JP2004175101A - Water discoloring writing material, and water discoloring writing set using the same - Google Patents
Water discoloring writing material, and water discoloring writing set using the same Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は水変色性被筆記体及びそれを用いた水変色性筆記セットに関する。更に詳細には、乾燥した状態と、水の付着手段を介して水を含浸した状態では異なる様相を示す水変色性被筆記体及びそれを用いた水変色性筆記セットに関する。
【０００２】
【従来の技術】
従来より、基材上に低屈折率顔料を含有する多孔質層を設け、前記多孔質層に液体を吸液させることにより透明化して、下層に設けた画像を現出させる加工紙が開示されている（例えば、特許文献１参照）。
前記した提案の主たる応用分野として、書道練習等に適用されており、紙を支持体とするものが主体であり、耐久性に乏しかった。
【０００３】
【特許文献１】
特公昭５０−５０９７号公報
【０００４】
【発明が解決しようとする課題】
本発明は、特定目付け量の布帛を水不浸透性の材料上に設けたものを基材として適用することにより、水吸収性が適正で明瞭な筆記像を現出させることができると共に、前記した従来の耐久性不足を解消できることを見出し、この種の画像形成要素の商品性を更に高めるものである。
【０００５】
【課題を解決するための手段】
本発明は、低屈折率顔料をバインダー樹脂に分散状態に固着させた多孔質層を基材表面に設け、吸液状態と非吸液状態で透明性を異にする水変色性被筆記体において、前記基材が、水不浸透材上面に目付け量５ｇ／ｍ2 〜３０ｇ／ｍ2 の範囲にある布帛を設けたものである水変色性被筆記体を要件とする。
更には、前記水不浸透材がプラスチックフィルム、合成樹脂、合成紙から選ばれること、前記水不浸透材が不透明であること、前記低屈折率顔料が微粒子状珪酸であること等を要件とする。
更には、前記水変色性被筆記体と、水付着手段をセットにした水変色性筆記セットを要件とする。
【０００６】
【発明の実施の形態】
前記基材上に形成される多孔質層は、低屈折率顔料をバインダー樹脂と共に分散状態に固着させた層である。
前記低屈折率顔料としては、微粒子状珪酸、バライト粉、沈降性硫酸バリウム、炭酸バリウム、沈降性炭酸カルシウム、石膏、クレー、タルク、アルミナホワイト、塩基性炭酸マグネシウム等が挙げられ、これらは屈折率が１．４〜１．７の範囲にあり、液状組成物を吸液すると良好な透明性を示すものである。
前記低屈折率顔料の粒径は特に限定されるものではないが、０．０３〜１０．０μｍのものが好適に用いられる。
又、前記低屈折率顔料は２種以上を併用することもできる。
尚、好適に用いられる低屈折率顔料としては微粒子状珪酸が挙げられる。
前記微粒子状珪酸は、乾式法によるものであってもよいが、湿式法により製造される微粒子状珪酸（以下、湿式法微粒子状珪酸と称する）が特に効果的であり、実用性を満たす。
この点を以下に説明する。
微粒子状珪酸は非晶質の無定形珪酸として製造され、その製造方法により、四塩化ケイ素等のハロゲン化ケイ素の熱分解等の気相反応を用いる乾式法によるもの（以下、乾式法微粒子状珪酸と称する）と、ケイ酸ナトリウム等の酸による分解等の液相反応を用いる湿式法によるものとに大別されるが、本発明の意図する隠蔽性多孔質層として機能させるためには、湿式法微粒子状珪酸が最適である。
これは、乾式法微粒子状珪酸と湿式法微粒子状珪酸とでは構造が異なり、前記乾式法微粒子状珪酸は以下に示されるような珪酸が密に結合した三次元構造を形成するのに対して、湿式法微粒子状珪酸は、珪酸が縮合して長い分子配列を形成した、所謂、二次元構造部分を有している。
従って、前記乾式法微粒子状珪酸と比較して分子構造が粗になるため、湿式法微粒子状珪酸を多孔質層に適用した場合、乾式法微粒子状珪酸を用いる系と比較して乾燥状態における光の乱反射性に優れ、よって、常態での隠蔽性が大きくなるものと推察される。
又、前記本発明の多孔質層においては、水を吸液させるものであるから、湿式法微粒子状珪酸は乾式法微粒子状珪酸に比べて粒子表面にシラノール基として存在する水酸基が多く、親水性の度合いが大であり、好適に用いられる。
尚、前記多孔質層の常態での隠蔽性と吸液状態での透明性を調整するために、湿式法微粒子状珪酸と共に、他の汎用の低屈折率顔料を併用することもできる。
【０００７】
前記多孔質層中の湿式法微粒子状珪酸は、粒子径、比表面積、吸油量等の性状に左右されるが、常態での隠蔽性と吸液状態での透明性を共に満足するためには、塗布量が１ｇ／ｍ2 〜３０ｇ／ｍ2 であることが好ましく、より好ましくは、５ｇ／ｍ2 〜２０ｇ／ｍ2 である。１ｇ／ｍ2 未満では、常態で十分な隠蔽性を得ることが困難であり、又、３０ｇ／ｍ2 を越えると吸液時に十分な透明性を得ることが困難である。
前記微粒子状珪酸の粒径は特に限定されるものではないが、０．０３〜１０．０μｍのものが好適に用いられる。
前記微粒子状珪酸はバインダー樹脂を結合剤として含むビヒクル中に分散され、基材に塗布した後、揮発分を乾燥させて多孔質層を形成する。
前記バインダー樹脂としては、ウレタン系樹脂、ナイロン樹脂、酢酸ビニル樹脂、アクリル酸エステル樹脂、アクリル酸エステル共重合樹脂、アクリルポリオール樹脂、塩化ビニル−酢酸ビニル共重合樹脂、マレイン酸樹脂、ポリエステル樹脂、スチレン樹脂、スチレン共重合樹脂、ポリエチレン樹脂、ポリカーボネート樹脂、エポキシ樹脂、スチレン−ブタジエン共重合樹脂、アクリロニトリル−ブタジエン共重合樹脂、メタクリル酸メチル−ブタジエン共重合樹脂、ブタジエン樹脂、クロロプレン樹脂、メラミン樹脂、及び前記各樹脂エマルジョン、カゼイン、澱粉、セルロース誘導体、ポリビニルアルコール、尿素樹脂、フェノール樹脂等が挙げられる。
前記微粒子状珪酸とこれらのバインダー樹脂の混合比率は、微粒子状珪酸の種類及び性状に左右されるが、好ましくは、微粒子状珪酸１重量部に対してバインダー樹脂固形分０．５〜２重量部であり、より好ましくは、０．８〜１．５重量部である。微粒子状珪酸１重量部に対してバインダー樹脂固形分が０．５重量部未満の場合には、前記多孔質層の実用的な皮膜強度を得ることが困難であり、２重量部を越える場合には、前記多孔質層内部への水の浸透性が悪くなる。
前記多孔質層は、従来より公知の一般的な塗膜と比較して着色剤に対するバインダー樹脂の混合比率が小さいため、十分な皮膜強度が得られ難い。そこで、耐擦過強度を高めるために、前記のバインダー樹脂のうち、ナイロン樹脂又はウレタン系樹脂を用いると効果的である。
前記ウレタン系樹脂としては、ポリエステル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂、ポリエーテル系ウレタン樹脂等があり、２種以上を併用することもできる。又、前記樹脂が水に乳化分散したウレタン系エマルジョン樹脂や、イオン性を有するウレタン樹脂（ウレタンアイオノマー）自体のイオン基により乳化剤を必要とすることなく自己乳化して、水中に溶解乃至分散したコロイド分散型（アイオノマー型）ウレタン樹脂を用いることもできる。
尚、前記ウレタン系樹脂は水性ウレタン系樹脂又は油性ウレタン系樹脂のいずれを用いることもできるが、本発明においては水性ウレタン系樹脂、殊に、ウレタン系エマルジョン樹脂やコロイド分散型ウレタン系樹脂が好適に用いられる。
前記ウレタン系樹脂は単独で用いることもできるが、支持体の種類や皮膜に必要とされる性能に応じて、他のバインダー樹脂を併用することもできる。ウレタン系樹脂以外のバインダー樹脂を併用する場合、実用的な皮膜強度を得るためには、前記多孔質層のバインダー樹脂中にウレタン系樹脂を固形分重量比率で３０％以上含有させることが好ましい。
前記バインダー樹脂において、架橋性のものは任意の架橋剤を添加して架橋させることにより、さらに皮膜強度を向上させることができる。
前記バインダー樹脂には、水との親和性に大小が存在するが、これらを組み合わせることにより、多孔質層中への浸透時間、浸透度合い、浸透後の乾燥の遅速を調整することができる。更には、適宜分散剤を添加して前記調整をコントロールすることができる。
【０００８】
なお、前記多孔質層中には、従来より公知の二酸化チタン被覆雲母、酸化鉄−二酸化チタン被覆雲母、酸化鉄被覆雲母、グアニン、絹雲母、塩基性炭酸鉛、酸性砒酸鉛、オキシ塩化ビスマス等の金属光沢顔料を添加したり、一般染料や顔料、蛍光染料や蛍光顔料を混在させて色変化を多様化させることができる。
又、温度変化により可逆的に色変化する、従来より公知の可逆熱変色顔料を混在させて、環境温度や付着させる水温により色変化させることができる。
更には、前記多孔質層の上層、下層、及び／又は近傍には着色層を配設して様相変化を更に多様化させることができる。
前記多孔質層及び着色層は、ベタ印刷状のものに限らず、文字、記号、図柄等の像であってもよい。
前記多孔質層及び着色層は、従来より公知の手段、例えば、スクリーン印刷、オフセット印刷、グラビヤ印刷、コーター、タンポ印刷、転写等の印刷手段、刷毛塗り、スプレー塗装、静電塗装、電着塗装、流し塗り、ローラー塗り、浸漬塗装、等により適宜、形成できる。
【０００９】
前記基材として水不浸透材上に設けられる布帛は、織布、編物、不織布等が挙げられる。具体的には、目付け量５ｇ／ｍ2 〜３０ｇ／ｍ2 、好ましくは１０ｇ／ｍ2 〜２５ｇ／ｍ2 の範囲にある布帛が用いられ、前記目付け量が５ｇ／ｍ2 未満の系では、水の吸収性が不均質且つ不十分であり、明瞭な筆記像を形成し難い。
前記布帛のうち、不織布を用いることにより、該不織布上に多孔質層を設けた状態で指触すると書道用紙のような触感を有し、書道の練習に近い状態を付与できるため、好適である。
【００１０】
前記布帛の裏面に設けられる水不浸透材は、ポリオレフィン系樹脂、可塑剤をブレンドして得た塩化ビニル樹脂等の軟質化プラスチック、スチレン系、ウレタン系、ポリエステル系、ポリアミド系、ポリブタジエン系、フッ素系等の熱可塑性エラストマーからなるフィルム形態のもの、或いは、従来より汎用の合成紙等を適宜手段により布帛と貼着させて、基材となす。
また、合成樹脂を溶解又は分散させた液状体を布帛に塗布し、合成樹脂の層を設けて基材とすることもできる。
前記基材の適用により、従来の紙を基材として適用する系に較べ、吸水性に富み、明瞭な筆記像を速やかに形成し易いと共に、吸水時における強度の低下もなく、繰り返しの実用性を満足させる。
特に、前記合成紙は、紙のような質感、柔軟性を有すると共に、耐水性を有するため、好適に用いられる。
前記水不浸透材は、透明、着色透明、或いは、半透明であってもよいが筆記体を載置する机等の色調の影響を受けることのない不透明なものが好適である。
前記したように基材を積層形態となしたことにより、誤って水をシート表面に零したり、過飽和の水を吸収させた場合における、シート背面よりの水漏れによる汚染を回避できると共に、滑り止め機能を果たすこともできる。
【００１１】
第２の発明は、前記水変色性被筆記体と水付着手段をセットにした水変色性筆記セットを要件とする。
前記水付着手段は、連続気孔を有するプラスチック多孔体又は繊維加工体、或いは前記プラスチック多孔体又は繊維加工体をペン先部材として適用した筆記又は塗布具を挙げることができる。
前記における連続気孔を有するプラスチック多孔体又は繊維加工体は、水を適宜量、吸収し、吐出させるものであればよく、従来より汎用のポリオレフィン系、ポリウレタン系、その他各種プラスチックの連続気孔体や繊維を集束させた毛筆状のもの、繊維の樹脂加工又は熱溶着加工によるもの、フェルト、不織布形態のものを挙げることができ、形状、寸法は目的に応じて任意に設定できる。
更に、前記した各種材料をペン先部材として適用し、水収容容器の先端に取り付けた筆記具又は塗布具形態のものが有効である。
前記水付着手段をセットにすることにより、任意の筆記像を自在に簡便に形成でき、実用性を高めることができる。
【００１２】
【実施例】
以下に実施例を示すが、本発明は実施例に限定されない。尚、実施例中の部は重量部を示す。
実施例１
目付け量２０ｇ／ｍ2 の赤色ポリエステル製不織布（２５０ｍｍ×３５０ｍｍ）の裏面に、水不浸透材として布帛と同一形状の白色合成紙（厚み１６０μｍ）をイソシアネート系接着剤を用いて貼り合わせ、基材を得た。
前記基材を構成する布帛上に、湿式法微粉末シリカ〔商品名：ニップシールＥ−２００、日本シリカ工業（株）製〕１５部、ウレタンエマルジョン〔商品名：ハイドランＨＷ−９３０、大日本インキ化学工業（株）製、固形分５０％〕３０部、水５０部、シリコーン系消泡剤０．５部、水系インキ用増粘剤３部、エチレングリコール１部、イソシアネート系架橋剤３部を均一に混合、攪拌してなる白色スクリーン印刷用インキを用いて、８０メッシュのスクリーン版にてベタ印刷し、８０℃で５分間乾燥硬化させて多孔質層を形成して水変色性被筆記体を得た。
前記水変色性被筆記体は、常態では布帛の赤色は隠蔽状態であり、多孔質層による全面が白色の状態が視覚され、前記多孔質層上を指触すると、書道用紙のような触感を有していた。
前記水変色性被筆記体と、毛筆を組み合わせて水変色性筆記セットを得た。
前記水変色性被筆記体上に、水を含浸させた毛筆で筆記すると、その部分の多孔質層が透明化して、下層の布帛による明瞭な赤色の筆跡が視覚される。
前記筆跡は、水が未乾燥状態では保持されており、水が乾燥すると元の白色に復し、筆跡は不可視状態となる。
前記様相変化は、水の付着により繰り返し行うことができ、耐水性も有していた。
また、机上に載置して筆記する場合、水不浸透材の合成紙に少量の水を付けて机上に置くと、被筆記体の滑りを防止でき、毛筆で筆記する際に被筆記体を手で押さえたり、文鎮を使用する必要もないため、被筆記体としての利便性に優れていた。
【００１３】
実施例２
目付け量１５ｇ／ｍ2 の白色ナイロン製不織布（２５０ｍｍ×３００ｍｍ）の裏面に、水不浸透材として布帛と同一形状の白色合成紙（厚み１１０μｍ）をアクリル樹脂系接着剤を用いて貼り合わせ、基材を得た。
前記基材を構成する布帛上に、青色顔料〔商品名：サンダイスーパーブルーＧＬＬ、山陽色素（株）社製〕５部、アクリル酸エステルエマルジョン〔商品名：モビニール７６３、ヘキスト合成（株）社製、固形分４８％〕５０部、水性インキ増粘剤３部、レベリング剤０．５部、消泡剤０．３部、エポキシ系架橋剤５部を均一に混合攪拌してなる青色スクリーン印刷用インキを用いて、１５０メッシュのスクリーン版にて全面ベタ印刷し、７０℃で３分間乾燥硬化させて着色層を形成した。
次いで、前記着色層上の全面に、湿式法微粉末シリカ〔商品名：ニップシールＥ−２２０、日本シリカ工業（株）製〕１５部、黄色顔料〔商品名：サンダイスーパーイエロー１０ＧＳ、山陽色素（株）社製〕１部、ウレタンエマルジョン〔商品名：ハイドランＡＰ−２０、大日本インキ化学工業（株）社製、固形分３０％〕４５部、水４０部、シリコーン系消泡剤０．５部、水系インキ用増粘剤３部、エチレングリコール１部、イソシアネート系架橋剤３部を均一に攪拌混合して得た黄色スクリーン印刷用インキを用いて、１００メッシュのスクリーン版にてベタ印刷し、８０℃で５分間乾燥硬化させて多孔質層を形成して水変色性被筆記体を得た。
前記水変色性被筆記体は、常態では着色層による青色は隠蔽状態であり、多孔質層による全面が淡黄色の状態が視覚され、前記多孔質層上を指触すると、書道用紙のような触感を有していた。
前記水変色性被筆記体と、毛筆を組み合わせて水変色性筆記セットを得た。
前記水変色性被筆記体上に、水を含浸させた毛筆で筆記すると、その部分の多多孔質層が透明化して、着色層の青色と多孔質層の黄色が混色となった明瞭な緑色の筆跡が視覚される。
前記筆跡は、水が未乾燥状態では保持されており、水が乾燥すると元の淡黄色に復し、筆跡は不可視状態となる。
前記様相変化は、水の付着により繰り返し行うことができ、耐水性も有していた。
また、机上に載置して筆記する場合、水不浸透材の合成紙に少量の水を付けて机上に置くと、被筆記体の滑りを防止でき、毛筆で筆記する際に被筆記体を手で押さえたり、文鎮を使用する必要もないため、被筆記体としての利便性に優れていた。
【００１４】
実施例３
目付け量２５ｇ／ｍ2 のポリプロピレンとポリエステルが５０：５０の比率で混合されてなる白色不織布（２５０ｍｍ×３５０ｍｍ）の裏面に、水不浸透材として布帛と同一形状の白色合成紙（厚み１６０μｍ）をウレタン樹脂系接着剤で貼り合わせ、基材を得た。
次いで、前記基材を構成する布帛上に、緑色顔料〔商品名：サンダイスーパーグリーンＬＸＢ、山陽色素（株）社製〕３部、アクリル酸エステルエマルジョン〔商品名：ＮＥＯＣＲＹＬ Ａ−６２２、アビシア（株）社製、固形分３２％〕５０部、水性インキ増粘剤３部、レベリング剤０．５部、消泡剤０．３部、エポキシ系架橋剤３部を均一に混合攪拌してなる緑色スクリーン印刷用インキを用いて、１５０メッシュのスクリーン版にて５０ｍｍ×５０ｍｍの複数の正方形を、互いの間隔が１ｍｍとなるように印刷し、７０℃で３分間乾燥硬化させて着色層を形成した。
更に、前記着色層上に、湿式法微粉末シリカ〔商品名：ニップシールＥ−２２０、日本シリカ工業（株）製〕１５部、ウレタンエマルジョン〔商品名：ハイドランＡＰ−２０、大日本インキ化学工業（株）社製、固形分３０％〕４５部、水４０部、シリコーン系消泡剤０．５部、水系インキ用増粘剤３部、エチレングリコール１部、イソシアネート系架橋剤３部を均一に攪拌混合して得た白色スクリーン印刷用インキを用いて、１８０メッシュのスクリーン版にて全面ベタ印刷し、７０℃で５分間乾燥硬化させて多孔質層を形成して水変色性被筆記体を得た。
前記水変色性被筆記体は、常態では淡緑色の多孔質層が線幅１ｍｍの罫線で分割された状態が視覚され、前記多孔質層上を指触すると、書道用紙のような触感を有していた。
前記水変色性被筆記体と、毛筆を組み合わせて水変色性筆記セットを得た。
前記水変色性被筆記体上に、水を含浸させた毛筆で筆記すると、その部分の多多孔質層が透明化して、着色層による明瞭な緑色の筆跡が視覚される。
前記筆跡は、水が未乾燥状態では保持されており、水が乾燥すると元の淡緑色に復し、筆跡は不可視状態となる。
前記様相変化は、水の付着により繰り返し行うことができ、耐水性も有していた。
また、机上に載置して筆記する場合、水不浸透材の合成紙に少量の水を付けて机上に置くと、被筆記体の滑りを防止でき、毛筆で筆記する際に被筆記体を手で押さえたり、文鎮を使用する必要もないため、被筆記体としての利便性に優れていた。
【００１５】
実施例４
目付け量２０ｇ／ｍ2 のポリプロピレン製不織布（５００ｍｍ×５００ｍｍ）の裏面に、水不浸透材として布帛と同一形状の白色軟質塩化ビニルフィルム（厚み５０μｍ）をウレタン樹脂系接着剤で貼り合わせ、基材を得た。
前記基材を構成する布帛上に、ピンク色蛍光顔料〔商品名：エポカラーＦＰ２０、（株）日本触媒製〕３部、アクリル酸エステルエマルジョン〔商品名：ＮＥＯＣＲＹＬ Ａ−６１２、アビシア（株）社製、固形分３５％〕５０部、水性インキ増粘剤３部、レベリング剤０．５部、消泡剤０．３部、エポキシ系架橋剤３部を均一に混合攪拌してなるピンク色スクリーン印刷用インキを用いて、１５０メッシュのスクリーン版にて全面ベタ印刷し、７０℃で３分間乾燥硬化させて着色層を形成した。
次いで、前記着色層上の全面に、湿式法微粉末シリカ〔商品名：ニップシールＥ−２２０、日本シリカ工業（株）製〕１５部、ウレタンエマルジョン〔商品名：ハイドランＡＰ−２０、大日本インキ化学工業（株）社製、固形分３０％〕４５部、水４０部、シリコーン系消泡剤０．５部、水系インキ用増粘剤３部、エチレングリコール１部、イソシアネート系架橋剤３部を均一に攪拌混合して得た白色スクリーン印刷用インキを用いて、１００メッシュのスクリーン版にて全面ベタ印刷し、７０℃で５分間乾燥硬化させて多孔質層を形成して水変色性被筆記体を得た。
前記水変色性被筆記体は、常態では着色層のピンク色は隠蔽状態であり、多孔質層による全面が白色の状態が視覚され、前記多孔質層上を指触すると、書道用紙のような触感を有していた。
前記水変色性被筆記体と、内部に水を収容可能なマーキングペンを組み合わせて水変色性筆記セットを得た。
前記水変色性被筆記体上に、水を収容したマーキングペンで筆記すると、その部分の多孔質層が透明化して、下層の着色層による明瞭なピンク色の筆跡が視覚される。
前記筆跡は、水が未乾燥状態では保持されており、水が乾燥すると元の白色に復し、筆跡は不可視状態となる。
前記様相変化は、水の付着により繰り返し行うことができ、耐水性も有していた。
また、前記被筆記体を乱暴に扱っても、折れ曲がったり、破れて破損する等の不具合もなく、且つ、収納する際に折り畳んでも、折り皺が発生することなく、被筆記体としての有用性はもちろんのこと、取り扱いの利便性にも優れており、子供用教習具に適していた。
【００１６】
実施例５
目付け量２５ｇ／ｍ2 のキュプラ製平織布（９００ｍｍ×９００ｍｍ）の裏面に、水不浸透材として布帛と同一形状の白色エチレン酢酸ビニルフィルム（厚み１５０μｍ）を位置させ、端部の周囲をバイアステープで縫製して基材を得た。
前記基材を構成する布帛上に、ピンク色蛍光顔料〔商品名：エポカラーＦＰ２０、（株）日本触媒製〕３部、アクリル酸エステルエマルジョン〔商品名：ＮＥＯＣＲＹＬ Ａ−６１２、アビシア（株）社製、固形分３５％〕５０部、水性インキ増粘剤３部、レベリング剤０．５部、消泡剤０．３部、エポキシ系架橋剤３部を均一に混合攪拌してなるピンク色スクリーン印刷用インキを用いて、１５０メッシュのスクリーン版にて中央部に７００ｍｍ×７００ｍｍの大きさにてベタ印刷し、６０℃で１０分間乾燥硬化させて着色層を形成した。
次いで、前記着色層上に、湿式法微粉末シリカ〔商品名：ニップシールＥ−２２０、日本シリカ工業（株）製〕１５部、ウレタンエマルジョン〔商品名：ハイドランＡＰ−２０、大日本インキ化学工業（株）社製、固形分３０％〕４５部、水４０部、シリコーン系消泡剤０．５部、水系インキ用増粘剤３部、エチレングリコール１部、イソシアネート系架橋剤３部を均一に攪拌混合して得た白色スクリーン印刷用インキを用いて、１００メッシュのスクリーン版にて着色層と同じ大きさで全面ベタ印刷し、６０℃で１０分間乾燥硬化させて多孔質層を形成した。
更に、多孔質層の近傍に、一般印刷インキにより、図柄と図柄に関連した文字を印刷して水変色性被筆記体を得た。
前記水変色性被筆記体は、常態では着色層のピンク色は隠蔽状態であり、多孔質層による白色部分と周囲に印刷された図柄と文字が視覚されている。
前記水変色性被筆記体と、内部に水を収容可能なマーキングペンを組み合わせて水変色性筆記セットを得た。
前記水変色性被筆記体上に、水を収容したマーキングペンで筆記すると、その部分の多孔質層が透明化して、下層の着色層による明瞭なピンク色の筆跡が視覚される。
前記筆跡は、水が未乾燥状態では保持されており、水が乾燥すると元の白色に復し、筆跡は不可視状態となる。
前記様相変化は、水の付着により繰り返し行うことができ、耐水性も有していた。
また、前記被筆記体を乱暴に扱っても、折れ曲がったり、破れて破損する等の不具合もなく、且つ、収納する際に折り畳んでも、折り皺が発生することなく、被筆記体としての有用性はもちろんのこと、取り扱いの利便性にも優れており、しかも、文字等の練習を行う際には多孔質層の周囲に印刷された図柄及び文字を真似して筆記することもできるため、子供用教習具に適していた。
【００１７】
実施例６
目付け量３０ｇ／ｍ2 の白色ポリエステル製タフタ布（７００ｍｍ×７００ｍｍ）の裏面に、アクリル樹脂溶液をナイフコーターで塗工し、乾燥硬化させることにより、厚さ１０μｍの水不浸透材を設けて基材を得た。
前記基材を構成する布帛上に、青色顔料〔商品名：サンダイスーパーブルーＧＬＬ、山陽色素（株）社製〕５部、アクリル酸エステルエマルジョン〔商品名：ボンコートＡＢ７８２、大日本インキ工業（株）社製、固形分４５％〕５０部、水性インキ増粘剤３部、レベリング剤０．５部、消泡剤０．３部、エポキシ系架橋剤５部を均一に混合攪拌してなる青色スクリーン印刷用インキを用いて、１５０メッシュのスクリーン版にて中央部に５００ｍｍ×５００ｍｍの大きさにてベタ印刷し、１３０℃で３分間乾燥硬化させて着色層を形成した。
次いで、前記着色層上の全面に、湿式法微粉末シリカ〔商品名：ニップシールＥ−２２０、日本シリカ工業（株）製〕１５部、ウレタンエマルジョン〔商品名：ハイドランＡＰ−２０、大日本インキ化学工業（株）社製、固形分３０％〕４５部、水４０部、シリコーン系消泡剤０．５部、水系インキ用増粘剤３部、エチレングリコール１部、イソシアネート系架橋剤３部を均一に攪拌混合して得た白色スクリーン印刷用インキを用いて、１００メッシュのスクリーン版にてベタ印刷し、８０℃で５分間乾燥硬化させて多孔質層を形成した。
次いで前記多孔質層の近傍に、一般印刷インキにより、図柄と図柄に関連した文字を印刷して水変色性被筆記体を得た。
前記水変色性被筆記体は、常態では着色層の青色は隠蔽状態であり、多孔質層による白色部分と周囲の図柄及び文字が視覚されている。
前記水変色性被筆記体と、内部に水を収容可能なマーキングペンを組み合わせて水変色性筆記セットを得た。
前記水変色性被筆記体上に、水を収容したマーキングペンで筆記すると、その部分の多孔質層が透明化して、下層の着色層による明瞭な青色の筆跡が視覚される。
前記筆跡は、水が未乾燥状態では保持されており、水が乾燥すると元の白色に復し、筆跡は不可視状態となる。
前記様相変化は、水の付着により繰り返し行うことができ、耐水性も有していた。
また、前記被筆記体を乱暴に扱っても、折れ曲がったり、破れて破損する等の不具合もなく、且つ、収納する際に折り畳んでも、折り皺が発生することなく、被筆記体としての有用性はもちろんのこと、取り扱いの利便性にも優れており、しかも、文字等の練習を行う際には多孔質層の周囲に印刷された図柄及び文字を真似して筆記することもできるため、子供用教習具に適していた。
【００１８】
【発明の効果】
本発明の水変色性被筆記体は、基材として水不浸透材上に特定目付け量の布帛を設けたものであるから、紙を基材とする系に較べて、多孔質層からの水の浸透、保持性が適正であり、明瞭な筆記像を速やかに形成して視覚させることができると共に、耐水性に優れる。
また、基材としてプラスチックフィルム、合成樹脂、合成紙等の水不浸透材上に布帛を設けることによって、紙のような触感を与えることもできるため、商品価値の高い水変色性被筆記体を提供できる。
更に、水付着手段と前記水変色性被筆記体をセットにすることにより、簡易に筆記像を現出させる実用性の高い水変色性筆記セットを提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a water discolorable writing object and a water discolorable writing set using the same. More specifically, the present invention relates to a water discolorable writing object which shows different aspects in a dry state and in a state impregnated with water through a water attaching means, and a water discolorable writing set using the same.
[0002]
[Prior art]
BACKGROUND ART Conventionally, a processed paper has been disclosed in which a porous layer containing a low refractive index pigment is provided on a base material, and the porous layer is made transparent by absorbing a liquid into the porous layer to reveal an image provided in a lower layer. (For example, see Patent Document 1).
As a main application field of the above-mentioned proposal, it has been applied to calligraphy practice and the like, and mainly uses paper as a support, and has poor durability.
[0003]
[Patent Document 1]
Japanese Patent Publication No. 50-5097
[Problems to be solved by the invention]
The present invention, by applying a specific basis weight of a cloth provided on a water-impermeable material as a base material, water absorbency can be appropriate and a clear written image can be produced, and It has been found that the conventional shortage of durability can be solved and the commercial value of this type of image forming element is further improved.
[0005]
[Means for Solving the Problems]
The present invention provides a water-discolorable writing object in which a low refractive index pigment is fixed to a binder resin in a dispersed state, and a porous layer is provided on the substrate surface, and the transparency differs between a liquid absorbing state and a non-liquid absorbing state. , wherein the substrate, the water-discoloring the cursive requirements is provided with a fabric water impermeable material upper surface is in the range of basis weight 5g / m 2 ~30g / m 2 .
Further, the water-impermeable material is selected from a plastic film, a synthetic resin, and synthetic paper, the water-impermeable material is opaque, and the low refractive index pigment is a particulate silica. .
Further, a water-discolorable writing set including the water-discolorable writing object and the water-adhering means is required.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The porous layer formed on the base material is a layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin.
Examples of the low-refractive-index pigment include particulate silica, barite powder, precipitated barium sulfate, barium carbonate, precipitated calcium carbonate, gypsum, clay, talc, alumina white, basic magnesium carbonate, and the like. Is in the range of 1.4 to 1.7, and shows good transparency when the liquid composition is absorbed.
The particle size of the low refractive index pigment is not particularly limited, but a particle having a particle size of 0.03 to 10.0 μm is preferably used.
Further, two or more low refractive index pigments may be used in combination.
In addition, as the low-refractive-index pigment that is preferably used, fine-particle silica may be used.
The particulate silica may be obtained by a dry method, but particulate silica produced by a wet method (hereinafter, referred to as a wet particulate silica) is particularly effective and satisfies practicality.
This will be described below.
The particulate silica is produced as an amorphous amorphous silicic acid, and is produced by a dry method using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as a dry method particulate silica). ) And a wet method using a liquid phase reaction such as decomposition with an acid such as sodium silicate. In order to function as the concealable porous layer intended in the present invention, a wet method is used. Processed particulate silica is most suitable.
This is because the dry process particulate silica and the wet process particulate silica have different structures, whereas the dry process particulate silica forms a three-dimensional structure in which silicic acid is tightly coupled as shown below, The wet-processed particulate silica has a so-called two-dimensional structure in which the silica is condensed to form a long molecular arrangement.
Therefore, since the molecular structure is coarser than that of the dry method particulate silica, when the wet method particulate silica is applied to the porous layer, the light in a dry state is lower than the system using the dry method particulate silica. It is presumed that it has excellent diffuse reflection properties, and thus has a large concealing property under normal conditions.
Further, in the porous layer of the present invention, since water is absorbed, the wet method particulate silica has more hydroxyl groups present as silanol groups on the particle surface than the dry method particulate silica, and has a hydrophilic property. Is large and is preferably used.
In order to adjust the concealing property of the porous layer in the normal state and the transparency in the liquid absorbing state, other general-purpose low-refractive-index pigments can be used together with the wet-processed particulate silica.
[0007]
The wet process particulate silica in the porous layer depends on properties such as the particle size, specific surface area, and oil absorption.However, in order to satisfy both the hiding property in the normal state and the transparency in the liquid absorbing state, it is preferable that the coating amount is 1g / m 2 ~30g / m 2 , more preferably 5g / m 2 ~20g / m 2 . If it is less than 1 g / m 2 , it is difficult to obtain sufficient concealing properties under normal conditions, and if it exceeds 30 g / m 2 , it is difficult to obtain sufficient transparency when absorbing liquid.
The particle size of the particulate silica is not particularly limited, but a particle size of 0.03 to 10.0 μm is preferably used.
The particulate silica is dispersed in a vehicle containing a binder resin as a binder, applied to a substrate, and then dried to form a porous layer by drying volatile components.
As the binder resin, urethane resin, nylon resin, vinyl acetate resin, acrylate resin, acrylate copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, polyester resin, styrene Resin, styrene copolymer resin, polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and Examples include resin emulsions, casein, starch, cellulose derivatives, polyvinyl alcohol, urea resins, phenol resins, and the like.
The mixing ratio of the particulate silica and the binder resin depends on the type and properties of the particulate silica, but preferably 0.5 to 2 parts by weight of the binder resin solid content to 1 part by weight of the particulate silica. And more preferably 0.8 to 1.5 parts by weight. When the binder resin solid content is less than 0.5 part by weight with respect to 1 part by weight of the particulate silica, it is difficult to obtain a practical film strength of the porous layer. In this case, the permeability of water into the inside of the porous layer becomes poor.
The porous layer has a small mixing ratio of the binder resin to the coloring agent as compared with a conventionally known general coating film, so that it is difficult to obtain sufficient film strength. Therefore, it is effective to use a nylon resin or a urethane-based resin among the binder resins described above in order to increase the rubbing resistance.
Examples of the urethane-based resin include a polyester-based urethane resin, a polycarbonate-based urethane resin, and a polyether-based urethane resin, and two or more urethane-based resins may be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid dissolved or dispersed in water by self-emulsifying without the need for an emulsifier due to the ionic groups of the urethane resin having an ionic property (urethane ionomer) itself. Dispersion type (ionomer type) urethane resins can also be used.
The urethane-based resin may be any of an aqueous urethane-based resin or an oil-based urethane-based resin, but in the present invention, an aqueous urethane-based resin, particularly, a urethane-based emulsion resin or a colloid-dispersed urethane-based resin is preferable. Used for
The urethane-based resin can be used alone, but other binder resins can be used in combination according to the type of the support and the performance required for the film. When a binder resin other than the urethane resin is used in combination, it is preferable that the binder resin of the porous layer contains the urethane resin in a solid content ratio of 30% or more in order to obtain practical film strength.
In the binder resin, a crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent to perform crosslinking.
The binder resin has different degrees of affinity with water, but by combining these, the penetration time into the porous layer, the degree of penetration, and the delay of drying after penetration can be adjusted. Furthermore, the adjustment can be controlled by adding a dispersant as appropriate.
[0008]
In the porous layer, conventionally known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, lead acid arsenate, bismuth oxychloride, etc. The color change can be diversified by adding a metallic luster pigment or mixing a general dye or pigment, a fluorescent dye or a fluorescent pigment.
In addition, a conventionally known reversible thermochromic pigment, which changes color reversibly with a change in temperature, can be mixed to change the color according to the environmental temperature or the temperature of the water to be attached.
Further, a color layer may be provided on the upper layer, the lower layer, and / or the vicinity of the porous layer to further diversify the aspect change.
The porous layer and the colored layer are not limited to those in a solid printing state, and may be images such as characters, symbols, and designs.
The porous layer and the colored layer may be formed by a conventionally known means, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, and electrodeposition coating. It can be appropriately formed by flow coating, roller coating, dip coating, or the like.
[0009]
Examples of the cloth provided on the water-impermeable material as the base include woven cloth, knitted cloth, and nonwoven cloth. Specifically, the weight per unit area 5g / m 2 ~30g / m 2 , the preferably used is a fabric in the range of 10g / m 2 ~25g / m 2 , the basis weight 5 g / m 2 less than the system, The water absorption is heterogeneous and insufficient, and it is difficult to form a clear handwritten image.
Of the above-mentioned cloths, it is preferable to use a non-woven fabric because it has a tactile sensation like a calligraphy paper when touched with a porous layer provided on the non-woven fabric, and can provide a state close to a practice of calligraphy. .
[0010]
The water-impermeable material provided on the back of the fabric is a polyolefin-based resin, a softened plastic such as a vinyl chloride resin obtained by blending a plasticizer, a styrene-based, a urethane-based, a polyester-based, a polyamide-based, a polybutadiene-based, or a fluorine-based resin. A film base made of a thermoplastic elastomer such as a thermoplastic elastomer, or a synthetic paper generally used in the past is pasted to a cloth by an appropriate means to form a base material.
Alternatively, a liquid material in which a synthetic resin is dissolved or dispersed may be applied to a cloth, and a synthetic resin layer may be provided as a base material.
By the use of the base material, compared to a system using a conventional paper as a base material, it is rich in water absorbability, easily forms a clear written image quickly, has no decrease in strength at the time of water absorption, and is practical for repetition. To satisfy.
In particular, the synthetic paper is suitably used because it has a texture and flexibility like paper and has water resistance.
The water-impermeable material may be transparent, colored transparent, or translucent, but is preferably an opaque material that is not affected by the color tone of a desk or the like on which the cursive is placed.
By forming the base material in the laminated form as described above, water can be spilled to the sheet surface by mistake, or when supersaturated water is absorbed, contamination due to water leakage from the back surface of the sheet can be avoided, and slippage can be prevented. It can also serve as a stop function.
[0011]
The second invention requires a water-discolorable writing set in which the water-discolorable writing object and the water attaching means are set.
Examples of the water adhering means include a plastic porous body or a fiber processed body having continuous pores, or a writing or applicator using the plastic porous body or the fiber processed body as a pen point member.
The porous plastic body or fiber processed body having continuous pores in the above may be any one that absorbs and discharges water in an appropriate amount, and is a general-purpose polyolefin-based, polyurethane-based, and other various plastic continuous pores or fibers. Can be enumerated, such as a brush-like shape, a resin-processed or heat-welded fiber, a felt, and a non-woven fabric. The shape and dimensions can be arbitrarily set according to the purpose.
Further, it is effective to apply the above-mentioned various materials as a pen tip member, and to use a writing instrument or an applicator in the form of a writing instrument or an applicator attached to the tip of a water storage container.
By setting the water adhesion unit as a set, an arbitrary handwritten image can be freely and easily formed, and practicality can be improved.
[0012]
【Example】
Examples are shown below, but the present invention is not limited to the examples. Parts in the examples are parts by weight.
Example 1
A red synthetic nonwoven fabric (250 mm × 350 mm) having a basis weight of 20 g / m 2 was bonded to the back surface of a white synthetic paper (thickness: 160 μm) having the same shape as the fabric as a water-impermeable material using an isocyanate-based adhesive. Got.
15 parts of wet-process fine silica (trade name: Nip Seal E-200, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran HW-930, Dainippon Ink and Chemicals, Ltd.] 30% of water, 50 parts of water, 0.5 part of silicone-based defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of isocyanate-based cross-linking agent. Using a white screen printing ink obtained by mixing and stirring, solid printing was performed on an 80-mesh screen plate, dried and cured at 80 ° C. for 5 minutes to form a porous layer, and a water-discolorable writing object was obtained. Obtained.
In the water discolorable writing object, the red color of the fabric is normally in a concealed state, and the entire surface of the porous layer is white, and when touching the porous layer, a touch like calligraphy paper is obtained. Had.
A water discolorable writing set was obtained by combining the water discolorable writing object and a brush.
When writing is performed on the water-discolorable writing object with a brush impregnated with water, the porous layer in that portion becomes transparent, and a clear red handwriting by the underlying fabric is visually recognized.
The handwriting is retained when the water is not dried. When the water dries, the handwriting returns to its original white color, and the handwriting becomes invisible.
The above-mentioned appearance change could be repeatedly performed by adhering water, and also had water resistance.
Also, when writing on a desk, writing a small amount of water on a synthetic paper made of water-impermeable material and placing it on the desk can prevent the writing object from slipping. Since there was no need to hold it by hand or use paperweight, it was very convenient as a cursive script.
[0013]
Example 2
A white synthetic paper (thickness: 110 μm) having the same shape as the cloth as a water-impermeable material is attached to the back surface of a white nylon nonwoven fabric (250 mm × 300 mm) having a basis weight of 15 g / m 2 using an acrylic resin adhesive. Wood was obtained.
5 parts of a blue pigment (trade name: Sundai Super Blue GLL, manufactured by Sanyo Pigment Co., Ltd.) and an acrylic ester emulsion [trade name: Movinyl 763, manufactured by Hoechst Gosei Co., Ltd.] 50% of solid ink, 3 parts of aqueous ink thickener, 0.5 parts of leveling agent, 0.3 parts of antifoaming agent, and 5 parts of epoxy crosslinking agent for uniform blue screen printing. The whole surface was solid-printed with a 150-mesh screen plate using ink, and dried and cured at 70 ° C. for 3 minutes to form a colored layer.
Next, 15 parts of wet-process fine silica (trade name: Nip Seal E-220, manufactured by Nippon Silica Industry Co., Ltd.) and 15 parts of yellow pigment [trade name: Sundai Super Yellow 10GS, Sanyo Pigment Co., Ltd.] 1 part), urethane emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink and Chemicals, Inc., solid content 30%] 45 parts, water 40 parts, silicone-based defoamer 0.5 part Using a yellow screen printing ink obtained by uniformly stirring and mixing 3 parts of a water-based ink thickener, 1 part of ethylene glycol, and 3 parts of an isocyanate cross-linking agent, solid printing was performed on a 100-mesh screen plate, After drying and curing at 80 ° C. for 5 minutes to form a porous layer, a water-discolorable writing body was obtained.
In the water discolorable writing object, the blue color by the colored layer is in a concealed state in a normal state, the entire surface of the porous layer is pale yellow, and when touching the porous layer, it is like a calligraphy paper. It had a tactile sensation.
A water discolorable writing set was obtained by combining the water discolorable writing object and a brush.
On the water-discolorable writing object, when writing with a water-impregnated brush, the portion of the porous layer becomes transparent, and a clear green color in which the blue color of the colored layer and the yellow color of the porous layer are mixed. The handwriting is visually recognized.
The handwriting is retained when the water is not dried. When the water dries, the handwriting returns to its original pale yellow color, and the handwriting becomes invisible.
The above-mentioned appearance change could be repeatedly performed by adhering water, and also had water resistance.
Also, when writing on a desk, writing a small amount of water on a synthetic paper made of water-impermeable material and placing it on the desk can prevent the writing object from slipping. Since there was no need to hold it by hand or use paperweight, it was very convenient as a cursive script.
[0014]
Example 3
On a back surface of a white nonwoven fabric (250 mm × 350 mm) in which polypropylene and polyester having a basis weight of 25 g / m 2 are mixed at a ratio of 50:50, white synthetic paper (thickness: 160 μm) having the same shape as the cloth is used as a water-impermeable material. A base material was obtained by bonding with a urethane resin-based adhesive.
Next, 3 parts of a green pigment (trade name: Sundai Super Green LXB, manufactured by Sanyo Dyeing Co., Ltd.) and an acrylic ester emulsion [trade name: NEOCRYL A-622, Abisia Co., Ltd.] 50%, aqueous ink thickener 3 parts, leveling agent 0.5 part, defoamer 0.3 part, epoxy-based cross-linking agent 3 parts uniformly mixed and stirred green Using a screen printing ink, a plurality of 50 mm × 50 mm squares were printed on a 150-mesh screen plate so that the distance between the squares was 1 mm, and dried and cured at 70 ° C. for 3 minutes to form a colored layer. .
Further, on the colored layer, 15 parts of wet-process fine powder silica (trade name: Nip Seal E-220, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran AP-20, Dainippon Ink and Chemicals, Inc. Co., Ltd., solid content 30%] 45 parts, water 40 parts, silicone defoamer 0.5 part, thickener for water-based ink 3 parts, ethylene glycol 1 part, isocyanate-based cross-linking agent 3 parts Using a white screen printing ink obtained by stirring and mixing, the entire surface was solid-printed on a 180-mesh screen plate, dried and cured at 70 ° C. for 5 minutes to form a porous layer, and a water-discolorable writing object was obtained. Obtained.
In the water discolorable writing object, in a normal state, a state in which a light green porous layer is divided by a ruled line having a line width of 1 mm is visually recognized, and when touching the porous layer, a touch like a calligraphy paper is obtained. Was.
A water discolorable writing set was obtained by combining the water discolorable writing object and a brush.
When writing is performed on the water-discolorable writing object with a writing brush impregnated with water, the polyporous layer at that portion becomes transparent, and a clear green handwriting by the colored layer is visually recognized.
The handwriting is retained when the water is not dried. When the water dries, the handwriting returns to its original light green color, and the handwriting becomes invisible.
The above-mentioned appearance change could be repeatedly performed by adhering water, and also had water resistance.
Also, when writing on a desk, writing a small amount of water on a synthetic paper made of water-impermeable material and placing it on the desk can prevent the writing object from slipping. Since there was no need to hold it by hand or use paperweight, it was very convenient as a cursive script.
[0015]
Example 4
A white soft vinyl chloride film (thickness: 50 μm) having the same shape as the cloth as a water-impermeable material is attached to the back surface of a polypropylene nonwoven fabric (500 mm × 500 mm) having a basis weight of 20 g / m 2 with a urethane resin-based adhesive. Got.
3 parts of a pink fluorescent pigment (trade name: Epocolor FP20, manufactured by Nippon Shokubai Co., Ltd.) and an acrylic ester emulsion [trade name: NEOCRYL A-612, manufactured by Avicia Co., Ltd.] 50% of solid ink, 3 parts of aqueous ink thickener, 0.5 parts of leveling agent, 0.3 parts of antifoaming agent, and 3 parts of epoxy cross-linking agent are uniformly mixed and stirred, and pink screen printing is performed. Using a 150-mesh screen stencil, solid printing was performed on the entire surface, and dried and cured at 70 ° C. for 3 minutes to form a colored layer.
Next, 15 parts of wet-process finely-divided silica (trade name: Nip Seal E-220, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran AP-20, Dainippon Ink & Chemicals, Ltd.] 45 parts of water, 40 parts of water, 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent. Using a white screen printing ink obtained by stirring and mixing uniformly, the entire surface was solid-printed on a 100-mesh screen plate, dried and cured at 70 ° C. for 5 minutes to form a porous layer, and water-discolorable writing was performed. Got a body.
In the water discolorable writing object, the pink color of the colored layer is in a concealed state in a normal state, and the entire surface of the porous layer is white, and when touching the porous layer, it is like a calligraphy paper. It had a tactile sensation.
A water-discolorable writing set was obtained by combining the water-discolorable writing object and a marking pen capable of storing water therein.
When writing is performed on the water-discolorable writing object with a marking pen containing water, the porous layer in that portion becomes transparent, and a clear pink handwriting due to the lower colored layer is visually recognized.
The handwriting is retained when the water is not dried. When the water dries, the handwriting returns to its original white color, and the handwriting becomes invisible.
The above-mentioned appearance change could be repeatedly performed by adhering water, and also had water resistance.
In addition, even if the written object is roughly handled, there is no problem such as bending or breakage, and even when folded when stored, there is no occurrence of wrinkles, and the usefulness as a written object. Of course, it was also excellent in handling convenience, and was suitable for children's training tools.
[0016]
Example 5
A white ethylene vinyl acetate film (thickness: 150 μm) having the same shape as the cloth was positioned as a water-impermeable material on the back surface of a cupra plain woven fabric (900 mm × 900 mm) having a basis weight of 25 g / m 2 , and a bias was applied around the edges. The base material was obtained by sewing with a tape.
3 parts of a pink fluorescent pigment (trade name: Epocolor FP20, manufactured by Nippon Shokubai Co., Ltd.) and an acrylic ester emulsion [trade name: NEOCRYL A-612, manufactured by Avicia Co., Ltd.] 50% of solid ink, 3 parts of aqueous ink thickener, 0.5 parts of leveling agent, 0.3 parts of antifoaming agent, and 3 parts of epoxy cross-linking agent are uniformly mixed and stirred, and pink screen printing is performed. Using a 150-mesh screen stencil, solid printing was performed at the center in a size of 700 mm × 700 mm using a printing ink, and dried and cured at 60 ° C. for 10 minutes to form a colored layer.
Next, 15 parts of wet-process finely divided silica (trade name: Nip Seal E-220, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran AP-20, Dainippon Ink and Chemicals, Ltd. Co., Ltd., solid content 30%] 45 parts, water 40 parts, silicone defoamer 0.5 part, thickener for water-based ink 3 parts, ethylene glycol 1 part, isocyanate-based cross-linking agent 3 parts Using a white screen printing ink obtained by stirring and mixing, the entire surface was solid-printed on a 100-mesh screen plate in the same size as the colored layer, and dried and cured at 60 ° C. for 10 minutes to form a porous layer.
Further, a pattern and characters related to the pattern were printed with a general printing ink in the vicinity of the porous layer to obtain a water-discolorable writing object.
In the water-discolorable writing object, the pink color of the colored layer is in a concealed state in a normal state, and the white portion formed by the porous layer and the design and characters printed on the periphery are visible.
A water-discolorable writing set was obtained by combining the water-discolorable writing object and a marking pen capable of storing water therein.
When writing is performed on the water-discolorable writing object with a marking pen containing water, the porous layer in that portion becomes transparent, and a clear pink handwriting due to the lower colored layer is visually recognized.
The handwriting is retained when the water is not dried. When the water dries, the handwriting returns to its original white color, and the handwriting becomes invisible.
The above-mentioned appearance change could be repeatedly performed by adhering water, and also had water resistance.
In addition, even if the written object is roughly handled, there is no problem such as bending or breakage, and even when folded when stored, there is no occurrence of wrinkles, and the usefulness as a written object. Of course, it is also easy to handle, and when practicing characters, it is possible to imitate the design and characters printed around the porous layer and write It was suitable for teaching tools.
[0017]
Example 6
An acrylic resin solution is applied on the back surface of a white polyester taffeta cloth (700 mm × 700 mm) with a basis weight of 30 g / m 2 using a knife coater and dried and cured to provide a water-impermeable material having a thickness of 10 μm. Wood was obtained.
5 parts of a blue pigment (trade name: Sundai Super Blue GLL, manufactured by Sanyo Pigment Co., Ltd.) and an acrylic ester emulsion [trade name: Boncoat AB782, Dainippon Ink Industries, Ltd.] Company, solid content 45%] 50 parts, aqueous ink thickener 3 parts, leveling agent 0.5 part, defoamer 0.3 part, epoxy-based cross-linking agent 5 parts uniformly mixed and stirred, blue screen Using a printing ink, solid printing was performed in the center at a size of 500 mm × 500 mm with a 150-mesh screen plate, and dried and cured at 130 ° C. for 3 minutes to form a colored layer.
Next, 15 parts of wet-process finely-divided silica (trade name: Nip Seal E-220, manufactured by Nippon Silica Industry Co., Ltd.) and urethane emulsion [trade name: Hydran AP-20, Dainippon Ink & Chemicals, Ltd.] 45 parts of water, 40 parts of water, 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent. Using a white screen printing ink obtained by stirring and mixing uniformly, solid printing was carried out on a 100-mesh screen plate, and dried and cured at 80 ° C. for 5 minutes to form a porous layer.
Next, a pattern and characters related to the pattern were printed near the porous layer with a general printing ink to obtain a water-discolorable writing object.
In the water-discolorable writing body, the blue color of the colored layer is in a concealed state in a normal state, and the white portion formed by the porous layer and the surrounding designs and characters are visible.
A water-discolorable writing set was obtained by combining the water-discolorable writing object and a marking pen capable of storing water therein.
When writing is performed on the water-discolorable writing object with a marking pen containing water, the porous layer at that portion becomes transparent, and a clear blue handwriting due to the lower colored layer is visually recognized.
The handwriting is retained when the water is not dried. When the water dries, the handwriting returns to its original white color, and the handwriting becomes invisible.
The above-mentioned appearance change could be repeatedly performed by adhering water, and also had water resistance.
In addition, even if the written object is roughly handled, there is no problem such as bending or breakage, and even when folded when stored, there is no fold wrinkle, and the usefulness as a written object. Of course, it is also very convenient to handle, and when practicing letters and the like, it is possible to imitate the design and letters printed around the porous layer and write It was suitable for teaching tools.
[0018]
【The invention's effect】
Since the water-discolorable writing object of the present invention is provided with a specific weight of fabric on a water-impermeable material as a base material, the water from the porous layer is lower than that of a paper-based material. Is suitable, and a clear handwritten image can be quickly formed and visualized, and is excellent in water resistance.
In addition, by providing a cloth on a water-impermeable material such as a plastic film, a synthetic resin, or synthetic paper as a base material, a tactile sensation such as paper can be given, so that a water-discolorable writing object with high commercial value can be obtained. Can be provided.
Furthermore, by setting the water-attaching means and the water-discolorable writing object as a set, it is possible to provide a highly practical water-discoloration writing set that easily displays a writing image.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003153946A JP2004175101A (en) | 2002-10-02 | 2003-05-30 | Water discoloring writing material, and water discoloring writing set using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002289617 | 2002-10-02 | ||
| JP2003153946A JP2004175101A (en) | 2002-10-02 | 2003-05-30 | Water discoloring writing material, and water discoloring writing set using the same |
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| JP2004175101A true JP2004175101A (en) | 2004-06-24 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006068962A (en) * | 2004-08-31 | 2006-03-16 | Tombow Pencil Co Ltd | Allochroic pressure-sensitive transfer correction tape and transfer implement |
| JP2007076052A (en) * | 2005-09-12 | 2007-03-29 | Pilot Ink Co Ltd | Reversibly discoloring writing plate and reversibly discoloring writing set using the same |
| JP2007212800A (en) * | 2006-02-10 | 2007-08-23 | Pilot Ink Co Ltd | Reversibly color changing display and reversibly color changing display set using same |
| JP2008037095A (en) * | 2006-07-12 | 2008-02-21 | Pilot Ink Co Ltd | Water discoloring wall adhering material and water discoloring wall adhering material set using the same |
| JP2010094971A (en) * | 2008-09-18 | 2010-04-30 | Pilot Ink Co Ltd | Water color-change fabric and water color-change plotting toy set using the same |
| JP2012236332A (en) * | 2011-05-12 | 2012-12-06 | Pilot Ink Co Ltd | Water color-changeable laminate |
| CN104494333A (en) * | 2014-11-18 | 2015-04-08 | 张国松 | Special water-writing newsprint paper for painting and calligraphy practice and manufacture process of special water-writing newsprint paper |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006068962A (en) * | 2004-08-31 | 2006-03-16 | Tombow Pencil Co Ltd | Allochroic pressure-sensitive transfer correction tape and transfer implement |
| JP2007076052A (en) * | 2005-09-12 | 2007-03-29 | Pilot Ink Co Ltd | Reversibly discoloring writing plate and reversibly discoloring writing set using the same |
| JP2007212800A (en) * | 2006-02-10 | 2007-08-23 | Pilot Ink Co Ltd | Reversibly color changing display and reversibly color changing display set using same |
| JP2008037095A (en) * | 2006-07-12 | 2008-02-21 | Pilot Ink Co Ltd | Water discoloring wall adhering material and water discoloring wall adhering material set using the same |
| JP2010094971A (en) * | 2008-09-18 | 2010-04-30 | Pilot Ink Co Ltd | Water color-change fabric and water color-change plotting toy set using the same |
| JP2012236332A (en) * | 2011-05-12 | 2012-12-06 | Pilot Ink Co Ltd | Water color-changeable laminate |
| CN104494333A (en) * | 2014-11-18 | 2015-04-08 | 张国松 | Special water-writing newsprint paper for painting and calligraphy practice and manufacture process of special water-writing newsprint paper |
| CN104494333B (en) * | 2014-11-18 | 2016-06-15 | 张国松 | Painting and calligraphy exercise dedicated water writes newsprint and manufacturing process thereof |
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