JP4309544B2 - Image peeling method - Google Patents
Image peeling method Download PDFInfo
- Publication number
- JP4309544B2 JP4309544B2 JP2000009480A JP2000009480A JP4309544B2 JP 4309544 B2 JP4309544 B2 JP 4309544B2 JP 2000009480 A JP2000009480 A JP 2000009480A JP 2000009480 A JP2000009480 A JP 2000009480A JP 4309544 B2 JP4309544 B2 JP 4309544B2
- Authority
- JP
- Japan
- Prior art keywords
- recording material
- image
- peeling
- fixing state
- peeling member
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Cleaning In Electrography (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、表面に熱溶融性または熱可塑性の画像形成物質よりなる画像を形成する薄膜を有する被記録材を、ドラムあるいはベルト状の剥離部材と加熱接触させることにより画像を剥離除去して被記録材を再生する被記録材の画像剥離方法に関する。
【0002】
【従来の技術】
最近のOA化により、プリンタ用紙や複写用紙が大量に使用されるようになってきた。そのために、森林の伐採による地球環境の悪化の問題まで引き起こすようになってしまった。従来、この問題に対しては、一度使用した用紙上のインキ等を取り除き、潰して再び抄いて、古紙といわれる紙に再生する方法しかなかった。しかし、最近、特許公報第2764066に示されるように一度使用した紙の上の文字画像をクリーニングにより取り去り、複写あるいはプリンティングに再利用することができる被記録材の再生方法が開発された。
この方法は、表面に熱溶融性または熱可塑性の画像形成物質より成る画像をその表面に形成している被記録材を、画像形成物質と被記録材との定着状態を低下させるために定着状態低下液を付着させた後、画像形成物質に加熱した剥離部材を密接させ、加熱軟化させた画像形成物質を被記録材から剥離し、被記録材の再生を行なう方法である。
この方法において、剥離部材に密接させられた被記録材は、画像形成物質を剥離部材によって剥離した後、再生のために剥離部材から剥離しなければならない。この剥離には一般的には剥離部材に接触するように設置されたブレードを使用するか、または、剥離部材を薄いベルト状にして急激に屈曲させることにより被記録材を曲率分離する方法が採用されている。
【0003】
この方法が開発された当時は、定着状態低下液の付着量も多く、また、一般の上質紙が使用されることも多かったため、上記の方法での分離に特に問題は生じていなかった。しかし、この再生方法の開発後、これに準ずる再生方法の改良が進み、特に画像形成物質の被記録材への定着状態を低下させるための定着状態低下液の使用量を減らすことが目標のひとつになった。これは被記録材を再生するためには一度付与した定着状態低下液を完全に乾燥しなければならず、液の使用量が少ないほど乾燥に要するエネルギーが小さくなるためである。例えば、特開平10−171319では定着状態低下液の使用量をA4サイズ当たり従来の4グラムから1グラムに少なくすると提案しており、特開平10−278380では0.05〜0.6グラムまで低下させることを提案しており、最終的には定着状態低下液の使用量をゼロにすることが目標となっているのが明らかである。しかし、このように定着状態低下液の使用量が低下すると、本来この再生方法の持つ定着状態低下液により画像形成物質と被記録材の定着を緩める効果は弱くならざるを得ず、被記録材に一般の上質紙を使用した場合は、画像形成物質の除去が不完全になり、これらの再生方法に使用する被記録材にも画像形成物質を除去しやすい特性が求められ始めるに至った。例えば、特開平11−143110では、表面エネルギーが温度によって変化するような物質をその表面に被覆した被記録材を提案しており、被記録材の表面を画像形成物質を除去しやすい何らかの被膜で覆うことを提案している。
ただし、このように定着状態低下液の使用量を少なくした場合、新たな問題が生じるようになった。すなわち、従来は一般の上質紙を使用していたが画像形成物質を除去しやすくするために付与するようになった被膜が、被記録材の再生時に加熱接触される剥離部材に加熱接着してしまい、剥離部材から被記録材が剥離できない問題を生じるようになった。
【0004】
【発明が解決しようとする課題】
本発明は、表面に熱溶融性または熱可塑性の画像形成物質より成る画像を形成する被膜を有する被記録材を、画像形成物質と被記録材との定着状態を低下させるために定着状態低下液を付着させた後、画像形成物質に加熱した剥離部材を密接させ、加熱軟化させた画像形成物質を被記録材から剥離し、被記録材の再生を行なう画像剥離方法および該画像剥離方法に使用する被記録材として、分離不良によるジャムの発生がなく、また、分離時の分離爪への接触による損傷のおこりにくい画像剥離方法の提供を目的とする。
【0005】
【課題を解決するための手段】
本発明者らは前記課題を解決するために種々検討の結果、熱溶融性または熱可塑性の画像形成物質より成る被膜を剥離部材によって被記録材から剥離するに際して生ずる、特に定着状態低下液の使用量を少なくした場合に生ずる剥離部材へ被記録材が加熱接着する問題は、以下に述べるように被記録材上の被膜による粘着性が大きく影響することを見出し、本発明に到達することができた。
従来、被記録材上の被膜による粘着性が問題にならなかったのは、定着状態低下液の使用量が多く、画像形成物質除去の際の剥離部材との密接下でも定着状態低下液が蒸発することなく存在し、その存在が被記録材と剥離部材との接着を防いでいた。
しかし、定着状態低下液の使用量を少なくした場合、画像形成物質除去の際の剥離部材との密接下で定着状態低下液が蒸発し、被記録材上の被膜と剥離部材が直接的に加熱接触されることにより、熱により軟化した被膜が剥離部材に接着してしまうこと、更に加えて、剥離部材から被記録材を剥離するのは、加熱したニップを通過後に剥離部材の温度が下がってからであることが被記録材と剥離部材との接着の問題を大きくすること、すなわち、被膜が熱により軟化しただけであれば問題を起こすほどに接着力が強くなかったのであるが、熱により軟化した後に密着した状態で剥離部材の温度が低下するために被膜が再び硬化し、この際に接着力を大きくしてしまっていること、このような状態においても、定着状態低下液が存在していれば、その接着力が減じられるのであるが、少ない使用量の場合には定着状態低下液が蒸発し、定着状態低下の効果が得られず、被記録材と剥離部材との接着を招いていること、さらには、再生処理を繰り返す剥離部材表面には、そこで再生処理を行なった被記録材表面の成分が付着、蓄積していること、すなわち、被記録材表面と剥離部材表面が同じ物質、すなわち被記録材表面に存在する物質どうしになり、これが接着現象の一助となっていると言うことを本発明者らは見出し、これら各知見に基づいて本発明者らは前記再生方法に必要な要件を絞り込んで問題の生じない被記録材の検討を続けた結果、本発明を完成させることができた。
【0006】
通常、被膜の形成に一般的に使用されるのは各種の高分子物質であり、この各種高分子の軟化点等の熱的特性は公知であり、これらが前記再生方法に必要な要件の目安として使用できることは否定できない。しかし、上述のように問題としている剥離部材への接着現象は一度加熱の後、冷却した段階での接着力であるため、軟化点等のような単純な熱的特定では前記課題を解決することができなかった。
そこで、本発明者らは、(1)最も接着性が高まる定着状態低下液を使用しない状況を想定して被記録材のみを使用する、(2)被記録材表面に存在する物質が剥離部材表面にも蓄積し接着を強める傾向にあることから、被記録材の被膜面どうしを密接させる、(3)この再生方法に使用される一般的な剥離部材の温度と圧力で加熱し、加熱後、冷却した状態で被膜面の引き剥がしに要する力の測定を行ない検討し、その結果得られる接着力、すなわち引き剥がしに要する力が25g/25mm以下、望ましくは15g/25mm以下であるような被記録材は、定着状態低下液の使用量が1グラム以下あるいは全く使用しない場合においても剥離部材に接着し、分離不良による搬送異常および/または分離不良によるそれ自身の損傷がないことを見いだし本発明を完成させることが出来た。
【0007】
すなわち、本発明は、基材と前記基材上に形成された被膜とを有する被記録材の該被膜表面に形成された熱溶融性または熱可塑性の画像形成物質よりなる画像を、剥離部材と加熱接触させることにより剥離除去する方法において、前記被記録材として、該被記録材の被膜面どうしを密着させ、2kg/平方センチメートルの圧力をかけた状態で105℃、5秒間加熱圧着させた後、室温まで冷却したときに該被膜どうしの引き剥がしに要する力が25g/25mm以下となるのものを用い、かつ前記加熱接触の前に前記被記録材の画像形成面にA4サイズ当たり1g以下の定着状態低下液を付与することを特徴とする画像剥離方法に関する。
【0008】
加熱接着は、例えば、(株)東洋精機製作所の熱傾斜試験機を本発明の加熱圧着条件に合わせて設定し、被記録材の被膜面どうしを密接させた状態でプレスして行うことができる。また、引き剥がしに要する力は、上記(株)東洋精機製作所の熱傾斜試験機を用いた場合は加熱接着部を横向きに(幅方向に25mmの長手方向が来るように)し、またその他の方法を用いて加熱圧着を行なった場合は、加熱圧着後のサンプルを幅25mmになるように切断し、その一部を手などを用いて剥離させ、これらを引張り試験機にチャッキングして引張り試験を行ない、その際に測定された値の平均値をもって引き剥がしに要する力とした。
【0009】
【発明の実施の形態】
実施の形態1
被記録材
前記のような該被記録材の被膜面どうしを密着させ、2kg/平方センチメートルの圧力を掛けた状態で105℃、5秒間加熱接着させたとき、この被膜の引き剥がしに要する力が25g/25mm以下であるような特性を有する被記録材を得るためには、例えば、シリコン油などの離型剤を被膜中および/またはその表面に付与する方法、シリカなどの填料を加えて被膜と被記録材との接触面積を落とす方法、セルロース系のエチルセルロースやメチルセルロース等や蛋白質系のゼラチンなどの軟化点の高い高分子物質を単独、あるいは低いものと混合して使用する方法等が挙げられるが、被記録材の画像形成物質を保持する最表面が架橋剤を含む水溶性高分子物質(水溶性バインダー)で形成されていることが好ましい(請求項2)。この場合は、架橋剤の効果により耐熱性が向上するためと考えられる接着力の低下が見られ、目安としての軟化点の低い水溶性バインダーを使用することもできるようになり、被膜に使用する高分子物質の選択範囲を広げることができる効果がある。
ここで使用できる水溶性バインダーは、従来公知の水溶性高分子及び/または水性高分子エマルジョンから適宜選択される。その具体例としては、水溶性高分子として、例えば、ポリビニルアルコール、デンプン及びその誘導体、メトキシセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、エチルセルロースなどのセルロース誘導体、ポリアクリル酸ソーダ、ポリビニルピロリドン、アクリルアミド/アクリル酸エステル共重合体、アクリルアミド/アクリル酸エステル/メタクリル酸三元共重合体、スチレン/無水マレイン酸共重合体アルカリ塩、ポリアクリルアミド、アルギン酸ソーダ、ゼラチン、カゼインなどが挙げられる。また、水性高分子エマルジョンとしては、スチレン/ブタジエン共重合体、スチレン/ブタジエン/アクリル系共重合体などのラテックスや酢酸ビニル樹脂、酢酸ビニル/アクリル酸共重合体、スチレン/アクリル酸エステル共重合体、アクリル酸エステル樹脂、ポリウレタン樹脂などのエマルジョンなどが挙げられる。
架橋剤としては、エポキシ架橋剤、イソシアネート架橋剤、放射線架橋剤などが挙げられる。その中でもポリビニルアルコールをポリアミドエピクロルヒドリンで架橋させたものが材料の取り扱いやすさからも望ましい。
【0010】
本発明の被記録材が基材を使用するものである場合には、該基材としては樹脂または紙、あるいはそれらの複合材または積層材等が挙げられる(請求項3)。
樹脂はシート状フィルムとして使用することが好ましく、熱可塑性樹脂、熱硬化性樹脂などが使用可能である。紙としては、少なくとも一部がセルロース繊維を主成分とした紙質層で構成されているものが使用でき、一般的には上質紙をベースとしたものが使用される。複合材とは、セルロース繊維をその構成材の一部として使用した樹脂フィルムや樹脂繊維とセルロース繊維を混抄したり、不織布として使用するもの等が挙げられる。また、積層材とはシート状の樹脂と紙を張り合わせたものを指し、例えば紙の上に任意の樹脂をエクストルージョン加工により塗設したり、予めシート状に加工された樹脂フィルム上に接着剤を塗布し、これに別の紙を貼り合わせたりしたものが挙げられる。
【0011】
本発明の被記録材としては、20℃×65%RHで調湿した際に、被記録材の表裏の表面電気抵抗値が1×1013Ω以下であるものが好ましい。
これは、最表層に使用している被膜の影響で被記録材の電気抵抗値が高くなってしまうことが観察された。この電気抵抗値が高くなってしまった状況で電子写真用複写機に使用すると、帯電によるシート間の密着による給紙不良や高すぎる電気抵抗の影響で定着前のトナーが散るために生じる画像異常(「ベタチリ」などと呼ばれることが多い)などが生じてしまうことが分かった。この現象は抵抗値を1×1013Ω、望ましくは1×1012Ωまで低下させることで改善することが分かった。この調整は市販の各種の導電剤を使用することで可能であり、導電剤を基材、塗工層、中間層に含ませたり、基材表面や塗工層表面などに塗工してもよい。
【0012】
実施の形態2
被記録材の再生方法
画像再生方法処理する画像形成物質(PPCにおいてはトナー画像)が保持されている被記録材からその画像形成物質を剥離するために、画像面に定着状態低下液(界面活性剤を含む水溶液)を供給、保持させた状態、あるいは全く定着状態低下液を添加しない状態で、剥離部材と加熱接触させ、画像形成物質を被記録材から剥離し剥離部材へと転移させる。定着状態低下液を使用するタイプでは被記録材の画像面への定着状態低下液の供給、保持は浸布、浸漬、吹きつけ等による含浸が採用できる。この画像形成物質の剥離には、図1に示すような剥離試験装置によるのが好ましい。ただし、定着状態低下液の量が少なく、被記録材の乾燥を行なう必要がない場合は仕上部を省くことができる。また、定着状態低下液を使用しない場合は給液部を使用しない、あるいは省くことができる。画像形成物質が剥離された被記録材は繰り返し複写機やプリンタでの画像形成が可能である。
【0013】
画像剥離部材を構成する材料としては、高分子材料、特に画像を構成する物質と似ているSP値を有する有機高分子材料、表面活性エネルギーの高い金属材料、その蒸着材料、セラミック材料等の無機材料等が好ましい。剥離部材を形成する高分子材料としては、前記のような水溶性樹脂およびトナー成分樹脂あるいは、にかわ、ゼラチン、アルブミン、カゼインなどのタンパク質系樹脂、でんぷん系、セルロース繊維系、複合多糖類系(アラビアゴム、トラガントゴムなど)の炭水化物系樹脂、酢酸ビニルの重合体及び共重合体、アクリル系、エチレン共重合物、ポリアミド、ポリエステル、ポリウレタンなどの熱可塑性樹脂、ポリクロロプレン系、ニトリルゴム系、SBR系、天然ゴム系のゴム系樹脂等のような接着剤の成分樹脂が挙げられる。但し、樹脂の種類は、画像に対して接着性を有するものであればよく、また、水溶性のものあるいは非水溶性のものであってもよい。
【0014】
前記の画像剥離部材を形成する樹脂は、他の支持体、例えばローラ、シート、ベルトあるいはテープ等の表面に担持させて用いることができる。画像形成物質の剥離手段の例としては、セロハンテープ、クラフト紙テープ、ポリ塩化ビニールテープ、アセテートテープ、フィラメントテープの支持体上にゴム系、アクリル系などの感圧接着剤層を設けた接着テープ等が挙げられる。また、前記樹脂自体でローラ、シート、ベルトあるいはテープ等の形状を有する剥離手段を形成して用いることもできる。さらに、前記支持体は、その表面がポーラスな、あるいは凹凸を有する材料で形成されるか、あるいは該支持体表面を凹凸加工したものが好ましい。なお、ここにいう「剥離手段」とは加熱又は加圧接触時、画像と接着する性質のある剥離部材と画像とを接触させ、画像を剥離部材に転写させることにより、画像を被記録材から剥離する手段を言う。
【0015】
定着状態低下液に使用する界面活性剤としては、非常に多くの種類があり、一般的には脂肪酸誘導体硫酸エステル、スルホン酸型、リン酸エステル型などの陰イオン(アニオン)界面活性剤、四級アンモニウム塩、複素環アミン、アミン誘導体などの陽イオン(カチオン)界面活性剤、両性界面活性剤、非イオン界面活性剤、などが挙げられ、これらいずれの種類の界面活性剤でも用い得るが、再生した紙の表面抵抗を変化させにくいという観点から、ノニオン系界面活性剤の使用が望ましい。また、シリコーン系界面活性剤、特に疎水性基の少なくとも一部がメチルシロキサンからなり、また、親水性基の少なくとも一部がポリアルキレンオキシドおよび/またはカルボン酸基であるシリコーン系界面活性剤は、定着時に付着するシリコーンオイルによる再生劣化を改善し、白色度を高め、再複写および再印字を良好にすることができ、さらに好ましい。前記界面活性剤は、前記のように水を含む液体として使用されるが、画像を形成する前の被記録材自体に含有させても良く、この場合には、定着状態低下液として水を用いることができる。
【0016】
【実施例】
以下、実施例により本発明を説明するが、これらは本発明の一態様にすぎず、本発明はこれら実施例によっては限定されない。
【0017】
実施例1
エチルセルロース 10部
(固形分100%、ハーキュレス社製N−22)
エタノール 90部
上記配合からなる混合物を十分に撹拌して塗工層形成液を調整し、これを付着量が2g/m2になるように市販の電子写真用転写紙(坪量70g/m2)の表面にワイヤーバーを用いて塗布・乾燥させ、実施例1の被記録材を得た。この被記録材の被膜面どうしを密着させ2kg/平方センチメートル圧、105℃×5秒間加熱により接着後、室温まで冷却後の接着力は20g/25mmであった。この被記録材をリコー製電子写真複写機(Spirio7000)で画像コピーした後、図1の剥離装置を用いて画像の剥離を行なった。なお、この際には、定着状態低下液は三井サイテック社製エアロゾルOTの0.5%界面活性剤水溶液を付着量が0.5g/m2になるように被記録材の画像コピー面に付着させ、剥離温度は120℃、剥離速度は30mm/秒で画像剥離を行なったとき、剥離部材である剥離ベルトへの被記録材の加熱接着は見られず、剥離ベルトから被記録材の分離は問題なく行なわれた。
また、同じ画像コピー済み被記録材を、定着状態低下液を付着させない以外の剥離条件を同じにして画像剥離を行なっても、被記録材の加熱接着は見られず、剥離ベルトから被記録材の分離は問題なく行なわれた。
【0018】
実施例2
ポリビニルアルコール水溶液 60部
(固形分10%、クラレ社製PVA117)
無機顔料 30部
水 10部
上記配合からなる混合物を使用した以外は実施例1に同様に実施例2の被記録材を得た。この被記録材の接着力を実施例1と同様に測定した結果、23g/25mmであった。また、実施例1と同様に定着状態低下液の付着量が0.5g/m2と、定着状態低下液を使用しない2つの条件でそれぞれ被記録材の再生を行なった結果、両方の定着状態低下液の付着量条件の場合に被記録材の剥離ベルトへの僅かながらの加熱接着が見られたが、剥離ベルトからの被記録材の分離には問題なく、被記録材の損傷も見られなかった。
【0019】
実施例3
ポリビニルアルコール 70部
(固形分10%、クラレ社製PVA117)
ポリアミドアミンエピクロルヒドリン 20部
(固形分12.5%、日本PMC社製WS570)
水 10部
上記配合からなる混合物を使用した以外は実施例1と同様に実施例3の被記録材を得た。この被記録材の接着力を実施例1と同様に測定した結果、接着力は1g/25mm以下であった。また、実施例1と同様に定着状態低下液の付着量が0.5g/m2と、定着状態低下液を使用しない2つの条件でそれぞれが像保持支持体の再生を行なった結果、いずれの定着状態低下液の付着両条件の場合においても被記録材の剥離ベルトへの加熱接着は全く見られず、剥離ベルトから被記録材の分離には何らの問題も生じなかった。
【0020】
比較例1
ポリビニルアルコール水溶液 70部
(固形分10%、クラレ社製PVA318)
水 30部
上記配合からなる混合物を使用した以外は実施例1と同様に比較例1の被記録材を得た。この被記録材の接着力を実施例1と同様に測定した結果、接着力は95g/25mmであった。また、実施例1と同様に定着状態低下液の付着量が0.5g/m2と、定着状態低下液を使用しない2つの条件でそれぞれ被記録材の再生を行なった結果、何れの定着状態低下液の付着量条件の場合においても被記録材が剥離ベルトへ加熱接着されてしまい、剥離ベルトから被記録材が分離しなかった。
【0021】
比較例2
ポリビニルアルコール水溶液 14部
(固形分10%、クラレ社製PVA318)
酸化デンプン水溶液 56部
(固形分10%、日本食品化工社製MS♯3800)
水 30部
上記配合からなる混合物を使用した以外は実施例1と同様に比較例2の被記録材を得た。この被記録材の接着力を実施例1と同様に測定した結果、接着力は110g/25mmであった。また、実施例1と同様に定着状態低下液の付着量が0.5g/m2と、定着状態低下液を使用しない2つの条件でそれぞれ被記録材の再生を行なった結果、何れの定着状態低下液の付着量条件の場合においても被記録材が剥離ベルトへ加熱接着されてしまい、剥離ベルトから被記録材が分離しなかった。
【0022】
【発明の効果】
1.請求項1
定着状態低下液の使用がA4サイズ当たり1g以下の使用においても被記録材の剥離部材への顕著な粘着現象がなく、無理なく剥離部材から被記録材を剥離でき、搬送トラブルや被記録材の分離における損傷もない効果を奏する被記録材再生方法が提供される。
2.請求項2
架橋剤を使用することにより、一般的で使用しやすい水溶性高分子を使用しても、請求項1の要件を満足し、被記録材の剥離部材への顕著な粘着現象がなく、無理なく剥離部材から被記録材を剥離でき、搬送トラブルや被記録材の分離における損傷もない効果を有する被記録材再生方法が提供される。
3.請求項3
被膜の形成により被記録材の支持体を特に選ばない効果を有する被記録材再生方法が提供される。
【図面の簡単な説明】
【図1】画像剥離評価で採用した剥離試験装置を説明した図である。
【符号の説明】
1 剥離部材(剥離ベルト)
2 定着状態低下液
P 画像形成物質(トナー画像を有する紙)
R1 対向ローラ
R2 塗布ローラ
R3 画像剥離ローラ[0001]
BACKGROUND OF THE INVENTION
In the present invention, a recording material having a thin film that forms an image made of a heat-meltable or thermoplastic image-forming substance on the surface is heated and brought into contact with a drum or belt-like peeling member to peel off and remove the image. It relates to an image stripping method of the recording material for reproducing the recorded material.
[0002]
[Prior art]
With recent OA, printer paper and copy paper have been used in large quantities. As a result, the problem of deteriorating the global environment due to the felling of forests has been caused. Conventionally, there has been only a method for solving this problem by removing the ink etc. on the paper once used, crushing and re-making it, and recycling it to paper called used paper. However, recently, as disclosed in Japanese Patent No. 2764066, a method for reproducing a recording material has been developed that can remove a character image on paper once used by cleaning and reuse it for copying or printing.
In this method, a recording material having an image formed of a heat-meltable or thermoplastic image-forming substance on the surface is fixed in order to reduce the fixing state between the image-forming substance and the recording material. In this method, after the lowering liquid is attached, the heated release member is brought into close contact with the image forming substance, and the heat-softened image forming substance is peeled off from the recording material to reproduce the recording material.
In this method, the recording material brought into close contact with the peeling member must be peeled off from the peeling member for reproduction after the image forming substance is peeled off by the peeling member. In general, this separation uses a blade installed in contact with the peeling member, or a method of separating the recording material by curvature by making the peeling member into a thin belt and bending it abruptly. Has been.
[0003]
At the time when this method was developed, there was a large amount of fixing state-reducing liquid attached, and general high-quality paper was often used, so there was no particular problem in the separation by the above method. However, after the development of this reproduction method, improvement of the reproduction method corresponding to this has progressed, and one of the goals is to reduce the amount of fixing state lowering liquid used to reduce the fixing state of the image forming substance to the recording material. Became. This is because, in order to reproduce the recording material, the fixing state reducing liquid once applied must be completely dried, and the energy required for drying becomes smaller as the amount of liquid used is smaller. For example, Japanese Patent Laid-Open No. 10-171319 proposes to reduce the amount of fixing state reducing liquid used from 4 grams per conventional A4 size to 1 gram, and Japanese Patent Laid-Open No. 10-278380 is reduced to 0.05 to 0.6 grams. It is clear that the goal is to zero the amount of use of the fixing state lowering liquid in the end. However, when the usage amount of the fixing state reducing liquid is reduced in this way, the effect of loosening the fixing of the image forming substance and the recording material by the fixing state reducing liquid inherent in this reproduction method has to be weakened. In addition, when general high quality paper is used, the removal of the image forming substance is incomplete, and the recording material used in these reproduction methods has started to be required to have a characteristic that can easily remove the image forming substance. For example, Japanese Patent Laid-Open No. 11-143110 proposes a recording material in which a material whose surface energy changes with temperature is coated on the surface, and the surface of the recording material is coated with some kind of film that can easily remove the image forming material. Propose to cover.
However, when the usage amount of the fixing state lowering liquid is reduced, a new problem has arisen. In other words, conventional high-quality paper has been used, but the coating applied to facilitate removal of the image-forming substance is heated and adhered to the peeling member that is heated and contacted during reproduction of the recording material. As a result, the recording material cannot be peeled off from the peeling member.
[0004]
[Problems to be solved by the invention]
The present invention relates to a fixing state-reducing liquid for reducing a fixing state between an image forming substance and a recording material by using a recording material having a film that forms an image made of a heat-meltable or thermoplastic image-forming substance on the surface. Is attached to the image forming substance, and the heated release member is brought into intimate contact, and the heat-softened image forming substance is peeled off from the recording material, and the recording material is regenerated and used in the image peeling method. An object of the present invention is to provide an image peeling method that does not cause jamming due to poor separation as a recording material to be recorded, and is less likely to be damaged by contact with a separation claw during separation.
[0005]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventors have used a fixing state-reducing liquid, particularly when a film made of a heat-meltable or thermoplastic image-forming substance is peeled off from a recording material by a peeling member. The problem that the recording material heat-adheres to the peeling member that occurs when the amount is reduced is found to be greatly affected by the adhesiveness of the coating on the recording material as described below, and the present invention can be reached. It was.
Conventionally, the adhesiveness due to the coating on the recording material has not been a problem because the amount of fixing state lowering liquid used is large, and the fixing state lowering liquid evaporates even in close contact with the peeling member when removing the image forming substance. The presence of the recording material prevented the adhesion between the recording material and the peeling member.
However, when the amount of fixing state lowering liquid used is reduced, the fixing state lowering liquid evaporates in close contact with the peeling member when removing the image forming substance, and the coating on the recording material and the peeling member are directly heated. The film softened by heat adheres to the peeling member due to contact, and in addition, the recording material is peeled from the peeling member because the temperature of the peeling member decreases after passing through the heated nip. This increases the problem of adhesion between the recording material and the peeling member, that is, the adhesive force was not strong enough to cause a problem if the film was only softened by heat. Since the temperature of the peeling member is lowered after being softened and the temperature of the peeling member is lowered, the coating is cured again, and the adhesive force is increased at this time. Even in such a state, there is a fixing state lowering liquid. If The adhesive force is reduced, but in the case of a small amount of use, the fixing state lowering liquid evaporates, the effect of lowering the fixing state cannot be obtained, and the recording material and the peeling member are bonded. Furthermore, components on the surface of the recording material that has undergone the reproduction process adhere to and accumulate on the surface of the peeling member that repeats the reproduction process, that is, the surface of the recording material and the surface of the peeling member are the same substance, The present inventors have found that the substances present on the surface of the recording material are mutually linked, and this helps the adhesion phenomenon, and based on these findings, the present inventors have established the requirements necessary for the reproducing method. As a result of continuing examination of recording materials that are narrowed down and cause no problems, the present invention has been completed.
[0006]
Usually, various polymer substances are generally used for the formation of a coating, and the thermal properties such as softening points of these various polymers are known, and these are guidelines for the requirements necessary for the regeneration method. It cannot be denied that it can be used as. However, since the adhesion phenomenon to the peeling member, which is a problem as described above, is an adhesive force at the stage of cooling after heating once, the above-mentioned problem can be solved by simple thermal identification such as a softening point. I could not.
Therefore, the present inventors (1) use only the recording material assuming that the fixing state lowering liquid with the highest adhesiveness is not used, and (2) the substance existing on the surface of the recording material is a peeling member. Since it tends to accumulate on the surface and strengthen the adhesion, the coated surfaces of the recording material are brought into close contact with each other. (3) Heating is performed at the temperature and pressure of a general peeling member used in this reproducing method, and after heating Then, the force required for peeling off the coated surface in the cooled state is measured and examined, and the resulting adhesive force, that is, the force required for peeling, is 25 g / 25 mm or less, preferably 15 g / 25 mm or less. The recording material adheres to the peeling member even when the amount of the fixing state lowering liquid used is 1 g or less or is not used at all, and is free from abnormal conveyance due to poor separation and / or damage to itself due to poor separation. We were able to complete the present invention found.
[0007]
That is, the present invention provides an image formed of a heat-meltable or thermoplastic image-forming substance formed on the surface of a recording material having a base material and a film formed on the base material, as a peeling member. a method of separating and removing by heating contact, said as a recording medium, are brought into close contact with the film surface each other of該被recording material, 2 kg / cm 105 ° C. while applying a pressure of, after thermocompression bonding for 5 seconds, Fixing with 1 g or less per A4 size on the image forming surface of the recording material prior to the heating contact is performed using a material that requires a force of 25 g / 25 mm or less when the coating film is peeled off when cooled to room temperature. The present invention relates to an image peeling method characterized by applying a state reducing liquid .
[0008]
Heat bonding can be performed, for example, by setting a thermal inclination tester of Toyo Seiki Seisakusho Co., Ltd. according to the thermocompression bonding conditions of the present invention and pressing the coated surfaces of the recording materials in close contact with each other. . In addition, the force required for peeling is such that when the above-mentioned Toyo Seiki Seisakusho thermal inclination tester is used, the heat-bonded portion is turned sideways (so that the longitudinal direction of 25 mm comes in the width direction), and other When thermocompression bonding is performed using this method, the sample after thermocompression bonding is cut to a width of 25 mm, a part of the sample is peeled off by hand, and these are chucked by a tensile tester. The test was performed, and the average value of the values measured at that time was defined as the force required for peeling.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Recording material When the coating surfaces of the recording material as described above are brought into close contact with each other and heated and bonded at 105 ° C. for 5 seconds under a pressure of 2 kg / square centimeter, the force required for peeling off the coating is 25 g. In order to obtain a recording material having characteristics such as / 25 mm or less, for example, a method of applying a release agent such as silicone oil to and / or the surface of the coating, a filler such as silica and the like, Examples thereof include a method of reducing the contact area with the recording material, a method of using a high-softening polymer material such as cellulose-based ethylcellulose or methylcellulose or a protein-based gelatin alone or mixed with a low one. The outermost surface of the recording material holding the image forming substance is preferably formed of a water-soluble polymer substance (water-soluble binder) containing a crosslinking agent. 2 ). In this case, the adhesive strength is considered to decrease due to the heat resistance improved by the effect of the crosslinking agent, and a water-soluble binder having a low softening point can be used as a guide, which is used for coating. There is an effect that the selection range of the polymer substance can be expanded.
The water-soluble binder that can be used here is appropriately selected from conventionally known water-soluble polymers and / or aqueous polymer emulsions. Specific examples thereof include water-soluble polymers such as polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylic. Examples thereof include acid ester copolymers, acrylamide / acrylic ester / methacrylic acid terpolymers, styrene / maleic anhydride copolymer alkali salts, polyacrylamide, sodium alginate, gelatin, and casein. Examples of aqueous polymer emulsions include styrene / butadiene copolymers, latexes such as styrene / butadiene / acrylic copolymers, vinyl acetate resins, vinyl acetate / acrylic acid copolymers, and styrene / acrylic acid ester copolymers. And emulsions such as acrylic ester resins and polyurethane resins.
Examples of the crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, and a radiation crosslinking agent. Among them, polyvinyl alcohol crosslinked with polyamide epichlorohydrin is desirable from the viewpoint of easy handling of the material.
[0010]
When the recording material of the present invention is to use substrate, such as a resin or paper, or their composite or laminate can be cited as a base material (claim 3).
The resin is preferably used as a sheet-like film, and a thermoplastic resin, a thermosetting resin, or the like can be used. As the paper, at least a part of which is composed of a paper layer mainly composed of cellulose fibers can be used, and generally a paper based on fine paper is used. Examples of the composite material include a resin film using cellulose fiber as a part of its constituent material, a mixture of resin fiber and cellulose fiber, and a material used as a nonwoven fabric. The laminated material refers to a laminate of sheet-shaped resin and paper. For example, an arbitrary resin is coated on paper by extrusion processing, or an adhesive is applied to a resin film that has been processed into a sheet shape in advance. The thing which apply | coated and bonded another paper to this is mentioned.
[0011]
The recording material of the present invention, when the humidified at 20 ℃ × 65% RH, one surface electrical resistance of the front and back of the recording material is not more than 1 × 10 13 Ω is preferred.
It was observed that the electrical resistance value of the recording material was increased due to the effect of the coating used for the outermost layer. If this electrical resistance value is high and used in an electrophotographic copying machine, an image abnormality caused by toner being scattered before fixing due to poor feeding due to adhesion between sheets due to charging or an excessively high electrical resistance. (Often referred to as “sticky” etc.). It has been found that this phenomenon can be improved by reducing the resistance value to 1 × 10 13 Ω, preferably 1 × 10 12 Ω. This adjustment is possible by using various commercially available conductive agents. Even if the conductive agent is included in the substrate, coating layer, intermediate layer, or coated on the surface of the substrate or coating layer, etc. Good.
[0012]
Reproduction method of recording material Image reproduction method In order to peel off the image forming material from the recording material on which the image forming material (toner image in PPC) to be processed is held, a fixing state reducing liquid (surfactant activity) In a state where an aqueous solution containing an agent) is supplied and held, or in a state where no fixing state lowering liquid is added, the image forming substance is peeled off from the recording material and transferred to the peeling member. In the type using the fixing state reducing liquid, impregnation by dipping, dipping, spraying or the like can be used for supplying and holding the fixing state decreasing liquid to the image surface of the recording material. For peeling the image forming substance, it is preferable to use a peeling test apparatus as shown in FIG. However, when the amount of the fixing state lowering liquid is small and it is not necessary to dry the recording material, the finish can be omitted. Further, when the fixing state lowering liquid is not used, the liquid supply unit is not used or can be omitted. The recording material from which the image forming substance has been peeled can be repeatedly formed with a copying machine or a printer.
[0013]
The material constituting the image peeling member is an inorganic material such as a polymer material, particularly an organic polymer material having an SP value similar to the material constituting the image, a metal material having a high surface active energy, a vapor deposition material thereof, a ceramic material, etc. Materials etc. are preferred. Examples of the polymer material that forms the release member include water-soluble resins and toner component resins as described above, or protein resins such as glue, gelatin, albumin, and casein, starch-based materials, cellulose fiber-based materials, and complex polysaccharide-based materials (Arabic Rubber, tragacanth rubber, etc.) carbohydrate resins, vinyl acetate polymers and copolymers, acrylic resins, ethylene copolymers, polyamides, polyesters, polyurethanes, and other thermoplastic resins, polychloroprene, nitrile rubber, SBR, Examples of the component resin of the adhesive include natural rubber-based rubber resins. However, the type of resin is not particularly limited as long as it has adhesiveness to the image, and may be water-soluble or water-insoluble.
[0014]
The resin forming the image peeling member can be used by being carried on the surface of another support, for example, a roller, a sheet, a belt or a tape. Examples of image forming substance peeling means include cellophane tape, kraft paper tape, polyvinyl chloride tape, acetate tape, adhesive tape with a pressure sensitive adhesive layer such as rubber or acrylic on the support of filament tape, etc. Is mentioned. The resin itself can also be used by forming a peeling means having a shape such as a roller, a sheet, a belt or a tape. Further, it is preferable that the support is formed of a material having a porous or uneven surface, or the support surface is processed to have an uneven surface. The “peeling means” as used herein refers to a peeling member having a property of adhering to an image when heated or pressurized, and the image is transferred to the peeling member by contacting the image with the peeling member. Means to peel.
[0015]
There are a great many types of surfactants used in the fixing state reducing solution, and generally, anionic (anionic) surfactants such as fatty acid derivative sulfate ester, sulfonate type, phosphate ester type, etc. Cationic surfactants such as quaternary ammonium salts, heterocyclic amines, and amine derivatives, amphoteric surfactants, nonionic surfactants, and the like, and any of these types of surfactants can be used. From the viewpoint of hardly changing the surface resistance of the recycled paper, it is desirable to use a nonionic surfactant. Further, a silicone-based surfactant, particularly a silicone-based surfactant in which at least a part of the hydrophobic group is made of methylsiloxane and at least a part of the hydrophilic group is a polyalkylene oxide and / or a carboxylic acid group, It is more preferable because it can improve regeneration deterioration due to silicone oil adhering to fixing, increase whiteness, and improve re-copying and re-printing. The surfactant is used as a liquid containing water as described above. However, the surfactant may be contained in the recording material itself before forming an image. In this case, water is used as the fixing state reducing liquid. be able to.
[0016]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, these are only one aspect | mode of this invention and this invention is not limited by these Examples.
[0017]
Example 1
10 parts of ethyl cellulose (100% solid content, N-22 manufactured by Hercules)
Mixture consisting of ethanol and 90 parts The above ingredients is stirred thoroughly prepare a coating layer forming solution, which coating weight of a commercially available electrophotographic transfer paper to be 2 g / m 2 (basis weight 70 g / m 2 The recording material of Example 1 was obtained by applying and drying on the surface of (1) using a wire bar. The film surfaces of the recording material were brought into close contact with each other and bonded by heating at 105 ° C. for 5 seconds at a pressure of 2 kg / square centimeter, and the adhesive force after cooling to room temperature was 20 g / 25 mm. An image of this recording material was copied using a Ricoh electrophotographic copying machine (Spirior 7000), and the image was peeled off using the peeling device shown in FIG. At this time, the fixing state lowering liquid adheres to the image copy surface of the recording material with a 0.5% surfactant aqueous solution of Aerosol OT manufactured by Mitsui Cytec Co., Ltd. so that the adhesion amount is 0.5 g / m 2. When the image peeling was performed at a peeling temperature of 120 ° C. and a peeling speed of 30 mm / second, no thermal adhesion of the recording material to the peeling belt as a peeling member was observed, and the separation of the recording material from the peeling belt was not It was done without problems.
In addition, even when the same image-copied recording material was subjected to image peeling under the same peeling conditions except that the fixing state lowering liquid was not attached, no heat adhesion of the recording material was observed, and the recording material was removed from the peeling belt. Separation was done without problems.
[0018]
Example 2
Polyvinyl alcohol aqueous solution 60 parts (solid content 10%, Kuraray PVA117)
Inorganic pigment 30 parts Water 10 parts A recording material of Example 2 was obtained in the same manner as in Example 1 except that the mixture having the above composition was used. The adhesive strength of this recording material was measured in the same manner as in Example 1. As a result, it was 23 g / 25 mm. Further, as in Example 1, the adhesion amount of the fixing state lowering liquid was 0.5 g / m 2, and the recording material was reproduced under two conditions without using the fixing state lowering liquid. In the case of the amount of dropping liquid attached, a slight amount of heat adhesion of the recording material to the peeling belt was observed, but there was no problem in separating the recording material from the peeling belt, and the recording material was also damaged. There wasn't.
[0019]
Example 3
70 parts of polyvinyl alcohol (solid content 10%, Kuraray PVA117)
Polyamide amine epichlorohydrin 20 parts (solid content 12.5%, WS570 manufactured by Japan PMC)
10 parts of water A recording material of Example 3 was obtained in the same manner as in Example 1 except that the mixture having the above composition was used. As a result of measuring the adhesive force of this recording material in the same manner as in Example 1, the adhesive force was 1 g / 25 mm or less. Similarly to Example 1, the adhesion amount of the fixing state reducing solution was 0.5 g / m 2, and each of the image holding supports was regenerated under two conditions without using the fixing state reducing solution. In both cases where the fixing state lowering liquid was adhered, no heat-bonding of the recording material to the peeling belt was observed, and no problem occurred in separating the recording material from the peeling belt.
[0020]
Comparative Example 1
70 parts of polyvinyl alcohol aqueous solution (solid content 10%, Kuraray PVA318)
30 parts of water A recording material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the mixture having the above composition was used. The adhesive strength of this recording material was measured in the same manner as in Example 1. As a result, the adhesive strength was 95 g / 25 mm. Further, as in Example 1, the amount of adhesion of the fixing state lowering liquid was 0.5 g / m 2, and the recording material was reproduced under two conditions without using the fixing state lowering liquid. Even in the case of the deposition amount condition of the lowering liquid, the recording material was heated and adhered to the peeling belt, and the recording material was not separated from the peeling belt.
[0021]
Comparative Example 2
Polyvinyl alcohol aqueous solution 14 parts (solid content 10%, Kuraray PVA318)
56 parts of oxidized starch aqueous solution (solid content 10%, MS # 3800 manufactured by Nippon Shokuhin Kako Co., Ltd.)
30 parts of water A recording material of Comparative Example 2 was obtained in the same manner as in Example 1 except that the mixture having the above composition was used. The adhesive strength of this recording material was measured in the same manner as in Example 1. As a result, the adhesive strength was 110 g / 25 mm. Further, as in Example 1, the amount of adhesion of the fixing state lowering liquid was 0.5 g / m 2, and the recording material was reproduced under two conditions without using the fixing state lowering liquid. Even in the case of the deposition amount condition of the lowering liquid, the recording material was heated and adhered to the peeling belt, and the recording material was not separated from the peeling belt.
[0022]
【The invention's effect】
1.
Even when the fixing state lowering liquid is used at 1 g or less per A4 size, there is no remarkable sticking phenomenon of the recording material to the peeling member, and the recording material can be peeled off from the peeling member without any trouble. There is provided a recording material reproducing method which exhibits an effect without damage in separation.
2.
By using a cross-linking agent, even if a general and easy-to-use water-soluble polymer is used, the requirement of
3. Claim 3
There is provided a recording material reproducing method having an effect of not particularly selecting a support for a recording material by forming a film.
[Brief description of the drawings]
FIG. 1 is a diagram illustrating a peeling test apparatus employed in image peeling evaluation.
[Explanation of symbols]
1 Peeling member (peeling belt)
2 Fixing state lowering liquid P Image forming substance (paper having toner image)
R1 Opposing roller R2 Coating roller R3 Image peeling roller
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000009480A JP4309544B2 (en) | 2000-01-18 | 2000-01-18 | Image peeling method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000009480A JP4309544B2 (en) | 2000-01-18 | 2000-01-18 | Image peeling method |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2001201990A JP2001201990A (en) | 2001-07-27 |
JP4309544B2 true JP4309544B2 (en) | 2009-08-05 |
Family
ID=18537628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2000009480A Expired - Fee Related JP4309544B2 (en) | 2000-01-18 | 2000-01-18 | Image peeling method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4309544B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8354468B2 (en) | 2008-03-07 | 2013-01-15 | Jsr Corporation | Thermoplastic elastomer composition |
-
2000
- 2000-01-18 JP JP2000009480A patent/JP4309544B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8354468B2 (en) | 2008-03-07 | 2013-01-15 | Jsr Corporation | Thermoplastic elastomer composition |
Also Published As
Publication number | Publication date |
---|---|
JP2001201990A (en) | 2001-07-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3345472B2 (en) | Reproduction method of image holding support | |
JPH08152731A (en) | Picture support for recycling, production of the support and device therefor | |
JP3250879B2 (en) | Reproduction method of image support and reproduction apparatus used for the reproduction method | |
JP4309544B2 (en) | Image peeling method | |
JPH1074025A (en) | Copying paper | |
JP3973130B2 (en) | Reproducible recording material and method for reproducing the reproducible recording material | |
JP2001255687A (en) | Recording material and method of peeling and removing image from recording material | |
JP4067777B2 (en) | Recording material for image peeling and removal | |
JP3285262B2 (en) | Method for reproducing image support and apparatus used for the method | |
JPH11174715A (en) | Image holding base body and its regenerating method | |
JP4017496B2 (en) | Image forming substance removing method and removing apparatus, image forming method and image forming apparatus | |
JP2003066795A (en) | Image peeling method, image peeling device and material to be recorded | |
JP3315232B2 (en) | Image carrier, method of reproducing image carrier and apparatus therefor | |
JP2002278123A (en) | Recording material | |
JP3975571B2 (en) | Image recording body and method for reproducing image recording body using the same | |
JP2002268262A (en) | Material to be recorded and method for reproducing it | |
JPH11305615A (en) | Reproducing device and reproducing method for material to be recorded | |
JP3543013B2 (en) | Method for regenerating image holding support and image stripping solution used in the method | |
JP3308439B2 (en) | Apparatus for removing image forming substance from image carrier | |
JP3483945B2 (en) | Method for reproducing image support and image holding support | |
JPH08292687A (en) | Regenerating device for image carrier | |
JPH0736327A (en) | Image forming material removing device from image holding body by use of adhesive unstabilizing solution, and image holding body processing device | |
JPH09197926A (en) | Device for removing image forming material from image holding body | |
JP3418237B2 (en) | Method and apparatus for removing image forming substance from image carrier, and papermaking direction detecting apparatus | |
JPH11143109A (en) | Re-recordable paper sheet and its regenerating method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050222 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070315 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070320 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070508 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070703 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070831 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080916 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081014 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090428 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090508 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120515 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120515 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130515 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140515 Year of fee payment: 5 |
|
LAPS | Cancellation because of no payment of annual fees |