provided with (F) generates carbon dioxide in advance in the reaction process. It has been found that a urethane urea member for OA equipment having excellent wear and chipping resistance can be obtained, and the present invention has been achieved.
[0007]
Further, when at least one of modified silicone oil and modified perfluoroether is used as the polyol (B), the friction coefficient can be reduced.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Next, embodiments of the present invention will be described in detail.
[0009]
The urethane urea member for OA equipment of the present invention uses a urethane urea imide composition comprising a mixture (A) of an isocyanate compound and an imide-modified isocyanate compound, a polyol (B), and a diamino compound (C). It is formed into various predetermined shapes.
[0010]
The mixture (A) of the isocyanate compound and the imide-modified isocyanate compound can be obtained, for example, by reacting the isocyanate compound and the acid anhydride in an excess state of the isocyanate compound in the absence of a solvent.
[0011]
The isocyanate compound is not particularly limited. For example, isophorone diisocyanate (IPDI), 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2, 6-tolylene diisocyanate (2,6-TDI), 3,3′-vitrylene-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 2,4-tolylene diisocyanate urea Thiidinedione (2,4-TDI dimer), 1,5-naphthylene diisocyanate, metaphenylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), carbodiimide-modified MDI, orthotoluidine The Examples thereof include diisocyanates such as socyanate, xylene diisocyanate, paraphenylene diisocyanate, and lysine diisocyanate methyl ester, triisocyanates such as triphenylmethane-4,4 ′, 4 ″ -triisocyanate, and polymeric MDI. Of these, isophorone diisocyanate (IPDI) and 4,4′-diphenylmethane diisocyanate (MDI) are preferably used from the viewpoints of processability and mechanical strength.
[0012]
The acid anhydride is not particularly limited, and examples thereof include pyromellitic anhydride (APA), 4,4′-biphthalic anhydride (BiPA), 4,4′-oxydiphthalic anhydride (ODPA), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic anhydride (DPSA), 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride and the like. These may be used alone or in combination of two or more. Among these, pyromellitic anhydride (APA) is preferably used from the viewpoint of mechanical strength.
[0013]
The mixing ratio of the isocyanate compound (a1) and the acid anhydride (a2) is preferably set in a range of a1 / a2 = 100/50 to 100 / 0.1, particularly preferably a1 /. It is the range of a2 = 100/35 to 100/5. That is, when the amount of the acid anhydride (a2) exceeds 50, the viscosity of the resulting mixture (A) of the isocyanate compound and the imide-modified isocyanate compound tends to be high and cast molding tends to be difficult. Further, when the acid anhydride (a2) is less than 0.1, imide modification is insufficient and sufficient heat resistance of urethane is difficult to obtain.
[0014]
In the mixture (A) of the isocyanate compound and the imide-modified isocyanate compound obtained by the reaction of the isocyanate compound (a1) and the acid anhydride (a2), the mixing ratio of both is the isocyanate compound (a1 ) And the acid anhydride (a2). Specifically, it is preferably set in the range of isocyanate compound / imide-modified isocyanate compound = 0/100 to 99.8 / 0.2. And the mixing ratio of the isocyanate type compound and imide modified isocyanate type compound in the mixture (A) obtained by reaction of the said compound can be measured by GPC (gel permeation chromatography), for example.
[0015]
The polyol (B) used together with the mixture (A) is not particularly limited, and examples thereof include polyester polyols such as polyethylene adipate (PEA), polybutylene adipate (PBA), polyhexylene adipate, polycaprolactone, Examples thereof include polyether polyols such as polycarbonate, polypropylene glycol (PPG), polyoxytetramethylene glycol (PTMG), and polyoxypropylene glycol, modified silicone oil, and modified perfluoroether. These may be used alone or in combination of two or more. Of these, polybutylene adipate (PBA), modified silicone oil, and modified perfluoroether are preferably used from the viewpoint of excellent wear resistance and low friction. In view of processability, it is preferable to use a polyol which is liquid at normal temperature.
[0016]
The number average molecular weight (Mn) of the polyol (B) is preferably in the range of 500 to 5000, particularly preferably 1000 to 3000. That is, when the Mn of the polyol (B) is less than 500, there is a tendency that the physical properties of OA equipment members (cleaning blades, various rolls, etc.) obtained by casting are reduced. It is because workability tends to be deteriorated when exceeding.
[0017]
The mixture ratio (A / B) of the mixture (A) of the isocyanate compound and the imide-modified isocyanate compound and the polyol (B) is in a molar ratio of A / B = 1.5 / 1 to 5/1. It is preferable to set, and particularly preferably 2.2 / 1 to 3.9 / 1. That is, when the A / B ratio is smaller than 1.5 / 1, the hard segment content formed by the isocyanate compound and the chain extender decreases, and the mechanical strength tends to decrease. Further, when the A / B ratio is larger than 5/1, the hard segment content becomes too large, the hardness becomes high, and it becomes difficult to obtain rubber elasticity.
[0018]
Although it does not specifically limit as a diamino compound (C) used with the said mixture (A) and a polyol (B), What has an aromatic hydrocarbon group in molecular structure is preferable, for example, following formula ( 1) 2,2 ', 3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, trimethylene-bis (4-aminobenzoate) ), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane and the like. These may be used alone or in combination of two or more. Among these, 2,2 ′, 3,3′-tetrachloro-4,4′-diaminodiphenylmethane is preferably used in terms of excellent workability.
[0019]
[Chemical 1]

[0020]
The blending ratio of the diamino compound (C) is preferably in the range of 0.1 to 75 parts, particularly preferably 0.5 to 35, with respect to 100 parts by weight (hereinafter abbreviated as “part”) of the polyol (B). Part. That is, if the diamino compound (C) is less than 0.1 part, high strength cannot be obtained, and conversely if it exceeds 75 parts, flexibility may not be obtained.
[0021]
The urethane urea imide composition includes, in addition to the mixture (A), polyol (B), and diamino compound (C) of the isocyanate compound and imide-modified isocyanate compound, a chain extender, a catalyst, if necessary. , Surfactants, flame retardants, colorants, fillers, plasticizers, stabilizers, mold release agents, electrical resistance modifiers, and the like can be appropriately blended and used.
[0022]
Examples of the chain extender include 1,4-butanediol (1,4-BD), ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexane. Examples thereof include polyols having a molecular weight of 300 or less such as dimethanol, xylene glycol, triethylene glycol, trimethylolpropane (TMP), glycerin, pentaerythritol, sorbitol, 1,2,6-hexanetriol. These may be used alone or in combination of two or more.
[0023]
Examples of the catalyst include amine compounds such as tertiary amines and organometallic compounds such as organotin compounds. Of these, amine compounds are preferably used.
[0024]
Examples of the tertiary amine include trialkylamines such as triethylamine; tetraalkyldiamines such as N, N, N ′, N′-tetramethyl-1,3-butanediamine; aminoalcohols such as dimethylethanolamine; Ethoxylated amines; Ethoxylated diamines; Ester amines such as bis (diethylethanolamine) adipate; Triethylenediamine; Cyclohexylamine derivatives such as N, N-dimethylcyclohexylamine; N-methylmorpholine, N- (2-hydroxypropyl)- Morpholine derivatives such as dimethylmorpholine; piperazine derivatives such as N, N′-diethyl-2-methylpiperazine, N, N′-bis- (2-hydroxypropyl) -2-methylpiperazine, and the like.
[0025]
Examples of the organic tin compound include dialkyltin compounds such as dibutyltin dilaurate and dibutyltin di (2-ethylhexoate), stannous 2-ethylcaproate, stannous oleate, and the like.
[0026]
The urethane urea imide composition is prepared as follows, for example, and is used as a molding material for various OA equipment members. That is, first, a mixture (A) of an isocyanate compound and an imide-modified isocyanate compound is prepared by reacting an isocyanate compound and an acid anhydride in an excess state of an isocyanate compound at a predetermined ratio in the absence of a solvent. To do. On the other hand, the polyol (B), the diamino compound (C) and other additives as necessary are blended and defoamed and dehydrated while stirring under reduced pressure to prepare a hardener solution. Next, the mixture (A) of the isocyanate compound and the imide-modified isocyanate compound is degassed in advance, added to the curing agent solution, and stirred and mixed under reduced pressure to prepare a urethane ureaimide composition. . Next, the urethane urea imide composition is poured into a pre-heated predetermined molding die and cured, and then the molded product is demolded from the molding die, and further, 100 to 100 as secondary curing. By performing the curing reaction at a temperature of 120 ° C., various members for OA equipment using the urethane ureaimide composition can be produced.
[0027]
For example, when producing a cleaning blade, a urethane urea imide composition is poured and cured in a molding die preheated and provided with a mounting metal plate, and then the molded product is removed from the molding die. Demold. Further, in the same manner as described above, the cleaning blade is manufactured by heating and secondary curing. Alternatively, it can be produced by centrifugal molding.
[0028]
And as a urethane urea member for OA equipment, other members other than the cleaning blade, for example, various rolls such as a sheet feeding / conveying roll, an intermediate transfer belt, and the like are used to form each of the urethane urea imide compositions. A metal mold is prepared and can be produced by cast molding or centrifugal molding as described above.
[0029]
The reaction of the mixture (A) of the isocyanate compound and the imide-modified isocyanate compound is preferably performed under a high temperature condition of 130 to 170 ° C. in an inert atmosphere such as nitrogen as well as in the absence of a solvent.
[0030]
Furthermore, in the manufacturing process of the mixture (A) of the isocyanate compound and the imide-modified isocyanate compound, other additives can be appropriately blended as needed in addition to the isocyanate compound and the acid anhydride.
[0031]
Examples of the other additives include the chain extenders, catalysts, surfactants, flame retardants, colorants, fillers, plasticizers, stabilizers, mold release agents, electrical resistance adjusters, and the like described above. .
[0032]
The decompression conditions for degassing the mixture (A) of the isocyanate compound and the imide-modified isocyanate compound in advance are preferably set in the range of 133.32 to 2666.4 Pa.
[0033]
The above-mentioned polyol (B), diamino compound (C), and other additives as required, and depressurization dehydration while stirring under reduced pressure to prepare a hardener solution, the pressure reduction conditions are 133.32 It is preferable to set in the range of ˜2666.4 Pa.
[0034]
It is preferable to set it as the pressure reduction conditions at the time of adding the said mixture (A) to a hardening | curing agent liquid, and carrying out mixing stirring in the range of 133.32-2666.4Pa.
[0035]
The urethane ureaimide composition is prepared by degassing the mixture (A), polyol (B) and diamino compound (C) in advance, and then dissolving them in a solvent such as dimethylformamide (DMF). It may be prepared by mixing and stirring under normal pressure.
[0036]
Alternatively, the urethane urea member for OA equipment of the present invention is a urethane urea imide comprising a prepolymer (D) comprising an isocyanate compound and a polyol, an acid anhydride (E), and a diamino compound (F). It is formed into various predetermined shapes using the composition.
[0037]
Although it does not specifically limit as an isocyanate type compound used for the said prepolymer (D), The thing similar to the isocyanate type compound used for the said mixture (A) is mention | raise | lifted.
[0038]
The polyol used for the prepolymer (D) is not particularly limited, and examples thereof include the same polyols as the polyol (B). Of these, polyester-based polyols and polycarbonate-based polyols are preferably used in terms of excellent wear resistance.
[0039]
The mixing molar ratio of the isocyanate compound used in the prepolymer (D) and the polyol is usually in the range of isocyanate compound / polyol = 1.2 / 1 to 11/1.
[0040]
The acid anhydride (E) used together with the prepolymer (D) is not particularly limited, and examples thereof include those similar to those used for the preparation of the mixture (A). Of these, pyromellitic anhydride (APA) is preferably used in terms of excellent mechanical strength.
[0041]
The weight mixing ratio of the prepolymer (D) to the acid anhydride (E) is preferably in the range of D / E = 100 / 0.8 to 100/30, particularly preferably D / E = 100/9 to 100. / 25. That is, when the weight mixing ratio of the acid anhydride (E) is less than 0.8, the imide modification is insufficient and it is difficult to obtain sufficient heat resistance of the urethane, and conversely the weight mixing ratio of the acid anhydride (E). This is because when the ratio exceeds 30, the imide content is excessively increased, the hardness is increased, and rubber elasticity is hardly obtained.
[0042]
Although there is no limitation in particular as a diamino compound (F) used with the said prepolymer (D) and an acid anhydride (E), The thing similar to the said diamino compound (C) is mention | raise | lifted.
[0043]
The prepolymer (D) is preferably dissolved in a solvent such as dimethylformamide (DMF) and used as a prepolymer solution. The acid anhydride (E) is also preferably dissolved in a solvent such as DMF and used as an acid anhydride solution. Furthermore, the diamino compound (F) is also preferably dissolved in a solvent such as DMF and used as a diamine solution.
[0044]
And the said urethane urea member for OA equipment can be produced as follows, for example. That is, first, an isocyanate compound is added to a polyol that has been vacuum degassed and dehydrated under predetermined conditions (preferably at 80 ° C. for 1 hour), and the predetermined conditions (preferably at 80 ° C. at 3 Time) to obtain an NCO-terminated prepolymer (D). Next, the prepolymer (D) is dissolved in a solvent such as DMF to prepare a prepolymer solution. Meanwhile, an acid anhydride solution (E) such as pyromellitic anhydride (APA) is dissolved in a solvent such as DMF to prepare an acid anhydride solution. Also ,Up The diamino compound (F) is dissolved in a solvent such as DMF to prepare a diamine solution. Then, the prepolymer solution, the acid anhydride solution, and the diamine solution are reacted while being mixed and stirred under a predetermined condition (preferably, at 110 ° C. for 2.5 hours) in a nitrogen atmosphere. If necessary, an electrical resistance adjuster is added to prepare a urethane ureaimide solution. Then, using this urethane ureaimide solution, various urethane urea members for OA equipment can be produced in the same manner as described above.
[0045]
For example, when producing an endless belt such as an intermediate transfer belt, the urethane urea imide solution is poured into a cylindrical mold, centrifuged under predetermined conditions, and then removed by removing the lid and removing the mold. be able to.
[0046]
Examples of the member for OA equipment of the present invention include various rolls such as a cleaning blade and a layer forming blade of an electrophotographic copying machine, a paper feeding and conveying roll, and an endless belt such as an intermediate transfer belt.
[0047]
Next, examples will be described together with comparative examples.
[0048]
First, prior to Examples and Comparative Examples, the following mixtures of isocyanate compounds and imide-modified isocyanate compounds were prepared.
[0049]
[Preparation of Mixture A]
By reacting 88.8 parts of isophorone diisocyanate (IPDI) and 21.8 parts of pyromellitic anhydride (APA) in a nitrogen atmosphere at 150 ° C. for 5 hours with stirring, an isocyanate compound and an imide-modified isocyanate compound A mixture A was prepared. In addition, the compounding ratio of the isocyanate component (IPDI) and the acid anhydride (APA) was 100/25 in molar ratio.
[0050]
[Preparation of mixture B]
By reacting 44.4 parts of IPDI, 50 parts of 4,4′-diphenylmethane diisocyanate (MDI) and 21.8 parts of pyromellitic anhydride (APA) in a nitrogen atmosphere at 150 ° C. with stirring for 5 hours, isocyanate A mixture B of an amide compound and an imide-modified isocyanate compound was prepared. In addition, the compounding ratio of the isocyanate component (IPDI + MDI) and the acid anhydride (APA) was 100/25 in molar ratio.
[0051]
[Preparation of mixture C]
A mixture C of an isocyanate compound and an imide-modified isocyanate compound was prepared by reacting 100 parts of MDI and 5.2 parts of APA in a nitrogen atmosphere while stirring at 150 ° C. for 5 hours. In addition, the mixture ratio of MDI and APA was 100/6 in molar ratio.
[0052]
[Preparation of Mixture D]
A mixture D of an isocyanate compound and an imide-modified isocyanate compound was prepared by reacting 88.8 parts of IPDI and 43.6 parts of APA in a nitrogen atmosphere while stirring at 150 ° C. for 5 hours. In addition, the mixture ratio of IPDI and APA was 100/50 by molar ratio.
[0053]
[Preparation of mixture E]
A mixture E of an isocyanate compound and an imide-modified isocyanate compound was prepared by reacting 100 parts of MDI and 0.09 part of APA in a nitrogen atmosphere while stirring at 150 ° C. for 5 hours. In addition, the mixture ratio of MDI and APA was 100 / 0.1 in molar ratio.
[0054]
[Example 1]
100 parts of polybutylene adipate (PBA) (Nipporan 4010 manufactured by Nippon Polyurethane Industry Co., Ltd.), 11 parts of pyromellitic anhydride (APA) and 30 parts of 4,4′-diphenylmethane diisocyanate (MDI) are blended, and 200 parts of DMF In a nitrogen atmosphere at 110 ° C. for 2.5 hours with mixing and stirring, 6 parts of 2,2 ′, 3,3′-tetrachloro-4,4′-diaminodiphenylmethane was added, A urethane ureaimide composition was prepared by reacting at 110 ° C. for 2.5 hours with mixing and stirring.
[0055]
Then, this urethane ureaimide composition was subjected to centrifugal molding with a mold preheated to 140 ° C., and then subjected to secondary curing (110 ° C. × 12 hours) to prepare a urethane urea imide sheet. Further, a cleaning blade was prepared by adhering the urethane ureaimide sheet to a sheet metal.
[0056]
[Example 2]
100 parts of polybutylene adipate (PBA) (Nipporan 4010 manufactured by Nippon Polyurethane Industry Co., Ltd., Mn: 2000) and 7.5 parts of 2,2 ′, 3,3′-tetrachloro-4,4′-diaminodiphenylmethane The mixture was blended and heated at 150 ° C. for 1 hour to dissolve the diamino compound (2,2 ′, 3,3′-tetrachloro-4,4′-diaminodiphenylmethane) in the polyol. Next, 4 parts of trimethylolpropane (TMP) was added, degassed and dehydrated at 80 ° C. for 20 minutes while stirring under reduced pressure (666.6 Pa), and then degassed under reduced pressure (666.6 Pa for 20 minutes at 80 ° C.). 47 parts of the above mixture A was added and stirred and mixed for 60 seconds to prepare a urethane ureaimide composition A.
[0057]
Then, this urethane ureaimide composition A is cast and molded into a sheet molding die preheated to 140 ° C., then demolded, and then subjected to secondary curing (110 ° C. × 12 hours). Thus, a urethane ureaimide sheet was produced.
[0058]
Further, the urethane urea imide composition A is cast and molded on a cleaning blade molding die preheated to 140 ° C., then demolded, and then subjected to secondary curing (110 ° C. × 12 hours). As a result, a cleaning blade which is an integrally molded body with the sheet metal was produced.
[0059]
[Example 3]
A urethane urea imide composition B was prepared in the same manner as in Example 2 except that the mixture B was used in place of the mixture A. Then, using this urethane ureaimide composition B, a urethane ureaimide sheet and a cleaning blade were produced in the same manner as in Example 2.
[0060]
[Example 4]
Example 2 with the exception that the amount of 2,2 ′, 3,3′-tetrachloro-4,4′-diaminodiphenylmethane was increased to 22.4 parts and 45 parts of the mixture C were used instead of 47 parts of the mixture A. Similarly, a urethane ureaimide composition C was prepared. Then, using this urethane ureaimide composition C, a urethane ureaimide sheet and a cleaning blade were produced in the same manner as in Example 2.
[0061]
[Example 5]
100 parts of modified silicone oil (Carbinol-modified silicone oil SF8427 manufactured by Toray Dow Corning Silicone, Mn: 2400) and 1.9 parts of 2,2 ', 3,3'-tetrachloro-4,4'-diaminodiphenylmethane And heated at 150 ° C. for 1 hour to dissolve the diamino compound (2,2 ′, 3,3′-tetrachloro-4,4′-diaminodiphenylmethane) in the polyol. Next, 2 parts of trimethylolpropane (TMP) was added and degassed and dehydrated at 80 ° C. for 20 minutes while stirring under reduced pressure (666.6 Pa), and then degassed under reduced pressure (666.6 Pa for 20 minutes at 80 ° C.). 47 parts of the above mixture D was added and stirred and mixed for 60 seconds to prepare a urethane ureaimide composition D. Then, using this urethane ureaimide composition D, a urethane ureaimide sheet and a cleaning blade were produced in the same manner as in Example 2.
[0062]
[Example 6]
100 parts of polybutylene adipate (PBA) (Nipporan 4010, Mn: 2000, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 33.6 parts of 2,2 ', 3,3'-tetrachloro-4,4'-diaminodiphenylmethane The mixture was blended and heated at 150 ° C. for 1 hour to dissolve the diamino compound (2,2 ′, 3,3′-tetrachloro-4,4′-diaminodiphenylmethane) in the polyol. Next, 2 parts of trimethylolpropane (TMP) was added and degassed and dehydrated at 80 ° C. for 20 minutes while stirring under reduced pressure (666.6 Pa), and then degassed under reduced pressure (666.6 Pa for 20 minutes at 80 ° C.). 47 parts of the above mixture E was added and stirred and mixed for 60 seconds to prepare a urethane ureaimide composition E. Then, using this urethane ureaimide composition E, a urethane ureaimide sheet and a cleaning blade were produced in the same manner as in Example 2.
[0063]
[Comparative Example 1]
100 parts of polybutylene adipate (PBA) (Nipporan 4010 manufactured by Nippon Polyurethane Industry Co., Ltd.), 6 parts of 1,4-BD, and 4 parts of TMP were blended and stirred at 80 ° C. under reduced pressure (666.6 Pa). After defoaming and dewatering for 20 minutes, 38 parts of IPDI was added thereto and stirred and mixed for 60 seconds to prepare urethane composition a. Then, using this urethane composition a, a urethane sheet and a cleaning blade were produced in the same manner as in Example 2.
[0064]
[Comparative Example 2]
A urethane composition b was prepared in the same manner as in Comparative Example 1 except that 44 parts of MDI was used instead of 38 parts of IPDI. Then, using this urethane composition b, a urethane sheet and a cleaning blade were produced in the same manner as in Example 2.
[0065]
Using the urethane urea imide sheet and cleaning blade of the example thus obtained, and the urethane sheet and cleaning blade of the comparative example, each characteristic was evaluated according to the following criteria. These results are also shown in Table 1 below.
[0066]
[Tensile strength (T _B )]
In accordance with JIS K 6251, the tensile strength of each urethane ureaimide sheet (urethane sheet) (T _B ) Was measured at each temperature of 25 ° C and 50 ° C.
[0067]
(Abrasion resistance)
Each cleaning blade is incorporated into a commercially available laser printer (LBP), and after printing 30,000 sheets in A4 size under normal temperature and humidity (25 ° C x 60% RH), the cleaning blade is scanned with a scanning electron microscope. The amount of wear at the edge of the wire was observed, and the cross-sectional area of the worn portion (U μm ² ) And the unit length (X μm) of the tip, and the amount of wear (W μm) according to the formula: W = U × X ^Three ) Was calculated. In addition, it can be said that it is excellent in abrasion resistance, so that this amount of wear is small. And this wear amount is 50 μm. ^Three Less than ○, 50μm ^Three The above was evaluated as x.
[0068]
(Edge chip resistance)
Each cleaning blade was incorporated into a commercially available laser printer (LBP), and 30,000 sheets were printed in A3 size under a low temperature and low humidity environment (15 ° C. × 10% RH). Then, the presence or absence of chipping of the edge portion of the cleaning blade after the 30,000 sheets were printed was observed at a magnification of 500 times using a scanning electron microscope. Then, the case where there was no chip was evaluated as ◯, and the case where there was a chip was evaluated as x.
[0069]
[Table 1]

[0070]
From the above results, all of the example products were excellent in wear resistance and edge chipping resistance. Further, it can be seen that the tensile strength is high even at a high temperature of 50 ° C. as well as 25 ° C., and the strength is excellent in frictional heat and the like.
[0071]
On the other hand, the comparative products were inferior in wear resistance and edge chipping resistance. As for the tensile strength, a good value was obtained at 25 ° C., but the value was remarkably lowered at a high temperature of 50 ° C.
[0072]
[Example 7]
First, a urethane ureaimide composition A was prepared in the same manner as described above. Then, this urethane ureaimide composition A was cast into a layer-forming braid molding die to produce a layer-forming blade under the same conditions as the cleaning blade.
[0073]
Examples 8 to 11, Comparative Examples 3 and 4
A layer forming blade was produced in the same manner as in Example 7 except that the urethane urea imide composition or the urethane composition shown in Table 2 below was used instead of the urethane urea imide composition A.
[0074]
Using the layer forming blades of Examples and Comparative Examples thus obtained, the wear resistance was evaluated according to the following criteria. The results are shown in Table 2 below.
[0075]
(Abrasion resistance)
Each layer forming blade is incorporated into a developing machine of a laser beam printer LJ4000 manufactured by Hewlett-Packard Co., and a 6000-sheet endurance test is performed by stopping a few seconds each time a character image is printed (using an A4 printed portion of 5% original). After this, the wear depth generated on the surface of the layer forming blade was measured with a surface roughness meter Surfcom (manufactured by Tokyo Seimitsu Co., Ltd.). As a result, the case where the wear depth was 20 μm or less was marked with ○, and the case where the wear depth was over 20 μm was marked with ×.
[0076]
[Table 2]

[0077]
From the above results, it can be seen that the layer-forming blade of the example product was excellent in wear resistance, and a good urethane urea member for OA equipment was obtained. On the other hand, the comparative product was inferior in wear resistance.
[0078]
Example 12
First, a urethane ureaimide composition A was prepared in the same manner as described above. Then, this urethane ureaimide composition A was cast into a roll molding die provided with a cylindrical shaft, and a paper feed roll was produced under the same conditions as the cleaning blade.
[0079]
Examples 13 to 16, Comparative Examples 5 and 6
A sheet feeding roll was produced in the same manner as in Example 12 except that the urethane ureaimide composition or the urethane composition shown in Table 3 below was used instead of the urethane ureaimide composition A.
[0080]
Using the thus obtained paper rolls of Examples and Comparative Examples, wear resistance was evaluated according to the following criteria. The results are shown in Table 3 below.
[0081]
(Abrasion resistance)
Each paper feed roll was installed in a commercially available copying machine, and 60,000 sheets were evaluated for durability under normal temperature and humidity conditions. The outer diameters before and after the evaluation were measured. The outer diameter change was less than 60 μm, and the outer diameter change was 60 μm or more.
[0082]
[Table 3]

[0083]
From the above results, it can be seen that the paper feed rolls of the examples were excellent in wear resistance and a good urethane urea member for OA equipment was obtained. On the other hand, the comparative product was inferior in wear resistance.
[0084]
[Preparation of Urethane Ureaimide Composition A ′]
1 part of an electrical resistance adjuster (LR-147 manufactured by Nippon Carlit Co., Ltd.) was added to the urethane ureaimide composition A to prepare a urethane ureaimide composition A ′.
[0085]
[Preparation of urethane ureaimide composition B ′]
1 part of an electrical resistance adjuster (LR-147 manufactured by Nippon Carlit Co., Ltd.) was added to the urethane ureaimide composition B to prepare a urethane ureaimide composition B ′.
[0086]
[Preparation of Urethane Ureaimide Composition C ′]
1 part of an electrical resistance adjuster (LR-147 manufactured by Nippon Carlit Co., Ltd.) was added to the urethane ureaimide composition C to prepare a urethane ureaimide composition C ′.
[0087]
[Preparation of Urethane Ureaimide Composition D ′]
1 part of an electrical resistance adjusting agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) was added to the urethane ureaimide composition D to prepare a urethane ureaimide composition D ′.
[0088]
[Preparation of urethane ureaimide composition E ′]
1 part of an electrical resistance modifier (LR-147 manufactured by Nippon Carlit Co., Ltd.) was added to the urethane ureaimide composition E to prepare a urethane ureaimide composition E ′.
[0089]
[Preparation of Urethane Composition a ′]
1 part of an electrical resistance adjuster (LR-147 manufactured by Nippon Carlit Co., Ltd.) was added to the urethane composition a to prepare a urethane composition a ′.
[0090]
[Preparation of urethane composition b ']
1 part of an electrical resistance adjuster (LR-147 manufactured by Nippon Carlit Co., Ltd.) was added to the urethane composition b to prepare a urethane composition b ′.
[0091]
[Example 17]
The urethane urea imide composition A ′ was cast into a centrifugal molding machine preheated to 140 ° C. to form an intermediate transfer belt, and secondary curing was performed under the same conditions as the cleaning blade to prepare an intermediate transfer belt. .
[0092]
Examples 18 to 21, Comparative Examples 7 and 8
An intermediate transfer belt was produced in the same manner as in Example 17 except that the urethane urea imide composition or the urethane composition shown in Table 4 below was used instead of the urethane urea imide composition A ′.
[0093]
Using the intermediate transfer belts of Examples and Comparative Examples thus obtained, durability was evaluated according to the following criteria. The results are shown in Table 4 below.
[0094]
〔durability〕
An intermediate transfer unit of a commercially available color copying machine was taken out and a rotation test was conducted for 720 hours. In the meantime, the case where the belt was rotated stably and normally was marked with ◯, and the belt inner surface was rubbed and the belt was slipped by the friction powder was marked with X.
[0095]
[Table 4]

[0096]
From the above results, it can be seen that the intermediate transfer belt of the example product was excellent in durability and a good urethane urea member for OA equipment was obtained. On the other hand, the comparative product was inferior in durability.
[0097]
[Preparation of Prepolymer Solution A]
Addition of 58 parts of 4,4'-diphenylmethane diisocyanate (MDI) to 100 parts of polybutylene adipate (PBA) (Nipporan 4009, Mn: 1000, manufactured by Nippon Polyurethane Industry Co., Ltd.) vacuum degassed and dehydrated at 80 ° C for 1 hour And reacted at 80 ° C. for 3 hours under a nitrogen atmosphere to obtain an NCO-terminated prepolymer. Subsequently, this was dissolved in 300 parts of dimethylformamide (DMF) to prepare a prepolymer solution (NCO%: 7% by weight).
[0098]
[Preparation of prepolymer solution B]
Instead of polybutylene adipate (PBA) (Nipporan 4009, manufactured by Nippon Polyurethane Industry, Mn: 1000), polycarbonate diol (PCD) (Nipporan 981, manufactured by Nippon Polyurethane Industry, Mn: 1000) was used. Other than that was carried out similarly to the said prepolymer solution A, and prepared the prepolymer solution (NCO%: 7 weight%).
[0099]
(Preparation of acid anhydride solution)
An acid anhydride solution was prepared by dissolving 10 parts of pyromellitic anhydride (APA), which is an acid anhydride, in 90 parts of DMF.
[0100]
(Preparation of diamine solution)
A diamine solution was prepared by dissolving 10 parts of 2,2 ', 3,3'-tetrachloro-4,4'-diaminodiphenylmethane in 90 parts of DMF.
[0101]
(Preparation of chain extender solution)
A chain extender solution (containing no acid anhydride) was prepared by dissolving 10 parts of a chain extender 1,4-butanediol (1,4-BD) in 90 parts of DMF.
[0102]
[Example 22]
After reacting 435 parts of the prepolymer solution A and 182 parts of the acid anhydride solution with mixing and stirring at 110 ° C. for 2.5 hours under a nitrogen atmosphere, 140 parts of the diamine solution was added, and under a nitrogen atmosphere. The reaction was carried out at 110 ° C. for 2.5 hours with mixing and stirring. Thereafter, 1.4 parts of an electric resistance adjuster (LR-147 manufactured by Nippon Carlit Co., Ltd.) was added to prepare a urethane ureaimide solution. Then, this urethane ureaimide solution was poured into a cylindrical mold, centrifuged, and then removed from the mold by removing the lid, thereby producing an intermediate transfer belt as an endless belt having a single layer structure (thickness 150 μm).
[0103]
Example 23
A urethane ureaimide solution was prepared in the same manner as in Example 22 except that the prepolymer solution B was used in place of the prepolymer solution A. Then, an intermediate transfer belt was produced in the same manner as in Example 22 using this urethane ureaimide solution.
[0104]
[Comparative Example 9]
290 parts of the prepolymer solution A and 75 parts of the chain extender solution (containing no acid anhydride) were reacted with mixing and stirring at 110 ° C. for 2.5 hours in a nitrogen atmosphere, and then an electric resistance adjusting agent. 1.1 parts of LR-147 manufactured by Nippon Carlit Co. were added to prepare a urethane solution. Using this urethane solution, an intermediate transfer belt was produced in the same manner as in Example 22.
[0105]
[Comparative Example 10]
A urethane solution was prepared in the same manner as in Comparative Example 9 except that the prepolymer solution B was used in place of the prepolymer solution A. Using this urethane solution, an intermediate transfer belt was produced in the same manner as in Example 22.
[0106]
[Comparative Example 11]
A polyimide solution was prepared by dissolving and mixing 100 parts of a polyimide resin (Rikacoat PN-20, manufactured by Shin Nippon Rika Co., Ltd.) and 1 part of an electrical resistance adjuster (LR-147, manufactured by Nippon Carlit Co., Ltd.) in 250 parts of DMF. Then, using this polyimide solution, an intermediate transfer belt was produced in the same manner as in Example 22.
[0107]
The durability was evaluated according to the following criteria using the intermediate transfer belts of the example product and the comparative product obtained as described above. The results are shown in Table 5 below.
[0108]
〔durability〕
For each intermediate transfer belt, an intermediate transfer unit of a commercially available color copying machine was taken out and subjected to a rotation test for 720 hours to evaluate durability. The evaluation was ○ that the belt rotated stably during the rotation test ○, the belt inner surface was worn and the belt slipped due to the wear powder, or the belt surface was cracked or cracked × It was.
[0109]
[Table 5]

[0110]
From the above results, it can be seen that the intermediate transfer belt of the example product is superior in durability to the comparative example product. In addition, since the intermediate transfer belt of Comparative Example 11 was formed using polyimide resin, it was not flexible and cracked or cracked during belt running.
[0111]
【The invention's effect】
As described above, the urethane urea member for OA equipment of the present invention is a urethane urea imide comprising a mixture (A) of an isocyanate compound and an imide-modified isocyanate compound, a polyol (B), and a diamino compound (C). The composition or a urethane ureaimide composition comprising a prepolymer (D) using an isocyanate compound and a polyol, an acid anhydride (E), and a diamino compound (F). . Therefore, carbon dioxide is not generated in the reaction process of the mixture (A), polyol (B), and diamino compound (C), or the prepolymer (D), acid anhydride (E), and diamino compound ( In order to generate carbon dioxide in advance in the course of reaction with F), the resulting cured products are non-foamed and excellent in strength, resulting in excellent wear resistance and chipping resistance, particularly at high temperatures such as frictional heat. The urethane urea member for OA equipment having high strength can be obtained.
[0112]
Further, when at least one of modified silicone oil and modified perfluoroether is used as the polyol (B), the friction coefficient can be reduced.
[0113]
The urethane urea member for OA equipment of the present invention is useful for, for example, a cleaning blade of an electrophotographic copying machine, various rolls such as a layer forming blade, a paper feeding and conveying roll, and an endless belt such as an intermediate transfer belt. Used for.

Claims (8)

Following (A) ~ (C) a urethane urea member for OA equipment, characterized in that formed by curing a constant shape where a urethane urea imide composition comprising a.
(A) A mixture of an isocyanate compound and an imide-modified isocyanate compound.
(B) Polyol.
(C) Diamino compound. The polyol of (B) is, modified silicone oils and perfluoro least one in which claim 1 Symbol placement of OA equipment urethane urea member ether. The urethane urea member for OA equipment according to claim 1 or 2 , wherein the polyol (B) is liquid at normal temperature. The urethane urea member for OA equipment according to any one of claims 1 to 3 , wherein the diamino compound (C) has an aromatic hydrocarbon group in the molecular structure. Following (D) ~ (F) urethane urea member for OA equipment, characterized in that formed by curing a constant shape where a urethane urea imide composition comprising a.
(D) A prepolymer comprising an isocyanate compound and a polyol.
(E) Acid anhydride.
(F) Diamino compound. The urethane urea member for office automation equipment according to claim 5 , wherein the polyol used in the prepolymer (D) is at least one of a polyester-based polyol and a polycarbonate-based polyol. The urethane urea member for OA equipment according to any one of claims 1 to 6 , wherein the urethane urea imide composition is a solution containing a solvent. The urethane urea member for OA equipment is a cleaning blade or an endless belt. The urethane urea member for OA equipment according to any one of claims 1 to 7 .