JP4127464B2 - Decolorization method for erasable images - Google Patents
Decolorization method for erasable images Download PDFInfo
- Publication number
- JP4127464B2 JP4127464B2 JP2001093627A JP2001093627A JP4127464B2 JP 4127464 B2 JP4127464 B2 JP 4127464B2 JP 2001093627 A JP2001093627 A JP 2001093627A JP 2001093627 A JP2001093627 A JP 2001093627A JP 4127464 B2 JP4127464 B2 JP 4127464B2
- Authority
- JP
- Japan
- Prior art keywords
- color
- image
- decoloring
- erasable
- developer
- 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
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Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Developing Agents For Electrophotography (AREA)
- Color Printing (AREA)
- Cleaning In Electrography (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は電子写真、熱転写記録、筆記具、印刷などの方法により画像形成媒体上に形成された、可消色性組成物を含む画像形成材料からなる可消色性画像の消色方法に関する。
【０００２】
【従来の技術】
近年、コンピューター、プリンター、複写機、ファクシミリなどの普及により、紙による情報の出力が増加している。紙への出力を削減すべく「情報の電子化によるペーパーレス化」が叫ばれるものの、視認性の良さ、高い携帯性、ページめくりによる情報検索の手軽さなどの特徴から、紙へのハードコピーの要望は絶えることがない。その結果、紙の原料となる天然資源の保護及びゴミ処理量の低減・二酸化炭素排出量の削減が解決すべき課題となるに至っている。従って、「紙の再生・再利用」は、天然資源の保護及びゴミ処理量の低減・二酸化炭素排出量の削減の各局面において、極めて今日的な課題である。
【０００３】
このような事情から、紙へ印刷・印字するための画像形成材料（各種印刷インキ、トナー、ジェットインクなど）を印刷・印字後に無色化する技術は、紙の再生・再利用を推進する上で極めて重要である。即ち、従来の紙の再生方法においては、回収紙を水で再解膠した後、いわゆる「脱墨工程」においてインク部分を浮遊分離する方法や漂白剤を用いて脱色する方法が用いられており、これらが、新規に製紙する場合に比べて工程経費を高くする要因となっている。
【０００４】
従って、発色状態の呈色性化合物を無色の消色状態へ変えることのできる可消色性着色剤を用いた画像形成材料によって印刷された紙は、従来のような手間の掛かる脱墨工程を経ることなしに、再利用或いは再生することが可能になると期待される。又、簡便且つ安全な操作によって可消色性着色剤を用いた画像形成材料を無色の消色状態にすることができれば、画像が形成された画像形成媒体（主に紙）を再生することなく、そのまま再利用することも可能となる。
【０００５】
近年、可消色性着色剤について種々検討が行われ、熱を加えることにより消色可能な可消色性着色剤が、例えば、特開平７−８１２３６号公報や特開平１０−８８０４６号公報に開示されている。前者の公開公報には、ロイコ染料などの呈色性化合物と、顕色剤と、消色作用を有する有機リン酸化合物とを含有する可消色性着色剤が、又、後者の公開公報には、ロイコ染料などの呈色性化合物と顕色剤との組み合わせに対して、熱を加えることによって消色作用を示す消色剤としてコール酸、リトコール酸、テストステロン、コルチゾンなどのステロール化合物を使用する可消色性着色剤が開示されている。
【０００６】
又、有機溶剤と接触させることにより消色可能な可消色性着色剤が、例えば特開２０００−１０９８９６号公報に開示されている。この可消色性着色剤は、ロイコ染料などの呈色性化合物、顕色剤、及び、消色剤からなるものであり、消色剤として、顕色剤を物理的又は化学的に吸着することが可能な電子供与性基を有する高分子化合物（例えば、デンプン、デンプン誘導体、セルロース誘導体など）を用いることが特徴であり、消色助剤としては、エーテル類、ケトン類、エステル類、芳香族炭化水素類、ハロゲン化炭化水素類、などの有機溶剤を用いることができる。
【０００７】
紙の消費量が多いオフィスで可消色性画像が形成された紙を消色処理して再利用することを考えると、防災、環境汚染防止、及び、臭気対策などの点から消色助剤として有機溶媒を安易に用いることは好ましくなく、大がかりな密閉循環式の溶剤回収装置付消色装置が必須となる。このような装置は、導入費用及び運転経費の点で、可消色性着色剤・画像形成材料の普及を推進する上で障害となる。又、紙を束にして一度で大量に消色処理できることが好ましいが、このような大量一括消色処理を加熱によって行う場合の加熱処理条件及びそれに適した可消色性組成物はこれまで検討されていないため、良好な消色状態が得られない場合もあることが判ってきた。
【０００８】
【発明が解決しようとする課題】
本発明の目的は、防災、環境汚染防止、臭気対策、及び経済性の点で優れ、更に紙を束にして一度で大量に消色処理することのできる可消色性画像の消色方法を提供することである。
【０００９】
【課題を解決するための手段】
上記の目的は以下の本発明によって達成される。即ち、本発明は、マトリックス材料を含み、又は含まず、少なくとも顕色剤、及び、前記顕色剤との分子間相互作用により発色する呈色性化合物からなる発色状態の可消色性組成物を含む画像形成材料によって、前記顕色剤と前記呈色性化合物との分子間相互作用よりも強く、前記顕色剤と分子間相互作用することによって消色作用を示す画像形成媒体の上に形成された可消色性画像に、固体の消色助剤の昇華によって発生させる消色助剤の気体を作用させることによって前記顕色剤と前記消色作用を示す画像形成媒体との分子間相互作用を起こさせて前記可消色性画像を消色させることを特徴とする可消色性画像の消色方法である。
【００１０】
【発明の実施の形態】
以下に発明の好ましい実施の形態を挙げて本発明を更に詳細に説明する。
［画像形成媒体］
本発明において、消色作用を示す画像形成媒体としては、セルロース繊維からなる通常の紙、ボール紙、ダンボール紙などの紙を用いることができる。紙には表面及び内部にも消色剤は含まれていない。
セルロース繊維からなる通常の紙は、特開２０００−１０９８９６号報に記載のように、顕色剤、及び、前記顕色剤との分子間相互作用により発色する呈色性化合物からなる発色状態の可消色性組成物を、加熱処理又は消色助剤処理によって消色する作用を示す。
【００１１】
［画像］
本発明において画像とは、画像形成媒体上に保持された画像形成材料によって構成される文字、記号、模様、意匠、絵画、写真などを言う。
以下、本発明で用いられる可消色性画像を形成する可消色性組成物を構成する材料について具体的に説明する。
【００１２】
［マトリックス材料］
可消色性組成物がマトリックス材料を含む場合、マトリックス材料としては、有機高分子化合物又は低分子化合物を使用することができる。以下、必要に応じて、有機高分子化合物からなるマトリックス材料を高分子マトリックス材料、又、低分子化合物からなるマトリックス材料を低分子マトリックス材料と呼ぶこととする。
本発明で用いられる可消色性組成物に用いられる高分子マトリックス材料は、可消色性組成物を画像形成材料として用いる際に通常追加して使用される結着剤樹脂と同一でも、異なっても良い。
例えば、ジェットインク（インクジェットプリンター用のインク）のように可消色性組成物からなる粒子を、そのまま、溶剤（水又は有機溶剤））に分散させた形態の画像形成材料の場合、画像形成材料として用いる際に追加して使用される結着剤樹脂乃至分散剤は前記溶剤に可溶であって、一方、可消色性組成物に用いられるマトリックス材料は前記溶剤に不溶性・不膨潤性であることが必要である。
【００１３】
又、例えば、オフセットインキのように可消色性組成物からなる粒子をワニスに分散させて使用する場合には、可消色性組成物に用いられるマトリックス材料は、ワニスの溶剤である亜麻仁油、大豆油、高沸点の石油系溶剤などに不溶性・不膨潤性であることが必要である。
更に、画像形成材料が、例えば、クレヨン、クレパス、熱転写インク、複写機用トナーなどの形態で用いられる場合には、可消色性組成物に用いられるマトリックス材料は、可消色性組成物を画像形成材料として用いる際に追加して使用される結着剤樹脂と同一であっても良い。
【００１４】
高分子マトリックス材料としては、画像形成材料のジェットインク、印刷インキなどの使用形態に応じ、公知の熱可塑性樹脂及び熱硬化性樹脂の中から、可消色性組成物が色素として発色状態で使用される温度範囲において、呈色性化合物及び顕色剤を固溶化（溶解して分子分散させる）することができ、且つ、画像形成材料としての形態を維持することのできる樹脂を適宜選択して使用することができ、特に制限されない。
【００１５】
具体的には、例えば、呈色性化合物としてロイコ色素、顕色剤としてフェノール化合物を用いる場合、次のような有機高分子化合物をマトリックス材料として好適に使用することができる。即ち、例えば、ケトン樹脂、ノルボルネン樹脂、ポリスチレン、ポリ（α−メチルスチレン）、ポリインデン、ポリ（４−メチル−１−ペンテン）、ポリアセタール、ポリビニルホルマール、ポリビニルアセタール、ポリビニルブチラール、ポリ酢酸ビニル、ポリプロピオン酸ビニル、ポリエチレン、ポリプロピレン、ポリブタジエン、ポリ塩化ビニル、塩素化ポリ塩化ビニル、塩素化ポリエチレン、塩素化ポリプロピレン、ポリ塩化ビニリデン、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、ポリビニルメチルエーテル、ポリビニルエチルエーテル、ポリビニルベンジルエーテル、ポリビニルメチルケトン、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ブチル、ポリメタクリル酸ベンジル、ポリメタクリル酸シクロヘキシル、
【００１６】
ポリクロラール、ポリエチレンオキシド、ポリプロピレンオキシド、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート類（ビスフェノール類＋炭酸）、ポリサルホン、ポリエーテルサルホン、ポリフェニレンサルファイド、ポリ（ジエチレングリコール・ビスアリルカーボネート）類、６−ナイロン、６，６−ナイロン、１２−ナイロン、６，１２−ナイロン、アルキド樹脂（無水フタル酸＋グリセリン）、脂肪酸変性アルキド樹脂（脂肪酸＋無水フタル酸＋グリセリン）、不飽和ポリエステル樹脂（無水マレイン酸＋無水フタル酸＋プロピレングリコール）、エポキシ樹脂（ビスフェノール類＋エピクロルヒドリン）、エポキシ樹脂（クレゾールノボラック＋エピクロルヒドリン）、ポリウレタン樹脂、フェノール樹脂、尿素樹脂、メラミン樹脂、キシレン樹脂、トルエン樹脂、フラン樹脂、グアナミン樹脂、ジアリルフタレート樹脂などの樹脂、ポリ（フェニルメチルシラン）などの有機ポリシラン、これらの重合体を構成する単量体同士の共重合体・共重縮合体および有機ポリゲルマンなどを好適に使用することができる。
【００１７】
更に、例えば、呈色性化合物としてロイコ色素、顕色剤としてフェノール化合物を用いて得られる可消色性組成物からなる粒子を、複写機又はプリンター用のトナーに用いる場合には、可消色性組成物のマトリックス材料兼画像形成材料の結着剤樹脂として、例えば、ポリスチレン、ポリスチレンとアクリル樹脂とのブレンドポリマー、スチレン−アクリル系共重合体、ポリエステル、エポキシ樹脂などを特に好適に用いることができる。ここで、スチレン−アクリル系共重合体を構成するアクリル系モノマーとしては、例えば、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、アクリル酸エチル、アクリル酸ｎ−ブチル、メタクリル酸メチル、メタクリル酸グリシジル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチル、アクリル酸ジエチルアミノプロピル、アクリル酸２−エチルヘキシル、アクリル酸ブチル、Ｎ−（エトキシメチル）アクリルアミド、メタクリル酸エチレングリコール、メタクリル酸４−ヘキサフルオロブチルなどが挙げられる。
【００１８】
低分子マトリックス材料としては低分子可塑剤、低分子滑剤、低分子ワックスなどの低分子化合物を用いることができる。即ち、可消色性組成物が色素として発色状態で使用される温度範囲において、呈色性化合物及び顕色剤を固溶化（溶解し分子分散させる）することができ、且つ、画像形成材料としての形態を維持することのできる低分子化合物を適宜選択して低分子マトリックス材料として使用することができる。
具体的には、例えば、呈色性化合物としてロイコ色素、顕色剤としてフェノール化合物を用いてクレヨンを作成する場合、低分子化合物（ワックス）として、例えば、１−ドコサノールを好適に使用することができる。
【００１９】
［呈色性化合物］
本発明で用いられる呈色性化合物としては、例えば、ロイコオーラミン類、ジアリールフタリド類、ポリアリールカルビノール類、アシルオーラミン類、アリールオーラミン類、ローダミンＢラクタム類、インドリン類、スピロピラン類、フルオラン類などの有機化合物を挙げることができる。
【００２０】
具体的な呈色性化合物として、例えば、クリスタルバイオレット・ラクトン（ＣＶＬ）、マラカイトグリーン・ラクトン、２−アニリノ−６−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）−３−メチルフルオラン、２−アニリノ−３−メチル−６−（Ｎ−メチル−Ｎ−プロピルアミノ）フルオラン、３−［４−（４−フェニルアミノフェニル）アミノフェニル］アミノ−６−メチル−７−クロロフルオラン、２−アニリノ−６−（Ｎ−メチル−Ｎ−イソブチルアミノ）−３−メチルフルオラン、２−アニリノ−６−（ジブチルアミノ）−３−メチルフルオラン、３−クロロ−６−（シクロヘキシルアミノ）フルオラン、２−クロロ−６−（ジエチルアミノ）フルオラン、７−（Ｎ，Ｎ−ジベンジルアミノ）−３−（Ｎ，Ｎ−ジエチルアミノ）フルオラン、３，６−ビス（ジエチルアミノ）フルオラン−γ−（４′−ニトロアニリノ）ラクタム、３−ジエチルアミノベンゾ［ａ］−フルオラン、３−ジエチルアミノ−６−メチル−７−アミノフルオラン、３−ジエチルアミノ−７−キシリジノフルオラン、
【００２１】
３−（４−ジエチルアミノ−２−エトキシフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド、３−（４−ジエチルアミノフェニル）−３−（１−エチル−２−メチルインドール−３−イル）フタリド、３−ジエチルアミノ−７−クロロアニリノフルオラン、３−ジエチルアミノ−７，８−ベンゾフルオラン、３，３−ビス（１−ｎ−ブチル−２−メチルインドール−３−イル）フタリド、３，６−ジメチルエトキシフルオラン、３−ジエチルアミノ−６−メトキシ−７−アミノフルオラン、２−（２−クロロアニリノ）−６−ジブチルアミノフルオラン、クリスタルバイオレットカルビノール、マラカイトグリーンカルビノール、Ｎ−（２，３−ジクロロフェニル）ロイコオーラミン、Ｎ−ベンゾイルオーラミン、ローダミンＢラクタム、Ｎ−アセチルオーラミン、Ｎ−フェニルオーラミン、
【００２２】
２−（フェニルイミノエタンジリデン）−３，３−ジメチルインドリン、Ｎ，３，３−トリメチルインドリノベンゾスピロピラン、８′−メトキシ−Ｎ，３，３−トリメチルインドリノベンゾスピロピラン、３−ジエチルアミノ−６−メチル−７−クロロフルオラン、３−ジエチルアミノ−７−メトキシフルオラン、３−ジエチルアミノ−６−ベンジルオキシフルオラン、１，２−ベンゾ−６−ジエチルアミノフルオラン、３，６−ジ−ｐ−トルイジノ−４，５−ジメチルフルオラン、フェニルヒドラジド−γ−ラクタム、３−アミノ−５−メチルフルオランなどを好適に使用することができる。これらは単独で、又は２種以上を混合して用いることができる。言うまでもなく、呈色性化合物を適宜選択すれば多様な色の発色状態が得られ、マルチカラー化が可能である。
これらの呈色性化合物は、例えば、一例を以下に化学式で示すように、無色型と発色型の両形態をとることの可能な互変異性化合物である。
【００２３】
［顕色剤］
上記のような互変異性を表す化学式において、下側に示される分子内塩型の化学構造が「発色型」に対応することが知られている。そして、このようなイオン性分子内塩型の構造をプロトンの授受乃至水素結合の形成、或いは金属錯塩の形成によって安定化することによって、発色型を安定化することのできる化合物が、いわゆる顕色剤である。
本発明で用いられる顕色剤としては、例えば、フェノール及びフェノール誘導体、フェノール誘導体の金属塩、フェノール性水酸基を有するベンゾフェノン誘導体、カルボン酸誘導体の金属塩、サリチル酸及びサリチル酸金属塩、スルホン酸類、スルホン酸塩類、リン酸類、リン酸金属塩類、酸性リン酸エステル類、酸性リン酸エステル金属塩類、亜リン酸類、亜リン酸金属塩類、ハロゲン化亜鉛などを挙げることができる。これらは単独で、又は２種以上を混合して用いることができる。
顕色剤として用いることのできるフェノール誘導体の具体例を以下に化学式で例示する。
【００２５】
これらのフェノール誘導体は、例えば、次に化学式で示すように発色型の呈色性化合物のカルボン酸残基と分子間で相互作用して水素結合を形成することによって、発色状態を安定化することができる。このような呈色性化合物と顕色剤の分子間相互作用は、両者がともにマトリックス材料中に固溶化（溶解して分子分散）している場合であっても起こりうる。
【００２７】
［発色及び消色の機構］
上記化学式に例示されるようにマトリックス材料中で呈色性化合物と顕色剤とが分子間で相互作用し、呈色性化合物が発色型として存在している可消色性組成物を含む画像形成材料が、前記の消色作用を示す画像形成媒体の表面に付着している場合、或いは、結着剤によって画像形成媒体の表面に接着されている場合、加熱や消色助剤処理による活性化が行われなければ、顕色剤と画像形成媒体中の消色作用を示す部分とは、大部分が離れ離れに存在するため、両者の分子間相互作用（化学平衡論的には呈色性化合物と顕色剤の相互作用よりも強い）は、起こり得ず、顕色剤によって安定化された呈色性化合物の発色状態は維持される。
一方、加熱及び／又は消色助剤処理による活性化が行われた場合、低分子化合物である顕色剤が可消色性組成物中を移動（マイグレーション）し、更に、消色性を示す画像形成媒体の消色作用を発現する部分と分子間相互作用することが可能となり、結果的に呈色性化合物は顕色剤を消色性を示す画像形成媒体の消色作用を発現する部分に奪われたこととなり、呈色性化合物は消色状態になる。本発明ではこの消色を促進するために後述する消色助剤の気体（気体状態の消色助剤）の存在下に加熱処理することが特徴である。
【００２９】
［配合比］
本発明で用いられる可消色性組成物は、マトリックス材料を含む場合、少なくとも呈色性化合物、及び、顕色剤から構成されるが、好ましい配合比は以下の通りである。
マトリックス材料は、呈色性化合物１重量部に対して通常０．１乃至１０００重量部、好ましくは０．５乃至１００重量部、更に好ましくは１乃至２０重量部の割合である。顕色剤は、呈色性化合物１重量部に対して通常０．１乃至１０重量部、好ましくは１乃至２重量部の割合である。顕色剤が０．１重量部未満の場合には、呈色性化合物と顕色剤との相互作用による粒子状可消色性着色剤の発色が不充分になる。顕色剤が１０重量部を超える場合には両者の相互作用を充分に減少させることが困難となる。
【００３０】
消色作用を示す画像形成媒体中の消色成分（化学構造単位）の顕色剤分子に対するモル比は、消色処理時に画像形成媒体中に顕色剤が浸透していく領域中、又は、可消色性画像形成材料中に消色成分が浸透していく領域中において、顕色剤１分子に対して、通常、５モル比、好ましくは１０モル比以上の割合であることが望ましい。消色成分が５モル比未満では、可消色性組成物の発色状態を完全に消色状態にさせることが困難になる。消色作用を示す画像形成媒体中の消色成分（化学構造単位）の顕色剤分子に対するモル比に、特に上限はない。
【００３１】
本発明で用いられる可消色性組成物が、マトリックス材料を含まない場合にも、使用される呈色性化合物、及び、顕色剤の配合比はマトリックス材料を含む場合と同じである。しかしながら、マトリックス材料を用いない場合には、呈色性化合物及び顕色剤の組み合わせ方の制約として、呈色性化合物と顕色剤は固体状態で互いに固溶化し、アモルファス状になる組み合わせが好ましい。例えば、クリスタルバイオレット・ラクトンとサリチル酸亜鉛の組み合わせを挙げることができる。
尚、本発明で用いられる可消色性画像形成材料には、その機能を損なわない限りにおいて、必要に応じて、低分子化合物からなる可塑剤、ワックス、滑剤、離型剤、光安定剤、酸化防止剤、帯電制御剤などの添加剤を適量、含有させることができる。
【００３２】
［消色助剤］
以上で説明した消色作用を示す画像形成媒体上に形成された可消色性組成物を含む画像形成材料からなる可消色性画像の消色には、上記可消色性画像に作用させることによって消色作用を促進させる物質、即ち、消色助剤が使用される。本発明における消色助剤は、常温で固体の物質であり、これらを気体状態で可消色性画像に作用させる。
消色助剤単体では消色作用を示さない物質であっても、その作用によって可消色性組成物中の顕色剤が可消色性組成物中を移動（マイグレーション）する現象が促進され、その結果、顕色剤と消色作用を示す画像形成媒体とが分子間相互作用を起こすことを促進することのできるものであれば、消色助剤として用いることができる。
可消色性組成物がマトリックス材料を含む場合、気体状態の消色助剤はマトリックス材料中に固溶化（固体中に分子分散）し、可塑化作用を示すものであることが好ましい。又、可消色性組成物がマトリックス材料を含まない場合は、気体状態の消色助剤は呈色性化合物と顕色剤との混合物中に固溶化又は溶解するものであることが好ましい。
【００３３】
常温、常圧においては固体として存在する有機化合物を閉じた容器の中に、例えば前記容器の内容積の５％乃至５０％程度の量で導入し、前記容器を室温乃至前記固体の融点未満の温度に保つと、容器中には前記固体から昇華した蒸気が徐々に充満し、やがて平衡状態に到達する。このようにして発生させた固体有機化合物の蒸気（温度は融点未満）を消色助剤として好適に用いることができる。但し、ナフタレンのように昇華性は高いが空気と爆発性混合気体を形成するものは、防災上、厳重な安全対策を必要とするため実用的ではない。防災上、及び人体への安全性の点で、「香料」として用いられる昇華性の有機化合物固体の中から、消色助剤として安全に利用できるものを選択することができる。
【００３４】
例えば、６−アセチル−１，１，２，４，４，７−ヘキサメチルテトラヒドロナフタレン（融点４６℃）、クマリン（融点６８℃；急性経口毒性ＬＤ５０：２９３ｍｇ／ｋｇ（ラット））、ケイ皮酸メチル（融点３８℃；急性経口毒性ＬＤ５０：２．５ｇ／ｋｇ（ラット））、酢酸イソオイゲノール（融点８０℃；急性経口毒性ＬＤ５０：３．４５ｇ／ｋｇ（ラット））、酢酸ジメチルベンジルカルビニル（融点３０℃；ライラック系香料；急性経口毒性ＬＤ５０：３．３ｇ／ｋｇ（ラット））、２−エトキシナフタレン（融点３７℃；急性経口毒性ＬＤ５０：３．１１ｇ／ｋｇ（ラット））、２−メトキシナフタレン（融点７２℃；急性経口毒性ＬＤ５０：５ｇ／ｋｇ（ラット））、ボルネオール（融点２０６〜２０８℃；急性経口毒性ＬＤ５０：６．５ｇ／ｋｇ（ラット））、マントール（融点１６１〜１６２℃；９３℃以上で昇華；急性経口毒性ＬＤ５０：２．３３ｇ／ｋｇ（ラット））、メントール（融点４３〜４５℃；急性経口毒性ＬＤ５０：３．１８ｇ／ｋｇ（ラット））、などから昇華して発生する蒸気を気体状態の消色助剤として好適に用いることができる。
【００３５】
その他、室温で固体の有機化合物であって、消色助剤として作用するものを例示すると、例えば、ベンゾフェノン（融点４８．５℃；急性経口毒性ＬＤ５０：＞１０ｇ／ｋｇ（ラット））、４，４′−ビス（ジエチルアミノ）ベンゾフェノン（融点９４℃）、４，４′−ビス（ジメチルアミノ）ベンゾフェノン（融点１７４℃）、４，４′−ジメトキシベンゾフェノン（融点１４５℃）、４，４′−ジメチルベンゾフェノン（融点９５℃）、４−メトキシベンゾフェノン（融点６０℃）、４−メチルベンゾフェノン（融点５６℃）、２−ｎ−プロポキシナフタレン（融点４０℃）、２，７−ジメトキシナフタレン（融点１３９℃）などの置換基を有しても良い芳香族炭化水素化合物、３−アセチルクマリン（融点１２２℃）、５，７−ジメトキシクマリン（融点１４６℃）、６，７−ジメトキシー４−メチルクマリン（融点１３９℃）、７−エトキシクマリン（融点９０℃）などの置換基を有しても良い芳香族複素環化合物、樟脳（融点１７９℃）、カンフェン（融点５１．２℃）、トリシクレン（融点６８℃）などのテルペン類、ヒノキチオール（融点５２℃）、ヒノキチオールの誘導体、２−ノルボルナノン（別名、ノルカンファー；融点９５℃）などの脂肪族環状ケトンなどを挙げることができる。
【００３６】
［消色処理の温度］
可消色性画像を形成している可消色性組成物に気体状態の消色助剤が固溶化することによって、消色助剤を含む可消色性組成物の軟化点又は融点は、消色助剤を含まない可消色性組成物の場合よりも低くなる。従って、気体状態の消色助剤を用いて消色を行う場合の温度の目安としては、「消色助剤を含む又は含まない可消色性組成物の軟化点又は融点」を推奨することができる。消色助剤を含む可消色性組成物の軟化点又は融点とは、消色助剤の気体が存在する状態における消色助剤が固溶化又は溶解した可消色性組成物の軟化点又は融点を意味し、消色助剤を含まない可消色性組成物の軟化点又は融点とは、消色助剤の気体が存在しない状態における可消色性組成物そのものの軟化点又は融点を意味する。
【００３７】
加熱に要するエネルギーを低減させるためには、できる限り低い温度が好ましい。それには、「消色助剤を含まない可消色性組成物の軟化点又は融点」を上限として、最適な消色処理の温度を実験的に求めれば良い。
一方、可消色性画像及び画像形成媒体を構成する成分の熱分解開始温度の内、最も低い温度を超えない温度を消色処理の温度の上限とする。言うまでもなく、この上限温度を超えると、可消色性画像及び画像形成媒体を構成する成分のいずれかが非可逆的な熱分解反応を起こしてしまうため、再利用・再生が困難となる。
【００３８】
【実施例】
以下に実施例及び参考例を挙げて本発明を更に詳しく説明する。文中の「部」は重量基準である。
【００３９】
実施例１
呈色性化合物として感熱色素Ｂｌｕｅ６３（山本化成株式会社製）４重量部、顕色剤として没食子酸プロピル２重量部、マトリックス樹脂として９３重量部のポリスチレン、及び、帯電制御剤としてＬＲ−１４７（日本カーリット株式会社製）１重量部を予め混合し、ニーダーを用いて９０℃を越えない温度で充分に混練りし、青色に発色した可消色性色素組成物を製造した。この可消色性色素組成物の軟化点を環球法（日本工業規格Ｋ２４０６）で測定したところ７６℃であった。
【００４０】
以上のように製造された可消色性色素組成物（マトリックス樹脂を含有するもの）を粉砕機により粉砕して平均粒径１２マイクロメートルの粉体を得た。この粉体１００重量部に対して１重量部の疎水性シリカを添加してトナーを調製した。
得られたトナーを電子写真方式複写機のトナーカートリッジに入れ、試験用画像（テストチャート）を複写機用中性紙（反射率０．０８）に転写した。得られた画像は充分な画像濃度であり、通常の使用条件で高い耐久性を示し、又、１００℃で３０分間加熱しても画像は維持された。即ち、消色助剤が存在しない場合、軟化点（この場合７６℃）よりもある程度高い温度まで加熱しても、短時間では消色が進行しないことが判った。
【００４１】
この可消色性画像は１５０℃以上まで加熱するか、或いは、以下に述べるような気体状態の消色助剤の存在下、７０℃乃至８０℃に加熱することで消色することができる。
上記の青色可消色性組成物からなるトナーによってコピー画像が形成された紙１００枚を、束ねた状態でステンレス製蓋付バット（シリコーンゴムパッキン付；内寸２６０ｍｍ×２３０ｍｍ×４０ｍｍ）に入れ、その上に、酢酸イソオイゲノール（融点８０℃）１０ｇを入れたガラスシャーレを乗せ、蓋付バットの蓋を閉じて密閉してから７５℃に温度調節された送風式恒温器（ヤマト科学製ＤＮ８３型）に入れ、同温度で１２時間放置した後、４時間を要して室温まで冷却してから取り出した。その結果、１００枚の紙に形成されたコピー画像は全て消色され、肉眼では確認できなくなった。消色後の可消色性画像記録紙各々の反射濃度を測定したところ、全て０．１０であった。即ち、優れた消色特性を発揮することが確認された。
【００４２】
上記の加熱消色によってコピー画像が消色された紙を６０℃で３００時間放置したが、画像が再び現れることはなかった。尚、前記ステンレス製蓋付バットを室温まで冷却する際、恒温器から取り出して急激に冷却すると酢酸イソオイゲノールの微結晶がステンレス製蓋付バットの内壁全面に析出してしまうが、恒温器中から取り出さずに恒温器内部の温度をプログラム温度制御によってゆっくり冷却させると、ガラスシャーレ中に残存した結晶を「種」として、それらの周囲に集中的に結晶化が起こるため、容器内壁を汚染することなく回収することが可能になる。
【００４３】
可消色性画像を上記の方法で処理して消色した紙に、別の画像を転写し、気体の消色助剤の存在下加熱処理で消色するプロセスを９回繰り返した。その後に転写した１０回目の画像は１回目の画像と同等の品質であった。更に、コピー及び消色を５０回まで繰り返した。その結果、紙は機械的に痛んだが、コピーされた画像の品質及び消色状態の品質は良好であった。
【００４４】
参考例１
呈色性化合物として感熱色素Ｂｌｕｅ６３（山本化成株式会社製）４重量部、顕色剤として没食子酸プロピル２重量部、マトリックス樹脂として９３重量部のポリスチレン、及び、帯電制御剤としてＬＲ−１４７（日本カーリット株式会社製）１重量部を予め混合し、この混合物をバンバリーミキサーを用いて混練りしたところ、摩擦熱により約２分で溶融・流動状態となった。混練り物を冷却して取り出し、青色に発色した可消色性色素組成物を得た。この可消色性色素組成物の軟化点を環球法（日本工業規格Ｋ２４０６）で測定したところ７８℃であった。
【００４５】
以上のように製造された可消色性色素組成物を粉砕機により粉砕して平均粒径１２マイクロメートルの粉体を得た。この粉体１００重量部に対して１重量部の疎水性シリカを添加してトナーを調製した。
得られたトナーを電子写真方式複写機のトナーカートリッジに入れ、試験用画像（テストチャート）を複写機用中性紙（反射率０．０８）に転写した。得られた画像は充分な画像濃度であり、通常の使用条件で高い耐久性を示し、又、１００℃で３０分間加熱しても画像は維持された。
この可消色性画像は１９０℃以上まで加熱するか、或いは、以下に述べるような気体の消色助剤の存在下、７０℃乃至８０℃に加熱することで消色することができる。
【００４６】
上記の青色可消色性組成物からなるトナーによってコピー画像が形成された紙１００枚を、束ねた状態でステンレス製蓋付バット（シリコーンゴムパッキン付；内寸２６０ｍｍ×２３０ｍｍ×４０ｍｍ）に入れ、その上に、ｐ−メチルアセトフェノン（融点２８℃；沸点２２８℃）１０ｇを入れたガラスシャーレを乗せ、蓋付バットの蓋を閉じて密閉してから７５℃に温度調節された送風式恒温器（ヤマト科学製ＤＮ８３型）に入れ、同温度で１２時間放置した後、１時間を要して室温まで冷却してから取り出した。その結果、１００枚の紙に形成されたコピー画像は全て消色され、肉眼では確認できなくなった。消色後の可消色性画像記録紙各々の反射濃度を測定したところ、全て０．１０であった。即ち、優れた消色特性を発揮することが確認された。加熱消色によってコピー画像が消色された紙を６０℃で３００時間放置したが、画像が再び現れることはなかった。
可消色性画像を上記の方法で処理で消色した紙に、別の画像を転写し、気体の消色助剤の存在下加熱処理で消色するプロセスを９回繰り返した。その後に転写した１０回目の画像は１回目の画像と同等の品質であった。更に、コピー及び消色を５０回まで繰り返した。その結果、紙は機械的に痛んだが、コピーされた画像の品質及び消色状態の品質は良好であった。
【００４７】
実施例２
参考例１で使用した可消色性組成物混練り物をカッター刃回転式粉砕機で粒子外径１ｍｍまで粗粉砕し、次いで、これをサイクロン式分級機を備えた循環式エアジェット粉砕機で最大粒子径４μｍ以下まで粉砕し、更に、これを別のサイクロン式分級機を用いて分級し、数平均粒子径１．０μｍ且つ体積平均粒子径２．０μｍの微粒子として可消色性着色剤を得た。この微粒子状可消色性着色剤２０部を結着剤としてメタクリル酸メチル−アクリル酸ブチル−アクリル酸（アンモニウム塩）共重合体２０重量部を含み、他にノニオン系分散剤２重量部、プロピレングリコール１０重量部、及び、水４８重量部を含む結着剤溶液へ、３本ロールを用いて分散させ、可消色性水性着色剤を作成した。
【００４８】
バーコーターを用いてこの可消色性水性着色剤を複写機用中性紙（反射率０．０８）の片面全面に塗工し、乾燥し、いわゆる「ベタ塗り」の画像を形成した。このような片面塗工紙を１００枚作成し、束ねた状態でステンレス製蓋付バット（シリコーンゴムパッキン付；内寸２６０ｍｍ×２３０ｍｍ×４０ｍｍ）に入れ、その上に、２−メトキシナフタレン（融点７２℃）１０ｇを入れたガラスシャーレを乗せ、蓋付バットの蓋を閉じて密閉してから７０℃に温度調節された送風式恒温器（ヤマト科学製ＤＮ８３型）に入れ、同温度で１２時間放置した後、４時間を要して室温まで冷却してから取り出した。その結果、１００枚の紙に形成された「ベタ塗り」画像は全て消色され、肉眼では確認できなくなった。消色後の可消色性画像形成紙各々の反射濃度を測定したところ、全て０．０９であった。即ち、優れた消色特性を発揮することが確認された。
【００４９】
加熱消色によってコピー画像が消色された紙を６０℃で３００時間放置したが、画像が再び現れることはなかった。尚、前記ステンレス製蓋付バットを室温まで冷却する際、恒温器から取り出して急激に冷却すると２−メトキシナフタレンの微結晶がステンレス製蓋付バットの内壁全面に析出してしまうが、恒温器中から取り出さずに恒温器内部の温度をプログラム温度制御によってゆっくり冷却させると、ガラスシャーレ中に残存した結晶を「種」として、それらの周囲に集中的に結晶化が起こるため、容器内壁を汚染することなく回収することが可能になる。
【００５０】
可消色性画像を上記の方法で処理して消色した紙に、再度、バーコーターを用いて上記の可消色性水性着色剤を塗工し、乾燥して「ベタ塗り」画像を形成し、気体の消色助剤の存在下加熱処理で消色するプロセスを９回繰り返した。その後に塗工して形成させた１０回目の「ベタ塗り」画像は１回目の画像と同等の品質であった。更に、画像形成及び消色を５０回まで繰り返した。その結果、紙は機械的に痛んだが、「ベタ塗り」画像の品質及び消色状態の品質は良好であった。
【００５１】
【発明の効果】
以上詳述したように、本発明の可消色性画像の消色方法によれば、紙の上に形成された可消色性画像を優れた消色特性で消色し、紙を再利用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for erasing an erasable image formed of an image forming material containing an erasable composition formed on an image forming medium by a method such as electrophotography, thermal transfer recording, writing instrument, and printing.
[0002]
[Prior art]
In recent years, with the spread of computers, printers, copiers, facsimiles, etc., the output of information by paper has increased. In order to reduce output to paper, “paperless by computerization of information” is screamed, but because of features such as good visibility, high portability, and ease of information retrieval by turning pages, hard copy on paper Requests never end. As a result, protection of natural resources that are raw materials for paper, reduction of waste disposal, and reduction of carbon dioxide emissions have become issues to be solved. Therefore, “paper recycling / reuse” is a very current issue in each aspect of protection of natural resources, reduction of waste disposal, and reduction of carbon dioxide emissions.
[0003]
Under these circumstances, the technology that makes image forming materials (various printing ink, toner, jet ink, etc.) for printing / printing on paper colorless after printing / printing promotes the recycling and reuse of paper. Very important. That is, in the conventional paper recycling method, after the recovered paper is re-flocculated with water, a method of floating and separating the ink part in a so-called “deinking step” or a method of decoloring using a bleaching agent is used. These are factors that increase process costs compared to the case of newly making paper.
[0004]
Therefore, a paper printed with an image forming material using a decolorizable colorant capable of changing a color developing compound in a colored state to a colorless decoloring state has a conventional deinking process. It is expected that it can be reused or recycled without going through. Further, if the image forming material using the erasable colorant can be brought into a colorless erasable state by a simple and safe operation, the image forming medium (mainly paper) on which the image is formed is not reproduced. It can be reused as it is.
[0005]
In recent years, various studies have been made on erasable colorants, and erasable colorants that can be erased by applying heat are disclosed in, for example, JP-A-7-81236 and JP-A-10-88046. It is disclosed. In the former publication, a decolorizable colorant containing a color developing compound such as a leuco dye, a developer, and an organic phosphoric acid compound having a decoloring action is also disclosed in the latter publication. Uses a sterol compound such as cholic acid, lithocholic acid, testosterone, or cortisone as a color erasing agent that exhibits a decoloring action by applying heat to a combination of a color developing compound such as a leuco dye and a developer. A erasable colorant is disclosed.
[0006]
Further, a decolorizable colorant which can be decolored by contacting with an organic solvent is disclosed in, for example, Japanese Patent Application Laid-Open No. 2000-109896. This decolorizable colorant is composed of a color developing compound such as a leuco dye, a color developer, and a color eraser, and physically or chemically adsorbs the color developer as the color eraser. It is characterized by using a polymer compound having an electron-donating group (for example, starch, starch derivatives, cellulose derivatives, etc.), and as a decoloring aid, ethers, ketones, esters, aromatics Organic solvents such as group hydrocarbons and halogenated hydrocarbons can be used.
[0007]
Decoloring aids from the standpoints of disaster prevention, environmental pollution prevention, odor control, etc., considering that papers with decolorizable images formed in offices with high paper consumption can be erased and reused. It is not preferable to easily use an organic solvent, and a large-scale closed circulation type decoloring device with a solvent recovery device is essential. Such an apparatus is an obstacle to promoting the spread of the erasable colorant and the image forming material in terms of introduction cost and operation cost. In addition, it is preferable that a large amount of color can be erased at once with a bundle of paper. However, heat treatment conditions and a decolorizable composition suitable for the heat treatment conditions when such a large amount of batch color erase is performed by heating have been studied. As a result, it has been found that a good decolored state may not be obtained.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for erasing a decolorizable image that is excellent in disaster prevention, environmental pollution prevention, odor countermeasures, and economical efficiency, and that can be erased in large quantities at once in a bundle of paper. Is to provide.
[0009]
[Means for Solving the Problems]
The above object is achieved by the present invention described below. That is, the present invention relates to a erasable color-developable composition in a colored state, comprising or not containing a matrix material, and comprising at least a developer and a color developing compound that develops color by intermolecular interaction with the developer. On an image forming medium exhibiting a decoloring action by an intermolecular interaction between the developer and the color developing compound, and stronger than an intermolecular interaction between the developer and the color developing compound. In the formed erasable image,Generated by sublimation of solid decoloring aidThe decolorizable image is decolored by causing an intermolecular interaction between the developer and the image forming medium exhibiting the decoloring effect by causing a gas of the decoloring aid to act. This is a method for erasing a erasable image.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the invention.
[Image forming medium]
In the present invention, as an image forming medium exhibiting a decoloring action, normal paper made of cellulose fibers, cardboard, cardboard, or the like can be used. Paper does not contain a decolorizer on the surface or inside.
As described in JP 2000-109896 A, ordinary paper made of cellulose fibers has a color development state composed of a color developer and a color developing compound that develops color by intermolecular interaction with the color developer. The action of decoloring the decolorizable composition by heat treatment or decoloring aid treatment is shown.
[0011]
[image]
In the present invention, an image refers to a character, a symbol, a pattern, a design, a painting, a photograph, or the like that is constituted by an image forming material held on an image forming medium.
Hereinafter, the material which comprises the erasable composition which forms the erasable image used by this invention is demonstrated concretely.
[0012]
[Matrix material]
When the erasable composition contains a matrix material, an organic polymer compound or a low molecular compound can be used as the matrix material. Hereinafter, the matrix material composed of an organic polymer compound is referred to as a polymer matrix material, and the matrix material composed of a low molecular compound is referred to as a low molecular matrix material as necessary.
The polymer matrix material used in the erasable composition used in the present invention may be the same as or different from the binder resin that is usually added when the erasable composition is used as an image forming material. May be.
For example, in the case of an image forming material in a form in which particles made of a decolorable composition such as jet ink (ink for an ink jet printer) are dispersed as they are in a solvent (water or organic solvent), the image forming material In addition, the binder resin or dispersant used when used as a solvent is soluble in the solvent, while the matrix material used in the decolorizable composition is insoluble and non-swellable in the solvent. It is necessary to be.
[0013]
Further, for example, when particles made of a decolorable composition such as offset ink are dispersed in a varnish, the matrix material used in the decolorizable composition is linseed oil which is a solvent for the varnish. It must be insoluble and non-swellable in soybean oil and high-boiling petroleum solvents.
Further, when the image forming material is used in the form of, for example, a crayon, a crepas, a thermal transfer ink, or a toner for a copying machine, the matrix material used for the decolorable composition is an erasable composition. It may be the same as the binder resin additionally used when used as an image forming material.
[0014]
As a polymer matrix material, an erasable composition is used as a coloring material in a colored state from among known thermoplastic resins and thermosetting resins, depending on the use form of jet ink, printing ink, etc. The resin capable of solidifying (dissolving and molecularly dispersing) the color developable compound and the developer in the temperature range to be used, and maintaining the form as the image forming material is appropriately selected. It can be used and is not particularly limited.
[0015]
Specifically, for example, when a leuco dye is used as the color developing compound and a phenol compound is used as the developer, the following organic polymer compound can be suitably used as the matrix material. That is, for example, ketone resin, norbornene resin, polystyrene, poly (α-methylstyrene), polyindene, poly (4-methyl-1-pentene), polyacetal, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl acetate, polypropion Vinyl acid, polyethylene, polypropylene, polybutadiene, polyvinyl chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl methyl ether, Polyvinyl ethyl ether, polyvinyl benzyl ether, polyvinyl methyl ketone, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polymethacrylate Ethyl Le acid, polybutyl methacrylate, poly benzyl methacrylate, poly cyclohexyl methacrylate,
[0016]
Polychloral, polyethylene oxide, polypropylene oxide, polyethylene terephthalate, polybutylene terephthalate, polycarbonates (bisphenols + carbonic acid), polysulfone, polyethersulfone, polyphenylene sulfide, poly (diethylene glycol bisallyl carbonate), 6-nylon, 6 , 6-nylon, 12-nylon, 6,12-nylon, alkyd resin (phthalic anhydride + glycerin), fatty acid-modified alkyd resin (fatty acid + phthalic anhydride + glycerin), unsaturated polyester resin (maleic anhydride + phthalic anhydride) Acid + propylene glycol), epoxy resin (bisphenols + epichlorohydrin), epoxy resin (cresol novolak + epichlorohydrin), polyurethane resin, phenol Resins, urea resins, melamine resins, xylene resins, toluene resins, furan resins, guanamine resins, diallyl phthalate resins, organic polysilanes such as poly (phenylmethylsilane), and monomers constituting these polymers Copolymers / copolycondensates of each other, organic polygermane, and the like can be preferably used.
[0017]
Further, for example, when particles made of a decolorizable composition obtained by using a leuco dye as a color developing compound and a phenol compound as a developer are used in toner for copying machines or printers, As the binder resin for the matrix material and the image forming material of the adhesive composition, for example, polystyrene, a blend polymer of polystyrene and acrylic resin, styrene-acrylic copolymer, polyester, epoxy resin, etc. are particularly preferably used. it can. Here, examples of the acrylic monomer constituting the styrene-acrylic copolymer include, for example, n-butyl methacrylate, isobutyl methacrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, glycidyl methacrylate, methacrylic acid. Examples include dimethylaminoethyl acid, diethylaminoethyl methacrylate, diethylaminopropyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, N- (ethoxymethyl) acrylamide, ethylene glycol methacrylate, 4-hexafluorobutyl methacrylate, and the like.
[0018]
As the low-molecular matrix material, low-molecular compounds such as low-molecular plasticizers, low-molecular lubricants, and low-molecular waxes can be used. That is, the color developable compound and the developer can be dissolved (dissolved and molecularly dispersed) in the temperature range in which the erasable composition is used as a pigment in a colored state, and as an image forming material. A low molecular weight compound capable of maintaining the above form can be appropriately selected and used as a low molecular weight matrix material.
Specifically, for example, when a crayon is prepared using a leuco dye as a color developing compound and a phenol compound as a developer, for example, 1-docosanol is preferably used as the low molecular weight compound (wax). it can.
[0019]
[Coloring compound]
Examples of the color developing compound used in the present invention include leucooramines, diarylphthalides, polyarylcarbinols, acylauramines, arylauramines, rhodamine B lactams, indolines, and spiropyrans. And organic compounds such as fluorans.
[0020]
Specific color-forming compounds include, for example, crystal violet lactone (CVL), malachite green lactone, 2-anilino-6- (N-cyclohexyl-N-methylamino) -3-methylfluorane, 2-anilino -3-methyl-6- (N-methyl-N-propylamino) fluorane, 3- [4- (4-phenylaminophenyl) aminophenyl] amino-6-methyl-7-chlorofluorane, 2-anilino- 6- (N-methyl-N-isobutylamino) -3-methylfluorane, 2-anilino-6- (dibutylamino) -3-methylfluorane, 3-chloro-6- (cyclohexylamino) fluorane, 2- Chloro-6- (diethylamino) fluorane, 7- (N, N-dibenzylamino) -3- (N, N-diethylamino) Luolan, 3,6-bis (diethylamino) fluorane-γ- (4′-nitroanilino) lactam, 3-diethylaminobenzo [a] -fluorane, 3-diethylamino-6-methyl-7-aminofluorane, 3-diethylamino- 7-xylidinofluorane,
[0021]
3- (4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl- 2-Methylindol-3-yl) phthalide, 3-diethylamino-7-chloroanilinofluorane, 3-diethylamino-7,8-benzofluorane, 3,3-bis (1-n-butyl-2-methyl) Indol-3-yl) phthalide, 3,6-dimethylethoxyfluorane, 3-diethylamino-6-methoxy-7-aminofluorane, 2- (2-chloroanilino) -6-dibutylaminofluorane, crystal violet carbinol , Malachite green carbinol, N- (2,3-dichlorophenyl) leucooramine, N-benzoyl Ramin, Rhodamine B lactam, N- acetyl auramine, N- phenyl auramine,
[0022]
2- (Phenyliminoethanedilidene) -3,3-dimethylindoline, N, 3,3-trimethylindolinobenzospiropyran, 8'-methoxy-N, 3,3-trimethylindolinobenzospiropyran, 3-diethylamino- 6-methyl-7-chlorofluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-6-benzyloxyfluorane, 1,2-benzo-6-diethylaminofluorane, 3,6-di-p- Toluidino-4,5-dimethylfluorane, phenylhydrazide-γ-lactam, 3-amino-5-methylfluorane and the like can be preferably used. These may be used alone or in admixture of two or more. Needless to say, various color development states can be obtained by appropriately selecting a color developing compound, and multicolorization is possible.
These color-forming compounds are tautomeric compounds capable of taking both colorless and colored forms, for example, as shown in the chemical formula below.
[0023]
[Developer]
In the chemical formulas showing the tautomerism as described above, it is known that the chemical structure of the inner salt type shown on the lower side corresponds to the “color-forming type”. A compound capable of stabilizing the chromogenic type by stabilizing such an ionic intramolecular salt type structure by exchanging protons or forming a hydrogen bond or forming a metal complex salt is a so-called color development. It is an agent.
Examples of the developer used in the present invention include phenol and phenol derivatives, metal salts of phenol derivatives, benzophenone derivatives having a phenolic hydroxyl group, metal salts of carboxylic acid derivatives, salicylic acid and salicylic acid metal salts, sulfonic acids, and sulfonic acids. Examples thereof include salts, phosphoric acids, phosphoric acid metal salts, acidic phosphoric acid esters, acidic phosphoric acid ester metal salts, phosphorous acids, phosphorous acid metal salts, and zinc halides. These may be used alone or in admixture of two or more.
Specific examples of the phenol derivative that can be used as the developer are illustrated by the following chemical formula.
[0025]
These phenol derivatives stabilize the color development state by, for example, interacting with the carboxylic acid residues of the color-developable color-forming compound and forming hydrogen bonds as shown in the chemical formula below. Can do. Such intermolecular interaction between the color developing compound and the developer may occur even when both are solid-solved (dissolved and molecularly dispersed) in the matrix material.
[0027]
[Coloring and erasing mechanism]
As illustrated in the above chemical formula, an image containing a decolorable composition in which a color developing compound and a developer interact with each other in a matrix material and the color developing compound exists as a coloring type. When the forming material adheres to the surface of the image forming medium exhibiting the above-mentioned decoloring action or is adhered to the surface of the image forming medium with a binder, the activity by heating or the decoloring aid treatment If the conversion is not performed, the color developer and the portion showing the decoloring action in the image forming medium are largely separated from each other, so the intermolecular interaction between them (coloration in terms of chemical equilibrium) Stronger than the interaction between the compound and the developer cannot occur, and the color development state of the color developing compound stabilized by the developer is maintained.
On the other hand, when activation is performed by heating and / or decoloring aid treatment, the developer, which is a low molecular compound, migrates in the decolorable composition and further exhibits decoloring properties. A part capable of intermolecular interaction with the part of the image forming medium that exhibits a decoloring action, and as a result, the color developing compound is a part of the image forming medium that exhibits the color erasing action of the developer. As a result, the color developing compound is decolored. In this invention, in order to promote this decoloring, it is the characteristics to heat-process in presence of the gas of the decoloring auxiliary agent (decoloring auxiliary in a gaseous state) mentioned later.
[0029]
[Combination ratio]
When the erasable composition used in the present invention contains a matrix material, it is composed of at least a color developing compound and a color developer. Preferred blending ratios are as follows.
The matrix material is usually in a proportion of 0.1 to 1000 parts by weight, preferably 0.5 to 100 parts by weight, and more preferably 1 to 20 parts by weight with respect to 1 part by weight of the color developing compound. The developer is usually in a proportion of 0.1 to 10 parts by weight, preferably 1 to 2 parts by weight, based on 1 part by weight of the color developing compound. When the developer is less than 0.1 parts by weight, the color development of the particulate decolorizable colorant due to the interaction between the color former and the developer becomes insufficient. When the developer exceeds 10 parts by weight, it becomes difficult to sufficiently reduce the interaction between the two.
[0030]
The molar ratio of the color erasing component (chemical structural unit) in the image forming medium exhibiting the color erasing function to the developer molecule is in a region where the color developer penetrates into the image forming medium during the color erasing process, or In the region where the decolorable component permeates into the decolorizable image forming material, the ratio is usually 5 mole ratio, preferably 10 mole ratio or more with respect to one molecule of the developer. When the decolorizable component is less than 5 molar ratio, it becomes difficult to completely bring the color development state of the decolorable composition to the decolored state. There is no particular upper limit to the molar ratio of the decoloring component (chemical structural unit) to the developer molecule in the image forming medium exhibiting the decoloring action.
[0031]
The present inventionUsed inErasable colorSex groupEven when the composition does not contain a matrix material, the mixing ratio of the color developing compound and the developer used is the same as when the matrix material is contained. However, when a matrix material is not used, a combination in which the color developing compound and the developer are solid-solved in a solid state and become an amorphous state is preferable as a restriction on the combination of the color developing compound and the developer. . For example, a combination of crystal violet lactone and zinc salicylate can be mentioned.
Incidentally, the erasable image forming material used in the present invention, as long as the function is not impaired, as needed, a plasticizer comprising a low molecular compound, a wax, a lubricant, a release agent, a light stabilizer, Appropriate amounts of additives such as antioxidants and charge control agents can be contained.
[0032]
[Discoloring aid]
For erasing the erasable image made of an image forming material containing the erasable composition formed on the image forming medium exhibiting the erasing action described above, the erasable image is caused to act. A substance that promotes the decoloring action, that is, a decoloring aid is used. The decoloring aid in the present invention is a normal temperatureHardThese are body substances that act on a decolorizable image in the gaseous state.
Even if the decoloring aid alone is a substance that does not exhibit a decoloring action, the action promotes the phenomenon that the developer in the decolorable composition migrates in the decolorable composition. As a result, any developer capable of facilitating intermolecular interaction between the developer and the image forming medium exhibiting a decoloring action can be used as a decoloring aid.
When the decolorizable composition contains a matrix material, it is preferable that the decolorization aid in the gaseous state is a solid solution (molecular dispersion in the solid) in the matrix material and exhibits a plasticizing action. Further, when the decolorizable composition does not contain a matrix material, the decoloring aid in the gaseous state is preferably one that dissolves or dissolves in the mixture of the color former and the developer..
[0033]
AlwaysAn organic compound present as a solid at a temperature and normal pressure is introduced into a closed container, for example, in an amount of about 5% to 50% of the internal volume of the container, and the container is cooled to room temperature or less than the melting point of the solid. If the temperature is maintained, the container may contain the solidSublimatedSteam gradually fills and eventually reaches equilibrium. The vapor of the solid organic compound thus generated (temperature is lower than the melting point) can be suitably used as a decoloring aid. However, it is not practical that naphthalene is highly sublimable but forms an explosive gas mixture with air because it requires strict safety measures for disaster prevention. From the viewpoint of disaster prevention and safety to the human body, it is possible to select a sublimable organic compound solid used as a “perfume” that can be safely used as a decoloring aid.
[0034]
For example, 6-acetyl-1,1,2,4,4,7-hexamethyltetrahydronaphthalene (melting point 46 ° C.), coumarin (melting point 68 ° C .; acute oral toxicity LD50: 293 mg / kg (rat)), cinnamic acid Methyl (melting point 38 ° C .; acute oral toxicity LD50: 2.5 g / kg (rat)), isoeugenol acetate (melting point 80 ° C .; acute oral toxicity LD50: 3.45 g / kg (rat)), dimethylbenzylcarbvinyl acetate ( Melting point 30 ° C .; lilac fragrance; acute oral toxicity LD50: 3.3 g / kg (rat)), 2-ethoxynaphthalene (melting point 37 ° C .; acute oral toxicity LD50: 3.11 g / kg (rat)), 2-methoxy Naphthalene (melting point 72 ° C .; acute oral toxicity LD50: 5 g / kg (rat)), borneol (melting point 206 to 208 ° C .; acute oral toxicity L 50: 6.5 g / kg (rat)), mantle (melting point 161-162 ° C; sublimation above 93 ° C; acute oral toxicity LD50: 2.33 g / kg (rat)), menthol (melting point 43-45 ° C; acute) Oral toxicity LD50: 3.18 g / kg (rat)), etc., vapor generated by sublimation can be suitably used as a decoloring aid in the gaseous state.
[0035]
Other examples of organic compounds that are solid at room temperature and act as decoloring aids include, for example, benzophenone (melting point: 48.5 ° C .; acute oral toxicity LD50:> 10 g / kg (rat)), 4, 4'-bis (diethylamino) benzophenone (melting point 94 ° C), 4,4'-bis (dimethylamino) benzophenone (melting point 174 ° C), 4,4'-dimethoxybenzophenone (melting point 145 ° C), 4,4'-dimethyl Benzophenone (melting point 95 ° C), 4-methoxybenzophenone (melting point 60 ° C), 4-methylbenzophenone (melting point 56 ° C), 2-n-propoxynaphthalene (melting point 40 ° C), 2,7-dimethoxynaphthalene (melting point 139 ° C) Aromatic hydrocarbon compounds which may have a substituent such as 3-acetylcoumarin (melting point: 122 ° C.), 5,7-dimeth Aromatic heterocyclic compounds which may have a substituent such as sicumarin (melting point 146 ° C.), 6,7-dimethoxy-4-methylcoumarin (melting point 139 ° C.), 7-ethoxycoumarin (melting point 90 ° C.), camphor (melting point 179 ° C), camphene (melting point 51.2 ° C), terpenes such as tricyclene (melting point 68 ° C), hinokitiol (melting point 52 ° C), derivatives of hinokitiol, 2-norbornanone (also known as norcamphor; melting point 95 ° C), etc. Examples include aliphatic cyclic ketones.
[0036]
[Decolorization temperature]
The softening point or melting point of the decolorizable composition containing the decoloring aid is obtained by solidifying the decolorizable composition in the gaseous state in the decolorizable composition forming the decolorizable image. It becomes lower than the case of the decolorizable composition which does not contain a decoloring aid. Therefore, as a guideline for the temperature when decoloring is performed using a decoloring aid in the gaseous state, “the softening point or melting point of the decolorizable composition with or without the decoloring aid” should be recommended. Can do. The softening point or melting point of the decolorizable composition containing the decoloring aid is the softening point of the decolorable composition in which the decoloring aid in the state where the gas of the decoloring aid is present is dissolved or dissolved. Or, it means the melting point, and the softening point or melting point of the decolorizable composition not containing the decoloring aid means the softening point or melting point of the decolorable composition itself in the absence of the decoloring aid gas. Means.
[0037]
In order to reduce the energy required for heating, the lowest possible temperature is preferred. For this purpose, the optimum temperature for the decoloring treatment may be determined experimentally, with the upper limit being the “softening point or melting point of the decolorizable composition not containing the decoloring aid”.
On the other hand, the temperature that does not exceed the lowest temperature among the thermal decomposition start temperatures of the components constituting the decolorizable image and the image forming medium is set as the upper limit of the decoloring temperature. Needless to say, when the upper limit temperature is exceeded, either the erasable color image or the component constituting the image forming medium causes an irreversible thermal decomposition reaction, making it difficult to reuse and regenerate.
[0038]
【Example】
Examples andreferenceThe present invention will be described in more detail with reference to examples. “Part” in the text is based on weight.
[0039]
Example 1
Thermal coloring dye Blue63 (manufactured by Yamamoto Kasei Co., Ltd.) as a color developing compound, 2 parts by weight of propyl gallate as a developer, 93 parts by weight of polystyrene as a matrix resin, and LR-147 as a charge control agent (Japan) 1 part by weight (made by Carlit Co., Ltd.) was mixed in advance and kneaded sufficiently at a temperature not exceeding 90 ° C. using a kneader to produce a decolorizable dye composition that developed a blue color. It was 76 degreeC when the softening point of this erasable dye composition was measured by the ring and ball method (Japanese Industrial Standard K2406).
[0040]
The erasable dye composition (containing a matrix resin) produced as described above was pulverized by a pulverizer to obtain a powder having an average particle diameter of 12 micrometers. Toner was prepared by adding 1 part by weight of hydrophobic silica to 100 parts by weight of this powder.
The obtained toner was put in a toner cartridge of an electrophotographic copying machine, and a test image (test chart) was transferred to neutral paper for a copying machine (reflectance 0.08). The obtained image had a sufficient image density, high durability under normal use conditions, and the image was maintained even when heated at 100 ° C. for 30 minutes. That is, in the absence of a decoloring aid, it was found that decolorization does not proceed in a short time even when heated to a temperature somewhat higher than the softening point (in this case, 76 ° C.).
[0041]
The decolorizable image can be decolored by heating to 150 ° C. or higher, or by heating to 70 ° C. to 80 ° C. in the presence of a decoloring aid in the gaseous state as described below.
100 sheets of paper on which a copy image was formed with the toner composed of the blue decolorable composition described above were put into a bat with a stainless steel lid (with silicone rubber packing; inner dimensions 260 mm × 230 mm × 40 mm) in a bundled state. A glass petri dish containing 10 g of isoeugenol acetate (melting point: 80 ° C.) was placed on the lid, and the air-cooled thermostat (DN83 model manufactured by Yamato Scientific Co., Ltd.) whose temperature was adjusted to 75 ° C. after closing the lid of the vat with lid. ) And allowed to stand at the same temperature for 12 hours, then took 4 hours to cool to room temperature and then taken out. As a result, all copy images formed on 100 sheets of paper were erased and could not be confirmed with the naked eye. The reflection density of each erasable image recording paper after erasing was measured and found to be 0.10. That is, it was confirmed that excellent decoloring characteristics were exhibited.
[0042]
The paper on which the copy image was erased by the above-described heat decoloring was left at 60 ° C. for 300 hours, but the image did not appear again. When cooling the stainless steel lid bat to room temperature, if it is taken out of the incubator and cooled rapidly, the crystallized isoeugenol acetate will precipitate on the entire inner wall of the stainless steel lid bat. If the temperature inside the incubator is slowly cooled by program temperature control without taking it out, the crystals remaining in the glass petri dish will become `` seed '' and crystallization will occur intensively around them, which will contaminate the inner wall of the container It becomes possible to collect without.
[0043]
The process of transferring another image to paper decolored by processing the decolorizable image by the above method and decoloring by heat treatment in the presence of a gas decoloring aid was repeated nine times. The tenth image transferred thereafter was of the same quality as the first image. Further, copying and erasing were repeated up to 50 times. As a result, the paper was mechanically damaged, but the quality of the copied image and the quality of the erased state were good.
[0044]
referenceExample1
Thermal coloring dye Blue63 (manufactured by Yamamoto Kasei Co., Ltd.) as a color developing compound, 2 parts by weight of propyl gallate as a developer, 93 parts by weight of polystyrene as a matrix resin, and LR-147 as a charge control agent (Japan) When 1 part by weight of Carlit Co., Ltd.) was mixed in advance and this mixture was kneaded using a Banbury mixer, it was melted and fluidized in about 2 minutes by frictional heat. The kneaded product was cooled and taken out to obtain a erasable dye composition that developed a blue color. It was 78 degreeC when the softening point of this erasable dye composition was measured by the ring and ball method (Japanese Industrial Standard K2406).
[0045]
The erasable dye composition produced as described above was pulverized by a pulverizer to obtain a powder having an average particle diameter of 12 micrometers. Toner was prepared by adding 1 part by weight of hydrophobic silica to 100 parts by weight of this powder.
The obtained toner was put in a toner cartridge of an electrophotographic copying machine, and a test image (test chart) was transferred to neutral paper for a copying machine (reflectance 0.08). The obtained image had a sufficient image density, high durability under normal use conditions, and the image was maintained even when heated at 100 ° C. for 30 minutes.
This decolorizable image can be decolored by heating to 190 ° C. or higher, or by heating to 70 ° C. to 80 ° C. in the presence of a gaseous decoloring aid as described below.
[0046]
100 sheets of paper on which a copy image was formed with the toner composed of the blue decolorable composition described above were put in a bat with a stainless steel lid (with silicone rubber packing; inner dimensions 260 mm × 230 mm × 40 mm) in a bundled state. On top of that, a glass petri dish containing 10 g of p-methylacetophenone (melting point 28 ° C .; boiling point 228 ° C.) was placed, the lid of the vat with lid was closed and sealed, and then the air-cooled incubator (temperature controlled to 75 ° C.) The sample was placed in a Yamato Scientific DN83 type) and allowed to stand at the same temperature for 12 hours, and after cooling to room temperature over 1 hour, it was taken out. As a result, all copy images formed on 100 sheets of paper were erased and could not be confirmed with the naked eye. The reflection density of each erasable image recording paper after erasing was measured and found to be 0.10. That is, it was confirmed that excellent decoloring characteristics were exhibited. The paper on which the copy image was erased by heating decolorization was left for 300 hours at 60 ° C., but the image did not appear again.
The process of transferring another image to paper on which the color erasable image was erased by the above-described method and then color erasing by heat treatment in the presence of a gas color erasing aid was repeated nine times. The tenth image transferred thereafter was of the same quality as the first image. Further, copying and erasing were repeated up to 50 times. As a result, the paper was mechanically damaged, but the quality of the copied image and the quality of the erased state were good.
[0047]
Example2
referenceExample1The kneaded product of the erasable composition used in the above was coarsely pulverized to a particle outer diameter of 1 mm with a cutter blade rotary pulverizer, and then the maximum particle diameter was 4 μm with a circulating air jet pulverizer equipped with a cyclone classifier. This was pulverized to the following, and further classified using another cyclonic classifier to obtain a decolorizable colorant as fine particles having a number average particle size of 1.0 μm and a volume average particle size of 2.0 μm. It contains 20 parts by weight of a methyl methacrylate-butyl acrylate-acrylic acid (ammonium salt) copolymer with 20 parts of this fine-particle color-removable colorant as a binder, and in addition, 2 parts by weight of a nonionic dispersant, propylene A three-roll roll was used to disperse the binder solution containing 10 parts by weight of glycol and 48 parts by weight of water to create a decolorizable water-based colorant.
[0048]
Using a bar coater, this erasable water-based colorant was applied to the entire surface of one side of a neutral paper for copying machines (reflectance: 0.08) and dried to form a so-called “solid coating” image. 100 sheets of such single-sided coated paper were prepared and put into a bat with a stainless steel lid (with silicone rubber packing; inner dimensions 260 mm × 230 mm × 40 mm), and then 2-methoxynaphthalene (melting point 72). ℃) Place a glass petri dish containing 10 g, close the lid of the bat with lid and seal it, then place it in an air-cooled incubator (DN83 model made by Yamato Kagaku) adjusted to 70 ° C and leave at that temperature for 12 hours. Then, it took 4 hours to cool to room temperature and then removed. As a result, all “solid” images formed on 100 sheets of paper were decolored and could not be confirmed with the naked eye. The reflection density of each erasable image-forming paper after erasing was measured and found to be 0.09. That is, it was confirmed that excellent decoloring characteristics were exhibited.
[0049]
The paper on which the copy image was erased by heating decolorization was left for 300 hours at 60 ° C., but the image did not appear again. When the stainless steel lid bat is cooled to room temperature, if it is taken out of the thermostat and cooled rapidly, 2-methoxynaphthalene microcrystals will be deposited on the entire inner wall of the stainless steel lid bat. If the temperature inside the incubator is slowly cooled by the program temperature control without taking it out of the container, the crystals remaining in the glass petri dish will be used as seeds, and crystallization will occur intensively around them. It becomes possible to collect without.
[0050]
Apply the above-mentioned erasable water-based colorant again using a bar coater to the paper that has been decolored by processing the erasable image by the above method and dry to form a “solid” image. The process of decoloring by heat treatment in the presence of a gas decoloring aid was repeated 9 times. Thereafter, the tenth “solid coating” image formed by coating was of the same quality as the first image. Further, image formation and erasing were repeated up to 50 times. As a result, the paper was mechanically damaged, but the quality of the “solid” image and the quality of the decolored state were good.
[0051]
【The invention's effect】
As described above in detail, according to the decolorizable image erasing method of the present invention, the erasable image formed on the paper is erased with excellent erasing characteristics, and the paper is reused. can do.
Claims (3)
（１）前記消色助剤の気体の存在下における可消色性組成物の軟化点又は融点、
（２）前記消色助剤の気体の不存在下における可消色性組成物の軟化点又は融点。The image forming medium on which the erasable color image is formed has the lowest temperature selected from the following temperatures, and is the lowest among the thermal decomposition start temperatures of the components constituting the erasable color image and the image forming medium. 3. The decolorizing method for an erasable image according to claim 1, wherein heating is performed in a temperature range in which a temperature not exceeding the upper limit is set.
(1) Softening point or melting point of the decolorizable composition in the presence of a gas of the decoloring aid,
(2) The softening point or melting point of the decolorizable composition in the absence of a gas of the decoloring aid.
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| JP2001093627A JP4127464B2 (en) | 2001-03-28 | 2001-03-28 | Decolorization method for erasable images |
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| JP2001093627A JP4127464B2 (en) | 2001-03-28 | 2001-03-28 | Decolorization method for erasable images |
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| US7184069B2 (en) * | 2003-12-08 | 2007-02-27 | Kabushiki Kaisha Toshiba | Image-erasing apparatus and image-erasing method |
| JP5376587B2 (en) | 2008-08-08 | 2013-12-25 | 花王株式会社 | Toner production method |
| JP5434321B2 (en) * | 2009-07-10 | 2014-03-05 | 富士ゼロックス株式会社 | COLOR TONER FOR PHOTOFIXING, MANUFACTURING METHOD THEREOF, ELECTROSTATIC IMAGE DEVELOPER, PROCESS CARTRIDGE, AND IMAGE FORMING DEVICE |
| EP3151066B1 (en) | 2009-11-23 | 2019-09-11 | Toshiba TEC Kabushiki Kaisha | Electrophotographic toner |
| EP2325699B1 (en) | 2009-11-23 | 2014-06-11 | Toshiba TEC Kabushiki Kaisha | Electrophotographic toner and method for producing the same |
| EP2325698A1 (en) | 2009-11-23 | 2011-05-25 | Toshiba TEC Kabushiki Kaisha | Electrophotographic toner and method for producing electrophotographic toner |
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