JP4056024B2 - Discoloration - Google Patents

Description

湿式法微粒子状珪酸は、以下に示されるように、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。
【化２】

又、前記多孔質層に含まれる低屈折率顔料は、浸透する媒体が主に水であることから、適度の親水性を有することが望ましい。従って、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存在するため親水性が高く、好適に用いられる。
【００１２】
前記湿式法微粒子状珪酸を低屈折率顔料として用いる場合、湿式法微粒子状珪酸の種類、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水状態での透明性を共に満足するためには、塗布量が１ｇ／ｍ^２〜３０ｇ／ｍ^２であることが好ましく、より好ましくは、５ｇ／ｍ^２〜２０ｇ／ｍ^２である。１ｇ／ｍ^２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／ｍ^２を越えると吸水時に十分な透明性を得ることが困難である。
【００１３】
前記低屈折率顔料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して塗布した後、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、カルボシキル化ＳＢＲ樹脂、カルボキシル化ＮＢＲ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、エポキシ樹脂等が挙げられる。
【００１４】
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顔料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。よって、耐洗濯性、耐擦過性が必要となる用途においては、上述のバインダー樹脂としてウレタン系樹脂又はナイロン樹脂を用いるか、或いは前記樹脂を少なくとも含有することが好ましい。
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、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、媒体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浸透時間、浸透度合い、浸透後の乾燥の遅速性をコントロールすることもできる。
【００１５】
本発明の変色体には、必要によって、一般染料、顔料を含む非変色性インキにより非変色層を設けたり、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含むインキにより金属光沢層を設けることもできる。
又、保護層や光安定剤層を適宜設けることもできる。具体的には、前記光安定剤層は紫外線吸収剤、酸化防止剤、老化防止剤、一重項酸素消光剤、スーパーオキシドアニオン消光剤、オゾン消色剤、可視光線吸収剤、赤外線吸収剤から選ばれる光安定剤を分散状態に固着した層である。
尚、帯電防止剤、極性付与剤、揺変性付与剤、消泡剤等を必要に応じ、可逆熱変色層や多孔質層に添加して機能を向上させることもできる。
【００１６】
本発明の構成において、可逆熱変色層自体が支持体であり、前記可逆熱変色層上に多孔質層を設ける系にあっては、可逆熱変色層が変色しない温度域の水等の媒体を付着させると、多孔質層に媒体が浸透して透明化し、下層の可逆熱変色層による色調が視認される。
一方、可逆熱変色層を変色させる温度域の水等の媒体を付着させると、多孔質層に媒体が浸透して透明化すると共に、下層の可逆熱変色層を変色させる。
又、具体例として、体温により変色する可逆熱変色層を設け、前記可逆熱変色層が変色しない温度域の水等の媒体を付着させて多孔質層を透明化状態となした後、手触により可逆熱変色層を変色させることができ、非変色層との併用等により更に多彩な変色を示す。
ここで、前記した構成における可逆熱変色層は、有色←→無色の可逆的変色、有色（１）←→有色（２）の可逆的変色のいずれであってもよい。
本発明変色体の構成において、３以上の色調の異なる様相を視覚させるためには、多孔質層の下層の色調が、乾燥状態における多孔質層の色調とは異なる２以上の色調を呈さなければならない。又、前記２以上の色調の異なる様相を視覚させるためには、可逆熱変色層自体がそれぞれ異なる色調を呈すること、可逆熱変色層が有色から無色に可逆的に変色する層の場合は、前記色調と異なる支持体を設けるか、或いは、着色層を設ける必要がある。
前記多孔質層はシリカ等の低屈折率顔料を含む層であるため、乾燥時には高い隠蔽性を示して下層の色調を完全に隠蔽することができるため、下層が濃色であったとしても、比較的明るい色調を視覚させる構成となすことができる。
更に、前記多孔質層上に可逆熱変色図柄層を設けてデザイン変化を多様にすることもできる。
【００１７】
次に、支持体上に多孔質層を設け、前記多孔質層上に可逆熱変色層を設ける系について説明すると、多孔質層に水等の媒体が浸透するためには、上層に設けた可逆熱変色層も水媒体が浸透する性質を有する層であることが好ましい。
可逆熱変色層が有色から無色に可逆的に変色すると共に環境温度において発色状態の場合は、前記組成物が変色する温度域の水等の媒体を変色体に付着させると、可逆熱変色層が消色すると共に多孔質層も透明化して支持体の色調が視認される。
又、手触したり、温風、冷風等を吹きつける等、水等の媒体を付着させずに加温、又は冷却すると、可逆熱変色層が消色して多孔質層の色調が視認される。
更に、可逆熱変色層が有色から無色に可逆的に変色し、環境温度において消色状態の場合は、可逆熱変色層が変色しない温度域の水等の媒体を付着させると多孔質層が透明化して支持体の色調が視認され、前記可逆熱変色層が変色する温度域の媒体を変色体に付着させると、熱変色層が発色状態で視認される。
尚、前記した構成における可逆熱変色層は、有色から無色に可逆的に変色するものが好適であり、３以上の色調の異なる様相を視覚させるためには、前記可逆熱変色層の下層が可逆熱変色層の色調とは異なる２以上の色調を呈さなければならない。前記２以上の異なる色調を呈する構成としては、支持体と乾燥状態の多孔質層がそれぞれ異なる色調を呈すること、或いは、乾燥状態の多孔質層とは色調の異なる着色層を前記多孔質層と支持体の間に介在させる必要がある。
更に、前記多孔質層はシリカ等の低屈折率顔料を含む層であるため、乾燥時には高い隠蔽性を示して下層の色調を完全に隠蔽することができ、上層に設けた可逆熱変色層は明るい色調を呈することができる。
更に、前記可逆熱変色層上に多孔質図柄層を設けてデザイン変化を多様にすることもできる。
【００１８】
前記した積層構造において、可逆熱変色層と多孔質層は必要により文字、記号、図形等の図柄層であってもよい。
又、非変色層を各層の間に介在させたり、上層に設けてもよく、同様に文字、記号、図形等の図柄層であってもよい。
前記可逆熱変色層、多孔質層、非変色層は、従来より公知の方法、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、等の手段により形成することができる。
【００１９】
本発明は前記した如く、可逆熱変色層と低屈折率顔料を含む多孔質層との積層構造において、変色の多様性を最も効果的に発現させる。
【００２０】
【発明の実施の形態】
本発明変色体は、平面状に限らず、線状、凹凸状、立体状等多様な形態が有効である。
【００２１】
【実施例】
以下に実施例を示す。尚、実施例中の部は重量部を示す。
実施例１（図１参照）
感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（青色←→無色、１５℃以下で青色、３０℃以上で無色）２０部、ピンク色蛍光顔料〔商品名：エポカラーＦＰ−１０、（株）日本触媒製〕１部、ベンゾトリアゾール系紫外線吸収剤２部、ビカット軟化点１００℃のポリプロピレン１０００部を均一に混合した後、押出成形機を用いて可逆熱変色性ペレットを得た。前記ペレットを射出成形にてシート状物を形成して可逆熱変色層２とした。
尚、前記可逆熱変色層２は、１５℃以下に冷却すると青紫色が視覚され、この色調は３０℃未満の温度域で保持され、又、３０℃以上に加温するとピンク色になり、この色調は１５℃を越える温度域で保持される層である。
次いで、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、アクリル酸エステルエマルジョン（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、ブロック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１８０メッシュのスクリーン版を用いて、前記可逆熱変色層２上に全面にベタ印刷し、１３０℃にて５分間乾燥硬化させて、乾燥状態で白色の多孔質層３を形成し、積層構造の変色体１を得た。
前記多孔質層３は、水もしくは水性媒体の付着により、白色状態から無色透明状態に変化する。
【００２２】
前記変色体１は、乾燥状態且つ２４℃の室温下では白色を呈し、冷却或いは加温しても同様に白色のままであるが、１５℃以下の冷水を付着させると多孔質層３が透明化して、下層の可逆熱変色層２による青紫色に瞬時に変化した。前記青紫色の変色体１を２４℃の室温下で放置したところ、水が付着した状態では青紫色を呈していたが、水が蒸発するに従い、徐々に青紫色から白色に戻り、乾燥状態に戻ると元の白色となった。
次に、前記変色体１に３０℃以上の温水を付着させると、多孔質層３が水の付着により透明化すると共に、可逆熱変色層２が紫色から蛍光ピンク色に変色して蛍光ピンク色の変色体が視覚できる。
前記青紫色の変色体１を２４℃の室温下で放置したところ、水が付着した状態では蛍光ピンク色を呈していたが、水が蒸発するに従い、徐々に蛍光ピンク色から白色に戻り、乾燥状態に戻ると元の白色となった。
次に、乾燥状態の変色体１に１５℃以下の冷水を付着させて青紫色に変色させた状態で、該変色体１の一部に３０℃以上の温水を付着させると青紫色からピンク色に変化し、この状態は水が蒸発して乾燥状態になるまでの間、青紫色とピンク色の両状態を保持していた。
この様に、前記変色体１は、全面が白色の状態から冷水又は温水の適用により、青紫色、或いは蛍光ピンク色に変化させることができ、乾燥させることにより、再び元の白色状態に戻すことができる多彩な色変化を示し、しかも前記様相変化は可逆的に再現される。
【００２３】
実施例２（図２参照）
支持体４としてピンク色のナイロンタフタ生地上に、感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（青色←→無色、１５℃以下で青色、３０℃以上で無色）１０部、アクリル酸エステルエマルジョン（固形分５０％）１０部、シリコーン系消泡剤０．２部、水１部、エチレングリコール０．５部、増粘剤０．５部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキを１０９メッシュのスクリーン版を用いて全面にベタ印刷を行ない、１３０℃にて５分間乾燥硬化させて可逆熱変色層２を形成した。
前記、支持体と可逆熱変色層を積層した状態では、１５℃以下に冷却すると支持体のピンク色と可逆熱変色層の青色が混色となった紫色が視覚され、この色調は３０℃未満の温度域で保持され、又、３０℃以上に加温すると、可逆熱変色層が無色となり、支持体のピンク色が視覚され、この色調は１５℃を越える温度域で保持されるものであった。
次いで、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、アクリル酸エステルエマルジョン（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、ブロック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１８０メッシュのスクリーン版を用いて、前記可逆熱変色層２上に全面にベタ印刷し、１３０℃にて５分間乾燥硬化させて、乾燥状態で白色の多孔質層３を形成し変色体１を得た。
前記多孔質層３は、水もしくは水溶性液体の付着により、白色状態から無色透明状態に変化する。
【００２４】
前記変色体１は、乾燥状態且つ２４℃の室温下では白色を呈し、冷却或いは加温しても同様に白色のままであるが、１５℃以下の冷水を付着させると多孔質層３が水の付着により透明化して、下層の可逆熱変色層２と支持体４の色調が混色となった紫色に瞬時に変化した。前記紫色の変色体１を２４℃の室温下で放置したところ、水が付着した状態では、紫色を呈していたが、水が蒸発するに従い、徐々に紫色から白色に戻り、乾燥状態に戻ると元の白色となった。
次に、前記変色体１に３０℃以上の温水を付着させると、多孔質層３が水の付着により透明化すると共に、可逆熱変色層２が青色から無色に変色して支持体４によるピンク色の変色体１として視覚された。
前記ピンク色の変色体１を２４℃の室温下で放置したところ、水が付着した状態では、ピンク色を呈していたが、水が蒸発するに従い、徐々にピンク色から白色に戻り、乾燥状態に戻ると元の白色となった。
次に、乾燥状態の変色体に１５℃以下の冷水を付着させて紫色に変色させた状態で、前記変色体の一部に３０℃以上の温水を付着させると紫色からピンク色に変化し、この状態は水が蒸発して乾燥状態になるまでの間、紫色とピンク色の両状態を保持していた。
この様に、前記変色体１は、全面が白色の状態から冷水又は温水の適用により、紫色、或いはピンク色に変化させることができ、乾燥させることにより、再び元の白色状態に戻すことができる多彩な色変化を示すことができ、前記様相変化を可逆的に再現させることができる。
【００２５】
実施例３
支持体４として白色のナイロンタフタ生地上に、感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（青色←→無色、１５℃以下で青色、３０℃以上で無色）１０部、ピンク色蛍光顔料〔商品名：エポカラーＦＰ−１０、（株）日本触媒製〕１部、アクリル酸エステルエマルジョン（固形分５０％）１０部、シリコーン系消泡剤０．２部、水１部、エチレングリコール０．５部、増粘剤０．５部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキ（青紫色←→ピンク色、１５℃以下で青紫色、３０℃以上でピンク色）を１０９メッシュのスクリーン版を用いて全面にベタ印刷を行ない、１３０℃にて５分間乾燥硬化させて可逆熱変色層２を形成した。
尚、前記可逆熱変色層２は、１５℃以下に冷却すると青紫色が視覚され、この色調は３０℃未満の温度域で保持され、又、３０℃以上に加温するとピンク色になり、この色調は１５℃を越える温度域で保持される層である。
次いで、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、アクリル酸エステルエマルジョン（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、ブロック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１８０メッシュのスクリーン版を用いて、前記可逆熱変色層２上に全面にベタ印刷し、１３０℃にて５分間乾燥硬化させて、乾燥状態で白色の多孔質層３を形成し変色体１を得た。
前記多孔質層３は、水もしくは水溶性液体の付着により、白色状態から無色透明状態に変化する。
【００２６】
前記変色体１は、乾燥状態且つ２４℃の室温下では白色を呈し、冷却或いは加温しても同様に白色のままであるが、１５℃以下の冷水を付着させると多孔質層３が水の付着により透明化して、下層の可逆熱変色層２による青紫色に瞬時に変化した。前記青紫色の変色体１を２４℃の室温下で放置したところ、水が付着した状態では、青紫色を呈していたが、水が蒸発するに従い、徐々に青紫色から白色に戻り、乾燥状態に戻ると元の白色となった。
次に、前記変色体１に３０℃以上の温水を付着させると、多孔質層３が水の付着により透明化すると共に、可逆熱変色層２が紫色から蛍光ピンク色に変色して蛍光ピンク色の変色体が視覚できる。
前記青紫色の変色体１を２４℃の室温下で放置したところ、水が付着した状態では、蛍光ピンク色を呈していたが、水が蒸発するに従い、徐々に蛍光ピンク色から白色に戻り、乾燥状態に戻ると元の白色となった。
次に、乾燥状態の変色体に１５℃以下の冷水を付着させて青紫色に変色させた状態で、前記変色体の一部分に３０℃以上の温水を付着させると青紫色からピンク色に変化し、この状態は水が蒸発して乾燥状態になるまでの間、青紫色とピンク色の両状態を保持していた。
この様に、前記変色体１は、全面が白色の状態から冷水又は温水の適用により、青紫色、或いは蛍光ピンク色に変化させることができ、乾燥させることにより、再び元の白色状態に戻すことができる多彩な色変化を示す変色体１を得ることができ、前記様相変化を繰り返し、再現させることができる。
【００２７】
実施例４（図３参照）
支持体４として白色のナイロンタフタ布上に、黄色蛍光顔料〔商品名：エポカラーＦＰ−１１７、（株）日本触媒製〕１０部、アクリル酸エステルエマルジョン（固形分５０％）５０部、シリコーン系消泡剤０．２部、増粘剤５部、レベリング剤１部、水１０部、エポキシ系架橋剤２．５部を均一に混合攪拌してなる蛍光黄色のスクリーン印刷用インキで、１５０メッシュのスクリーン版を用いて全面にベタ印刷を行い、１３０℃にて５分間乾燥硬化させて非変色層５を形成し、更にその上面に、感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（青色←→無色、１５℃以下で青色、３０℃以上で無色）１０部、アクリル酸エステルエマルジョン（固形分５０％）１０部、シリコーン系消泡剤０．２部、水１部、エチレングリコール０．５部、増粘剤０．５部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキを１０９メッシュのスクリーン版を用いて、全面にベタ印刷行ない、１３０℃にて５分間乾燥硬化させて可逆熱変色層２を形成した。
前記、非変色層５と可逆熱変色層２を積層した状態では、１５℃以下に冷却すると非変色層５の蛍光黄色と可逆熱変色層２の青色が混色となった緑色が視覚され、この色調は３０℃未満の温度域で保持される。又、３０℃以上に加温すると、可逆熱変色層２が無色となり、非変色層５の蛍光黄色が視覚され、この色調は１５℃を越える温度域で保持されるものであった。
前記可逆熱変色層２の上面に、実施例１で作製した白色スクリーン印刷用インキを用いて全面にベタ印刷し、乾燥硬化させて多孔質層３を形成して変色体１を得た。
前記多孔質層３は、水もしくは水溶性液体の付着により、白色状態から無色透明状態に変化する。
【００２８】
前記変色体１は、乾燥状態且つ２４℃の室温下では白色を呈し、冷却或いは加温しても同様に白色のままであるが、１５℃以下の冷水を付着させると多孔質層３が透明化して、下層の可逆熱変色層２と非変色層５の色調が混色となった緑色に瞬時に変化した。前記緑色の変色体１を２４℃の室温下で放置したところ、水が付着した状態では、緑色を呈していたが、水が蒸発するに従い、徐々に緑色から白色に戻り、乾燥状態に戻ると元の白色となった。
次に、前記変色体１に３０℃以上の温水を付着させると、多孔質層３が透明化すると共に、可逆熱変色層２が青色から無色に変色して非変色層５による蛍光黄色の変色体１が視覚できる。
前記蛍光黄色の変色体１を２４℃の室温下で放置したところ、水に濡れた状態では、蛍光黄色を呈していたが、水が蒸発するに従い、徐々に蛍光黄色から白色に戻り、乾燥状態に戻ると元の白色となった。
次に、乾燥状態の変色体に１５℃以下の冷水を付着させて緑色に変色させた状態で、前記変色体１の一部分に３０℃以上の温水を付着させると緑色から黄色に変化し、この状態は水が蒸発して乾燥状態になるまでの間、緑色と黄色の両状態を保持していた。
この様に、前記変色体１は、全面が白色の状態から冷水又は温水の適用により、緑色、或いは蛍光黄色に変化させることができ、乾燥させることにより、再び元の白色状態に戻すことができる多彩な色変化を示す変色体を得ることができ、前記様相変化を繰り返し、再現させることができた。
【００２９】
実施例５（図４参照）
支持体４として白色のポリエステルサテン生地上に、黄色蛍光顔料〔商品名：エポカラーＦＰ−１１７、（株）日本触媒製〕１０部、アクリル酸エステルエマルジョン（固形分５０％）５０部、シリコーン系消泡剤０．２部、増粘剤５部、レベリング剤１部、水１０部、エポキシ系架橋剤２．５部を均一に混合攪拌してなる蛍光黄色のスクリーン印刷用インキで、１５０メッシュのスクリーン版を用いて全面にベタ印刷を行い、１３０℃にて５分間乾燥硬化させて非変色層５を形成し、更にその上面に、可逆熱変色性材料を内包したマイクロカプセル顔料（青色←→無色、１５℃以未満青色、１５℃以上で無色）１０部、アクリル酸エステルエマルジョン（固形分５０％）１０部、シリコーン系消泡剤０．２部、水１部、エチレングリコール０．５部、増粘剤０．５部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキを１０９メッシュのスクリーン版を用いて、花の図柄を印刷して１３０℃にて５分間乾燥硬化させて可逆熱変色図柄層２１を形成した。
前記、非変色層５と可逆熱変色図柄層２１を積層した状態では、２４℃の室温下では非変色層５により全面が蛍光黄色であり、１５℃以下に冷却すると、可逆熱変色図柄層２１が青色に発色して、黄色地に緑色の花柄が視覚され、再び１５℃を越える温度になると可逆熱変色図柄層２１が消色して全面が蛍光黄色になる。
前記可逆熱変色図柄層２１の上面に、実施例１で作製した白色スクリーン印刷用インキを用いて全面にベタ印刷し、乾燥硬化させて多孔質層３を形成して変色体１を得た。
前記多孔質層３は、水もしくは水溶性液体の付着により、白色状態から無色透明状態に変化する。
【００３０】
前記変色体１は、乾燥状態且つ２４℃の室温下では白色を呈し、冷却或いは加温しても同様に白色のままであるが、１５℃以上の水を付着させると、多孔質層３が透明化するため全面が黄色となり、２４℃の室温下で放置すると水が蒸発、乾燥して白色に戻った。
次いで、１０℃の冷水を付着させると、多孔質層３が透明化すると共に、可逆熱変色図柄層２１が無色から青色になるため、黄色地に緑色の花柄が描かれた様相に変化した。２４℃の室温下で放置すると、１５℃を越える温度になった時点で可逆熱変色図柄層２１が消色して全面が黄色になり、暫くその状態を示していたが、乾燥すると白色に戻った。
この様に、前記変色体１は、全面が白色の状態から冷水又は温水の適用により、全面が黄色、或いは黄色地に緑色の花柄に変化させることができ、乾燥させることにより、再び元の白色状態に戻すことができる多彩な色変化を示す変色体を得ることができ、前記様相変化を繰り返し、再現させることができた。
【００３１】
実施例６（図５参照）
支持体４として白色のポリエステルサテン生地上に、黄色、ピンク色、紫色、緑色、赤色の蛍光一般色インキにて、花柄を印刷して非変色図柄層５１を設けた。
前記非変色図柄層５１上に、可逆熱変色性材料を内包したマイクロカプセル顔料（黒色←→無色、３０℃未満で黒色、３０℃以上で無色）１０部、ポリエステルステル系ウレタンエマルジョン（固形分３０％）２０部、シリコーン系消泡剤０．４部、水１部、エチレングリコール０．５部、増粘剤１．０部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキを１０９メッシュのスクリーン版を用いて、全面にベタ印刷を行ない、１３０℃にて５分間乾燥硬化させて可逆熱変色層２を形成した。
前記、非変色図柄層５１上に可逆熱変色層２を積層した状態では、２４℃の室温下では黒色を呈しており、３０℃以上に加温すると可逆熱変色層２が消色して非変色図柄層５１によるカラフルな花柄が視覚され、再び３０℃未満の温度になると可逆熱変色層２が黒色に発色して花柄が隠蔽されるものである。
次いで、前記可逆熱変色層２上に、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、ポリエステル系ウレタンエマルジョン（固形分３０％）５０部、水３０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、ブロックイソシアネート系架橋剤２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１５０メッシュのスクリーン版を用いて蝶の図柄を印刷し、１３０℃にて５分間乾燥硬化させて、蝶の図柄の多孔質図柄層３１を形成して変色体１を得た。
前記多孔質図柄層３１は、水もしくは水溶性液体の付着により、白色状態から無色透明状態に変化する。
【００３２】
前記変色体１は、２４℃の室温下では、黒地の可逆熱変色層２上に多孔質図柄層３１による白色の蝶の図柄が視覚される。前記変色体を３０℃以上に加温すると、可逆熱変色層２が黒色から無色に変色して、非変色図柄層５１によるカラフルな花柄が現出して、花柄に白色の蝶の図柄が描かれた様相となる。再び３０℃未満の温度になると黒地に白色の蝶の図柄が描かれた様相に戻った。
又、前記変色体１に２０℃の水を付着させると、多孔質図柄層３１が透明化するため蝶の図柄が消えて全面が黒色となり、２４℃の室温下で放置すると水が蒸発、乾燥するに従って白色の蝶の図柄が現出し、完全に乾燥した状態では、再び黒地に白色の蝶の図柄が視覚された。
次いで、４０℃の温水を付着させると、多孔質図柄層３１が透明化して蝶の図柄が消えると共に、可逆熱変色層２が黒色から無色になるため、非変色図柄層５１によるカラフルな花柄のみが視覚でき、２４℃の室温下で放置すると、３０℃未満の温度になった時点で可逆熱変色層２が発色して花柄が黒色に隠蔽され、暫くその状態を示していたが、乾燥するに従って黒地上に徐々に白色の蝶の図柄が現出し、完全乾燥すると、黒色上に白色の蝶の図柄が描かれた様相に戻った。
この様に、布帛の温度変化、温水、冷水への浸漬により、黒地に白色の蝶の図柄が描かれた様相、黒色ベタの様相、カラフルな花柄上に白色の蝶の図柄が描かれた様相、カラフルな花柄のみの様相の、４つの様相を現出させることができ、これは何度も繰り返し行なうことができた。
【００３３】
実施例７（図６参照）
支持体４として白色のポリエステルタフタ布上に、蛍光ピンク色顔料〔商品名：エポカラーＦＰ−１０、（株）日本触媒製〕１５部、アクリル酸エステルエマルジョン（固形分５０％）５０部、シリコーン系消泡剤０．２部、増粘剤５部、レベリング剤１部、水１０部、エポキシ系架橋剤２．５部を均一に混合攪拌して得た蛍光ピンク色スクリーン印刷用インキで、１５０メッシュのスクリーン版を用いて全面にベタ印刷し、１３０℃にて５分間乾燥硬化させて非変色層５を形成し、更にその上面に、微粉末シリカ〔商品名：ニップシールＥ−１０１１、日本シリカ工業（株）製〕１５部、ポリカーボネート系ウレタンエマルジョン（固形分：３０％）４５部、水２０部、シリコーン系消泡剤０．２部、エチレングリコール３部、水系増粘剤３部、ブロックイソシアネート系架橋剤１．５部を均一混合攪拌してなる白色スクリーン印刷用インキにて、１８０メッシュのスクリーン版を用いて印刷し、１３０℃にて５分間乾燥硬化させて白色の多孔質層３を設けた。
更にその上面に、感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（青色←→無色、１５℃以下で青色、３０℃以上で無色）１０部、ポリエステル系ウレタンエマルジョン（固形分３０％）１０部、シリコーン系消泡剤０．２部、水１部、エチレングリコール０．５部、増粘剤０．５部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキを１８０メッシュのスクリーン版を用いて全面にベタ印刷を行ない、１３０℃にて５分間乾燥硬化させて可逆熱変色層２を形成し、変色体１を得た。
前記多孔質層３は、水もしくは水溶性液体の付着により、白色状態から無色透明状態に変化する。
【００３４】
前記変色体１は、１５℃以下に冷却すると可逆熱変色層２が青色になり、この状態は３０℃未満の温度域で保持された。前記変色体をドライヤーで３０℃以上に加温すると、可逆熱変色層２が消色して、下層の多孔質層３による白色が視覚され、１５℃を越える温度域で保持された。前記白色の変色体を再び１５℃以下に冷却すると青色になる。
更に、青色を呈する変色体１に約４０℃の温水を付着させると、可逆熱変色層２は無色になり、且つ、多孔質層３も透明化して非変色層５によるピンク色が視覚される。この状態は、水が付着している状態ではピンク色を呈していたが、乾燥するに従って、ピンク色から白色に変化し、完全乾燥した状態では再び白色状態となった。
この白色状態の変色体１に、約１０℃の冷水を筆に含ませて筆記すると、筆跡部分の多孔質層３は透明化し、且つ、可逆熱変色層２は青色になり、下層の非変色層５のピンク色と混色になった紫色の筆跡が得られる。
この状態は、水が付着している状態では紫色を呈していたが、乾燥するに従って多孔質層３が白色になるため紫色から青色に変化し、完全乾燥した状態では再び青色状態となった。
前記変色体１に約５℃の冷水を付着させると、全面が紫色に変化し、約４０℃の温水を筆に含ませて筆記すると、筆跡部分は紫色からピンク色に変色し、１５℃を越える温度域で保持され、水が付着した状態では紫色とピンク色の両状態を呈していたが、乾燥して水が蒸発するに従い多孔質層３が白色になるため紫色の部分は青色に変色し、且つ、ピンク色の部分は白色に変化し、完全に水が蒸発し、完全乾燥した状態では、青色の部分と白色の部分の両状態が視覚された。
次いで、青色と白色の両状態の変色体に再び２０℃の水を付着させると、青色の部分は紫色に変化し、白色の部分はピンク色に変化する。又、前記紫色とピンク色の両状態の変色体は、水が付着した状態ではこの状態を呈していたが、約１０℃の冷水を付着させると全面が紫色になり、或いは、約４０℃の温水を付着させると、全面がピンク色の布帛に変化し、約２４℃の室温に取り出し、完全乾燥させると、紫色から青色に、ピンク色から白色にそれぞれ変化した。
このように、前記変色体は室温乾燥状態では、青色、白色、青色及び白色の２色が同時に存在する３状態が任意に選定でき、又、水が付着した状態では、ピンク色、紫色、及び、ピンク色と紫色の２色が同時に存在する３状態が任意に選定できるため、合わせて６状態を示す変色体を得ることができ、これは何度も繰り返し行なうことができた。
【００３５】
実施例８
支持体として白色のポリエステルタフタ布上に、蛍光ピンク色顔料〔商品名：エポカラーＦＰ−１０、（株）日本触媒製〕１５部、アクリル酸エステルエマルジョン（固形分５０％）５０部、シリコーン系消泡剤０．２部、増粘剤５部、レベリング剤１部、水１０部、エポキシ系架橋剤２．５部を均一に混合攪拌してなる蛍光ピンク色スクリーン印刷用インキで、１５０メッシュのスクリーン版を用いて全面にベタ印刷し、１３０℃にて５分間乾燥硬化させて非変色層を形成し、更にその上面に、微粉末シリカ〔商品名：ニップシールＥ−１０１１、日本シリカ工業（株）製〕１５部、ポリカーボネート系ウレタンエマルジョン（固形分：３０％）４５部、水２０部、シリコーン系消泡剤０．２部、エチレングリコール３部、水系増粘剤３部、ブロックイソシアネート系架橋剤１．５部を均一混合攪拌してなる白色スクリーン用インキにて、１８０メッシュのスクリーン版を用いて印刷し、１３０℃にて５分間乾燥硬化させて白色の多孔質層を設けた。
更にその上面に、可逆熱変色性材料を内包したマイクロカプセル顔料（青色←→無色、３０℃未満で青色、３０℃以上で無色）１０部、ポリエステル系ウレタンエマルジョン（固形分３０％）１０部シリコーン系消泡剤０．２部、水１部、エチレングリコール０．５部、増粘剤０．５部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキを１８０メッシュのスクリーン版を用いて全面にベタ印刷を行ない、１３０℃にて５分間乾燥硬化させて可逆熱変色層を形成し変色体を得た。
前記多孔質層は、水もしくは水溶性液体の付着により、白色状態から無色透明状態に変化する。
【００３６】
前記変色体は、２４℃の室温下では青色を呈していたが、ドライヤーで３０℃以上に加温すると、可逆熱変色層が無色になり、下層の多孔質層による白色が視覚される。又、３０℃以上では白色状態を呈していたが、再び３０℃未満の温度になると青色に戻る。
更に、青色の状態を呈している変色体に約４０℃の温水を付着させると、可逆熱変色層が無色になると共に、多孔質層も透明化するため、非変色層によるピンク色が視覚される。前記状態は水が付着している状態で３０℃未満の温度になると可逆熱変色層が青色になるため、非変色層と混色になった紫色に変色し、又、乾燥するに従って多孔質層が白色になるため紫色から青色に変化し、完全乾燥した状態では再び青色となった。
この青色の変色体に約２０℃の水を付着させると、多孔質層が透明化して可逆熱変色層の青色と非変色層のピンク色が混色となった紫色に瞬時に変化し、水が付着している状態では紫色を呈していたが、乾燥するに従って紫色から青色に変化し、完全乾燥した状態では再び青色状態となった。
このように、前記変色体は、青色、白色、紫色、ピンク色の４色を得ることができ、前記様相変化を繰り返し再現させることができた。
【００３７】
【００３８】
【００３９】
実施例９（図７参照）
支持体４として黄色のナイロンタフタ生地上に、感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（青色←→無色、１５℃以下で青色、３０℃以上で無色）１０部、アクリル酸エステルエマルジョン（固形分５０％）１０部、シリコーン系消泡剤０．２部、水１部、エチレングリコール０．５部、増粘剤０．５部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキを１０９メッシュのスクリーン版を用いて全面にベタ印刷を行ない、１３０℃にて５分間乾燥硬化させて可逆熱変色層２を形成した。
次いで、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、アクリル酸エステルエマルジョン（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、ブロック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１８０メッシュのスクリーン版を用いて、前記可逆熱変色層２上に全面にベタ印刷し、１３０℃にて５分間乾燥硬化させて、乾燥状態で白色の多孔質層３を形成した。
更に、感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（ピンク色←→無色、４０℃以下でピンク色、４０℃以上で無色）１０部、アクリル酸エステルエマルジョン（固形分５０％）１０部、シリコーン系消泡剤０．２部、水１部、エチレングリコール０．５部、増粘剤０．５部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキを１８０メッシュのスクリーン版を用いて、水玉模様を印刷し、１３０℃にて５分間乾燥硬化させて可逆熱変色図柄層２１を形成し、変色体１を得た。
【００４０】
前記変色体１は、乾燥状態且つ２４℃の室温下では多孔質層３による白色地に、可逆熱変色図柄層２１によるピンク色の水玉模様が視覚されていたが、４０℃以上に加温すると可逆熱変色図柄層２１が消色して全面が白色状態となり、その状態から加温を止めて４０℃以下に冷却させると、再び可逆熱変色図柄層２１によるピンク色の水玉模様が現出し、この現象は何度も繰り返し行なうことができた。
次に、前記変色体１に３５℃の温水を付着させると、多孔質層３が水の付着により透明化すると共に、可逆熱変色層２が青色から無色に変色するため、支持体４による黄色地に、可逆熱変色性図柄層２１のピンク色と支持体４の黄色が混色となった赤色の水玉模様が視覚された。
更に、４０℃以上の温水に浸漬させると、前記可逆熱変色性図柄層２１が消色して全面が黄色になったが、２４℃の室温下で放置したところ、水が付着した状態では、黄色地に赤色の水玉模様が現出し、水が蒸発するに従って徐々に黄色地が白色になり、乾燥状態に戻ると元の白色地にピンク色の水玉模様が視覚された。
次に、乾燥状態の変色体に１５℃以下の冷水を付着させると、支持体４の黄色と可逆熱変色層２の青色が混色となった緑色地に、前記緑色と可逆熱変色図柄層２１のピンク色が混色となった茶色の水玉模様が視覚され、この状態は、１５℃以下の冷水中、又は、２４℃の室温下で水が付着した状態では保持されたが、乾燥するに従って緑色が白色に変化し、完全に乾燥すると元の白色地にピンクの水玉模様が視覚された。
このように、前記変色体１は、デサイン及び色変化を水媒体の付着及び温度変化により、多様に変化することができ、前記様相変化を何度も可逆的に再現させることができる。
【００４１】
実施例１０（図８参照）
支持体４として、青色のＡＢＳ製のミニカーのボディに、可逆熱変色性材料を内包したマイクロカプセル顔料（ピンク色←→無色、３０℃未満でピンク色、３０℃以上で無色）１０部、油性アクリル樹脂溶液〔商品名：アクリディクＡ１６５、大日本インキ化学工業（株）製〕３０部、塩化ビニル酢酸ビニル共重合樹脂５部、キシレン３０部、ＭＩＢＫ４０部を均一に混合攪拌、溶解させてなる黄色の油性スプレーインキをスプレー塗装し、室温で乾燥させ、星柄の可逆熱変色図柄層２１を形成した。
次いで、低屈折率顔料として湿式法微粒子珪酸〔商品名：ニップシールＥ−２００Ａ、日本シリカ工業（株）製〕１０部、バインダーとして水性ウレタン樹脂〔商品名：ハイドランＡＰＸ１０１、大日本インキ化学工業（株）製〕３０部、水１０部、イソプロピルアルコール２０部、シリコーン系消泡剤０．５部を均一に混合攪拌してなる水性スプレーインキを用いて、前記可逆熱変色図柄層２１を隠蔽できる大きさの円形をスプレー塗装し、４０℃で約１時間乾燥させて多孔質図柄層３１を形成して変色体１を得た。
【００４２】
前記変色体１は、２４℃の室温下では青色のボディに多孔質図柄層３１による白色の円形が塗装された状態を示していたが、４０℃の温水中に浸漬させると多孔質図柄層３１層は透明化し、且つ、可逆熱変色図柄層２１は消色するため、全面が青色のボディとなり、温水中ではその状態を呈していたが、温水中から取り出して放置すると、可逆熱変色図柄層２１が発色してピンク色を呈するためボディの青色とピンク色が混色となった紫色の星柄が現出し、水が付着した状態ではその状態を示していたが、乾燥するに従って元の白色の円形に戻った。
ついで、２０℃の水中に浸漬させると、多孔質図柄層３１が透明化するため、白色の円形から紫色の星柄へと変化し、水中ではその状態を示していたが、水中から取り出して乾燥させると再び青色のボディに白色の円形が描かれた状態となった。
前記したように温度変化、水媒体の付着及び乾燥により、色調が変化し、又、この現象は何度も繰り返し行なうことができた。
【００４３】
実施例１１（図９参照）
支持体４として、青色のＡＢＳ製のミニカーのボディに、低屈折率顔料として湿式法微粒子珪酸〔商品名：ニップシールＥ−２００Ａ、日本シリカ工業（株）製〕１０部、バインダーとして水性ウレタン樹脂〔商品名：ハイドランＡＰＸ１０１、大日本インキ化学工業（株）製〕３０部、水１０部、イソプロピルアルコール２０部、シリコーン系消泡剤０．５部を均一に混合攪拌してなる水性スプレーインキを用いて星柄をスプレー塗装し、４０℃で約１時間乾燥させて多孔質図柄層３１を形成した。
次いで、前記多孔質図柄層３１上に、可逆熱変色性材料を内包したマイクロカプセル顔料（含水率５０％、ピンク色←→無色、３０℃未満でピンク色、３０℃以上で無色）２５部、水性ウレタン樹脂〔商品名：ハイドランＡＰＸ１０１、大日本インキ化学工業（株）製〕４０部、水１０部、イソプロピルアルコール２０部、シリコーン系消泡剤０．５部を均一に混合攪拌してなる水性スプレーインキを用いて、前記多孔質図柄層３１と同じ形状及び大きさの星柄をスプレー塗装して可逆熱変色図柄層２１を形成して変色体１を得た。
【００４４】
前記変色体１は、２４℃の室温下では青色のボディに可逆熱変色図柄層２１によるピンク色の星型が塗装された状態を示していたが、ドライヤーの温風で加温すると可逆熱変色図柄層２１が消色して多孔質図柄層３１による白色の星柄が視覚され、３０℃以上ではその状態を呈していたが、加温を止めて室温下で放置すると、再び可逆熱変色図柄層２１が発色してピンク色の星形に戻った。
ついで、４０℃の温水中に浸漬させると、可逆熱変色図柄層２１が消色し、且つ、多孔質図柄層３１が透明化するため、全面が青色のボディとなり、温水中ではその状態を示していたが、温水中から取り出して約２０℃の水中に浸漬させると、可逆熱変色図柄層が発色してピンク色になるため、支持体４の青色と可逆熱変色図柄層２１のピンク色が混色となった紫色の星形へと変化し、水中ではその状態を呈していたが、水中から取り出して乾燥させると再び青色のボディにピンク色の星形が描かれた状態となった。
前記したように温度変化、水媒体の付着及び乾燥により、色調が変化し、又、この現象は何度も繰り返し行なうことができた。
【００４５】
実施例１２（図１０参照）
支持体４として５０デニールポリエステルトリコット白色生地上に、オレンジ色蛍光顔料〔商品名：エポカラーＦＰ−４０、（株）日本触媒製〕１０部、水性アクリルエマルジョン〔商品名：ポリゾールＡＰ−５０、昭和高分子（株）製〕６０部、水１０部、エチレングリコール５部、シリコーン系水系インキ用消泡剤０．５部、水系インキ用増粘剤３部、レベリング剤１部、イソシアネート系架橋剤２部を均一に混合攪拌してなるオレンジ色の水性スクリーンインキ、及び、黄色蛍光顔料〔商品名：エポカラーＦＰ−１１７、（株）日本触媒製〕１０部、水性アクリルエマルジョン〔商品名：ポリゾールＡＰ−５０、昭和高分子（株）製〕６０部、水１０部、エチレングリコール５部、シリコーン系水系インキ用消泡剤０．５部、水系インキ用増粘剤３部、レベリング剤１部、エポキシ系架橋剤２部を均一に混合攪拌してなる黄色の水性スクリーンインキをそれぞれ用いて、１５０メッシュのスクリーン版にて縦縞模様を印刷し、１２０℃で約３分間乾燥硬化させて非変色図柄層５１を形成した。
次いで、低屈折率顔料として湿式法微粒子珪酸〔商品名：ミズカシルＰ−５２７、水澤化学工業（株）製〕２０部、バインダーとして水性ウレタンエマルジョン〔商品名：ハイドランＨＷ９３０、大日本インキ化学工業（株）製〕６０部、水１５部、プロピレングリコール３部、シリコーン系消泡剤０．５部、水性インキ用増粘剤３部、ブロックイソシアネート系水性インキ用架橋剤４．０部を均一に混合攪拌してなる白色水性スクリーンインキにて１５０メッシュのスクリーン版を用いて、前記非変色図柄層５１の全面に印刷し、多孔質層３を形成した。
更にその上面に、感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（含水率５０重量％、ピンク色←→無色、１５℃以下でピンク色、３０℃以上で無色）１５部、バインダーとして水性ウレタンエマルジョン〔商品名：ハイドランＨＷ９３０、大日本インキ化学工業（株）製〕３０部、水７部、プロピレングリコール１部、シリコーン系消泡剤０．２部、水性インキ用増粘剤２部、ブロックイソシアネート系水性インキ用架橋剤２．０部を均一に混合攪拌してなるピンク色水性スクリーンインキ、及び、感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（含水率５０重量％、青色←→無色、１５℃以下で青色、３０℃以上で無色）１５部を用いた以外は前記と同様に調製した青色水性スクリーンインキ（変色性材料）をそれぞれ用いて、１８０メッシュのスクリーン版にて前記非変色層４の縦縞模様と直交する横縞模様を印刷して可逆熱変色図柄層２１を形成し、変色体１を得た。
【００４６】
前記変色体１は、２４℃の室温下では可逆熱変色図柄層２１によるピンク色と青色の横縞模様が視覚されるが、ドライヤーで３０℃以上に加温すると可逆熱変色図柄層２１が消色して多孔質層３による白色が視覚され、室温下で放置してもその状態を保持していた。
前記変色体を約１０℃の冷風で冷却すると、可逆熱変色図柄層２１が発色して再び白色状態からピンク色と青色の横縞模様に変化し、室温下でその状態を保持していた。
ついで、約４０℃の温水中に前記変色体１を浸漬させると可逆熱変色図柄層２１は消色し、且つ、多孔質層３は透明化するため、非変色図柄層５１によるオレンジ色と黄色の縦縞模様に変化し、約４０℃の温水中ではその状態を示していたが、温水中から取り出して約１０℃の氷水中に浸漬させると可逆変色図柄層２１が発色するため、非変色図柄層５１と混色となった赤色、緑色、茶色からなる格子模様に変化し、約１０℃の水中ではその状態を呈していたが、水中から取り出して室温下で放置すると、乾燥するに従って格子模様から徐々に横縞模様へと変化し、完全乾燥によりピンク色と青色の横縞模様となった。
前記したように、温度変化、水媒体の付着及び乾燥により、色調及びデザインが変化し、又、この現象は何度も繰り返し行なうことができた。
【００４７】
実施例１３（図１１参照）
支持体４として、４０デニールナイロントリコット蛍光ピンク色生地上の全面に、低屈折率顔料として湿式法微粒子珪酸〔商品名：ニップシールＥ−１０１１、日本シリカ工業（株）製〕２０部、バインダーとして水性ウレタンエマルジョン〔商品名：ハイドランＡＰ−１０、大日本インキ化学工業（株）製〕６０部、水１５部、プロピレングリコール３部、シリコーン系消泡剤０．５部、水性インキ用増粘剤３部、ブロックイソシアネート系水性インキ用架橋剤４．０部を均一に混合攪拌してなる白色水性スクリーンインキにて１５０メッシュのスクリーン版を用いて印刷して多孔質層３を形成した。
ついで、前記多孔質層３上に、可逆熱変色性材料を内包したマイクロカプセル顔料（含水率５０重量％、黄色←→無色、１５℃未満で黄色、１５℃以上で無色）３０部、バインダーとして水性アクリルエマルジョン〔商品名：モビニール７００、ヘキスト合成（株）製〕３５部、水１５部、プロピレングリコール３部、シリコーン系消泡剤０．５部、水性インキ用増粘剤３部、ブロックイソシアネート系水性インキ用架橋剤３．５部を均一に混合攪拌してなる黄色水性スクリーンインキ（変色性材料）、及び、可逆熱変色性材料を内包したマイクロカプセル顔料（含水率５０重量％、青色←→無色、１５℃未満で青色、１５℃以上で無色）１５部を用いた以外は前記と同様に調製した青色水性スクリーンインキをそれぞれ用いて、１５０メッシュのスクリーン版にて波模様を印刷し、１００℃で３分間硬化乾燥させて可逆熱変色図柄層２１を形成した。
更に、前記可逆熱変色図柄層２１上に、蛍光ピンク色顔料〔商品名：エポカラーＦＰ−１０００Ｎ、（株）日本触媒製〕１０部、水性アクリルエマルジョン〔商品名：ポリゾールＡＰ−５０、昭和高分子（株）製〕６０部、水１０部、エチレングリコール５部、シリコーン系水系インキ用消泡剤０．５部、水系インキ用増粘剤３部、レベリング剤１部、イソシアネート系架橋剤２部を均一に混合攪拌してなるピンク色の水性スクリーンインキを用いて、１８０メッシュのスクリーン版にて水玉模様を印刷し、１３０℃で３分間硬化乾燥させて非変色図柄層５１を形成して変色体１を得た。
【００４８】
前記変色体１は、約２４℃の室温下では多孔質層３による白色地上に非変色図柄層５１による蛍光ピンク色の水玉模様が描かれた状態を示していたが、冷風で１５℃未満に冷却すると可逆熱変色図柄層２１が発色して白色地部分が黄色と青色の波柄に変化し、１５℃以下ではその状態を示していたが、冷却を止めて室温下で放置すると再び白色に変化した。
ついで、約２０℃の水中に浸漬させると、多孔質層３が透明化するため、非変色図柄層５１のピンク色と支持体４のピンク色が同調して全面が蛍光ピンク色になり、水中ではその状態を呈していた。前記変色体１を１０℃の水中に浸漬させると可逆熱変色図柄層２１が発色するため、青色と蛍光ピンク色が混色となった紫色、及び、黄色と蛍光ピンク色が混色となった赤色の波柄上に、非変色図柄層５１による蛍光ピンク色の水玉模様が描かれた状態へと変化し、水中ではその状態を維持していた。
前記変色体１を水中から取り出して室温下で放置すると可逆熱変色図柄層２１が消色し、水が付着した状態では前記した状態から全面がピンク色へと変化し、完全乾燥すると、白地に蛍光ピンク色の水玉模様が描かれた状態となった。
前記したように、温度変化、水媒体の付着及び乾燥により、色調及びデザインが変化し、又、この現象は何度も繰り返し行なうことができた。
【００４９】
比較例１
支持体としてピンク色のナイロンタフタ生地上に、感温変色性色彩記憶性材料を内包したマイクロカプセル顔料（青色←→無色、１５℃以下で青色、３０℃以上で無色）１０部、アクリル酸エステルエマルジョン（固形分５０％）１０部、シリコーン系消泡剤０．２部、水１部、エチレングリコール０．５部、増粘剤０．５部、イソシアネート系架橋剤０．５部を均一に混合攪拌してなる可逆熱変色性スクリーンインキを１０９メッシュのスクリーン版を用いて全面にベタ印刷を行ない、１３０℃にて５分間乾燥硬化させて可逆熱変色層を形成して変色体を得た。
【００５０】
前記変色体は、１５℃以下に冷却すると支持体のピンク色と可逆熱変色層の青色が混合して紫色が視覚され、この色調は３０℃未満の温度域で保持される。又、３０℃以上に加温すると、可逆熱変色層が無色となり、支持体のピンク色が視覚され、この色調は１５℃を越える温度域で保持されるものであるが、色調の変化は２状態しかなく、変化性に乏しいものであった。
【００５１】
比較例２
支持体としてピンク色のナイロンタフタ生地上に、微粉末シリカ〔商品名：ニップシールＥ−１０１１、日本シリカ工業（株）製〕１５部、ポリカーボネート系ウレタンエマルジョン（固形分：３０％）４５部、水２０部、シリコーン系消泡剤０．２部、エチレングリコール３部、水系増粘剤３部、ブロックイソシアネート系架橋剤１．５部を均一混合攪拌してなる白色スクリーン用インキにて、１８０メッシュのスクリーン版を用いて印刷し、１３０℃にて５分間乾燥硬化させて白色の多孔質層を設けて変色体を得た。
【００５２】
前記変色体は、乾燥状態で白色を呈し、水を付着させると多孔質層が透明化して支持体のピンク色が視覚さるものであるが、色調の変化は２状態しかなく、変化性に乏しいものであった。
【００５３】
【発明の効果】
本発明変色体は、可逆熱変色層と、低屈折率顔料を含む吸液により透明又は半透明化する多孔質層とを積層してなり、生活環境温度域の温度変化及び水等の媒体により、多彩に色変化させた様相を視覚させることができ、前記変化した様相は、繰り返し、可逆的に再現できるため、玩具、意匠、ファッション、装飾分野等に応用展開が可能な変色体を提供できる。
【図面の簡単な説明】
【図１】 本発明変色体の一実施例の縦断面説明図である。
【図２】 本発明変色体の他の実施例の縦断面説明図である。
【図３】 本発明変色体の他の実施例の縦断面説明図である。
【図４】 本発明変色体の他の実施例の縦断面説明図である。
【図５】 本発明変色体の他の実施例の縦断面説明図である。
【図６】 本発明変色体の他の実施例の縦断面説明図である。
【図７】 本発明変色体の他の実施例の縦断面説明図である。
【図８】 本発明変色体の他の実施例の縦断面説明図である。
【図９】 本発明変色体の他の実施例の縦断面説明図である。
【図１０】 本発明変色体の他の実施例の縦断面説明図である。
【図１１】 本発明変色体の他の実施例の縦断面説明図である。
【符号の説明】
１ 変色体
２ 可逆熱変色層
２１ 可逆熱変色図柄層
３ 多孔質層
３１ 多孔質図柄層
４ 支持体
５ 非変色層
５１ 非変色図柄層[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a color changing body. More specifically, the present invention relates to a discolored body that changes to a state different from a normal state by heat and / or water.
[0002]
[Prior art]
  2. Description of the Related Art Conventionally, a thermochromic processed body to which a reversible thermochromic material is applied has been widely applied to toys, decoration fields and the like. Also known is a processed paper (for example, Japanese Patent Publication No. 50-5097) which is provided with a porous layer containing a low refractive index pigment and is transparent in a liquid absorption state to produce a colored image different from the normal state.
[0003]
[Problems to be solved by the invention]
  The present inventor provides a color-changing body that exhibits a combined effect, which cannot be achieved by the single material, by combining the reversible thermochromic material and the liquid-absorbing transparent material, and to the field of toys and decorations. It is intended to develop the application of.
[0004]
[Means for Solving the Problems]
  The present inventionA reversible thermochromic layer and a porous layer that is made transparent or translucent by liquid absorption containing a low refractive index pigment are laminated,Require a discolored body that changes color by heat or water. Furthermore, SupportOn the bodySaidA reversible thermochromic layer is provided.YesOn the reverse thermochromic layerin frontPorous layerTheSettingJustTo become a,in frontA reversible thermochromic pattern layer is disposed on the porous layer, on the support.SaidProvide a porous layerManyThe reversible thermochromic layer on the porous layerTheSettingJustTo become a,in frontA porous design layer is provided on the reversible thermochromic layer., Said yesReverse heat discolorationLayer figureBe a patterned layer,The porous layer is a design layer;The requirement is that the support is a fabric.
[0005]
  Examples of the reversible thermochromic material used for forming the reversible thermochromic layer include an electron donating color-forming organic compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction of the both. Reversible thermochromic composition containing three components, liquid crystal, Ag₂HgI₄, Cu₂HgI₄Etc. are used.
  As a reversible thermochromic material containing three components of an organic compound medium that reversibly causes a color reaction between the electron-donating color-forming organic compound and the electron-accepting compound, specifically, Japanese Patent Publication No. 51-35414. Gazette, Japanese Patent Publication No. 51-44706, SpecialExamples thereof include those described in JP-B-51-44708, JP-B-52-7764, JP-B-1-29398, JP-A-7-186540, and the like. The color changes before and after a predetermined temperature (discoloration point), and only one specific state can exist in the normal temperature range among both states before and after the change. That is, the other state is maintained while the heat or cold necessary to develop the state is applied, but when the heat or cold is no longer applied, the state returns to the state exhibited in the normal temperature range, so-called, This is a type in which the temperature-color density due to temperature change shows a small hysteresis width (ΔH) and changes color.
[0006]
  In addition, the temperature-sensitive color-changing color that changes color with a large hysteresis characteristic described in Japanese Patent Publication No. 4-17154, Japanese Patent Application Laid-Open No. 7-179777, Japanese Patent Application Laid-Open No. 7-33997, etc. proposed by the present applicant. The shape of the memory material, that is, the curve plotting the change in color density due to the temperature change, lowers the temperature from the higher temperature side than the color change temperature, contrary to the case where the temperature is raised from the lower temperature side than the color change temperature range. It is a type of color change material that changes color by following a very different path, and changes at a temperature below the low temperature side color change point or above the high temperature side color change point in the normal temperature range between the low temperature side color change point and the high temperature side color change point. A reversible thermochromic material having the feature that the stored state can be stored and retained is also effective.
[0007]
  The above-described reversible thermochromic material containing three components of an organic compound medium that reversibly causes a color reaction with an electron-donating color-forming organic compound and an electron-accepting compound is effective even when applied as it is, It is preferable to use it in a capsule. That is, the reversible thermochromic material is maintained in the same composition under various use conditions, and can exhibit the same function and effect.
  By encapsulating in the microcapsule, a chemically and physically stable pigment can be formed, and a particle diameter of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 2 to 30 μm satisfies the practicality.
  Microencapsulation includes conventionally known interfacial polymerization methods, in situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, melt dispersion cooling methods, air suspensions. There are a coating method, a spray drying method, and the like, which are appropriately selected according to the application. Furthermore, the surface of the microcapsule can be provided with a secondary resin film according to the purpose to impart durability, or the surface characteristics can be modified for practical use.
[0008]
  The reversible thermochromic material (preferably, the microencapsulated pigment) is dispersed in a binder which is a film forming material, and is used as a coloring material such as ink or paint on various supports.reversibleA thermochromic layer can be formed. Moreover, it can also be applied as a support having itself reversible thermochromic properties, which is dispersed in a thermoplastic resin or a thermosetting resin and formed into a sheet or various forms.
  It should be noted that non-thermochromic general dyes and pigments can be mixed in the thermochromic layer and various colors can be changed.
[0009]
  As the support, paper, synthetic paper, fabric, flocked or raised cloth, non-woven fabric, synthetic leather, leather, plastic, glass, ceramics, wood, stone, etc. are all effective.
[0010]
  The resin contained in the binder is preferably a transparent film-forming resin, and is exemplified below.
  Ionomer resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile chlorinated polyethylene-styrene copolymer resin, ethylene-vinyl chloride Copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene Resin, chlorinated polypropylene resin, polyamide resin, high density polyethylene resin, medium density polyethylene resin, linear low density polyethylene resin, polyethylene terephthalate resin, polybutylene terephthalate Fat, polycarbonate resin, polystyrene resin, high impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylate resin, polymethyl methacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin modified phenolic resin, rosin modified alkyd resin, phenol Modified alkyd resin, epoxy modified alkyd resin, styrene modified alkyd resin, acrylic modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, epoxy resin, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion Resin, styrene-butadiene emulsion resin, acrylic ester emulsion resin, water-soluble alkyd resin, water-soluble melamine resin, water Sex urea resins, water-soluble phenolic resin, water-soluble epoxy resin, water-soluble polybutadiene resins, cellulose acetate, nitrate cellulose, mention may be made of ethylcellulose, and the like.
[0011]
  The porous layer is a layer in which a low-refractive-index pigment is fixed in a dispersed state together with a binder resin, concealing the lower layer in a dry state, and transparent or semi-transparent when liquid such as water is absorbed to visually recognize the lower layer It is a layer that returns to its original state when the liquid-absorbed portion is dried.
  In addition, when the colorant is included in the porous layer, it is colored and transparent in the dry state to conceal the lower layer, and when a medium such as water is absorbed, the colored transparent or colored translucent can be visualized and the lower layer can be visually recognized. It is a layer that returns to its original state when the part is dried.
  Examples of the colorant include general colored dyes and pigments, or fluorescent dyes and pigments. If desired, titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate. Further, metallic luster pigments such as acidic lead arsenate and bismuth oxychloride can also be used.
  Examples of the low refractive index pigment include fine particle silicic acid, 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 exhibits good transparency when water is absorbed.
  The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
  Two or more of the low refractive index pigments can be used in combination.
  In addition, a particulate silica is mentioned as a low refractive index pigment used suitably. Particulate silicic acid is produced as amorphous amorphous silicic acid, and is produced by a dry process using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as dry process particulate silicic acid). And by a wet method using a liquid phase reaction such as decomposition with an acid such as sodium silicate (hereinafter referred to as wet method fine particle silicic acid), and any of them can be used. When wet method fine particle silicic acid is used, since the concealment property in the normal state is larger than that of dry method fine particle silicic acid, it is possible to increase the mixing ratio of the binder resin to the fine particle silicic acid. Since the film strength of the film can be improved, it is more preferably used.
  As described above, as the fine particulate silicic acid used for satisfying the normal concealing property of the porous layer, wet method fine particulate silicic acid is preferable. This is because the dry method fine particle silicic acid and the wet method fine particle silicic acid have different structures, whereas the dry method fine particle silicic acid forms a three-dimensional structure in which silicic acid is closely bound as shown below. ,
[Chemical 1]

As shown below, the wet method fine particle silicic acid has a so-called two-dimensional structure part in which a long molecular arrangement is formed by condensation of silicic acid. Accordingly, since the molecular structure is coarser than that of the above-mentioned dry method fine particle silicic acid, when wet method fine particle silicic acid is applied to the porous layer, the light in the dry state compared to the system using the dry method fine particle silicic acid. Therefore, it is presumed that the concealability in the normal state is increased.
[Chemical formula 2]

  Further, the low refractive index pigment contained in the porous layer preferably has moderate hydrophilicity because the medium that permeates is mainly water. Accordingly, wet process fine particle silicic acid is preferably used because it has a higher hydrophilicity than the dry process fine particle silicic acid because it has more hydroxyl groups present as silanol groups on the particle surface.
[0012]
  When the wet method fine particle silicic acid is used as a low refractive index pigment, it depends on the properties of the wet method fine particle silicic acid, the particle diameter, the specific surface area, the oil absorption amount, etc. In order to satisfy both transparency, the coating amount is 1 g / m.²~ 30g / m²And more preferably 5 g / m.²~ 20g / m²It is. 1g / m²Is less than 30 g / m, it is difficult to obtain sufficient concealability in a normal state.²If it exceeds the range, it is difficult to obtain sufficient transparency upon water absorption.
[0013]
  The low refractive index pigment is dispersed and applied in a vehicle containing a binder resin as a binder, and then the volatile matter is dried to form a porous layer.
  Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic 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, carboxylated Examples include SBR resin, carboxylated NBR resin, and the above resin emulsions, casein, starch, cellulose derivatives, polyvinyl alcohol, urea resin, phenol resin, epoxy resin, and the like.
[0014]
  Since the porous layer has a small mixing ratio of the binder resin to the pigment as compared with a conventionally known general coating film, it is difficult to obtain a sufficient film strength. Therefore, in applications that require washing resistance and scratch resistance, it is preferable to use a urethane-based resin or a nylon resin as the above-mentioned binder resin, or to contain at least the resin.
  Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination. In addition, urethane emulsion resin in which the resin is emulsified and dispersed in water, or ionic urethane resin (urethane ionomer) itself self-emulsifies without requiring an emulsifier and dissolves in water.NoA highly dispersed colloidal dispersion type (ionomer type) urethane resin can also be used.
  The urethane-based resin may be either an aqueous urethane-based resin or an oil-based urethane-based resin, but an aqueous urethane-based resin, particularly a urethane-based emulsion resin or a colloidally dispersed urethane-based resin is preferably used.
  The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain 30% or more of the urethane resin in a solid content weight ratio in the binder resin of the porous layer.
  In the binder resin, the crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking.
  The binder resin has a large or small affinity with a medium. By combining these, the penetration time into the porous layer, the degree of penetration, and the slow speed of drying after the penetration can be adjusted. Furthermore, a dispersing agent can be added as appropriate to control the permeation time, the degree of permeation, and the slowness of drying after permeation.
[0015]
  If necessary, the discolored material of the present invention may be provided with a non-discoloring layer with a non-discoloring ink containing a general dye or pigment, or may be coated with titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, silk The metallic luster layer can also be provided by an ink containing a metallic luster pigment such as mica, basic lead carbonate, acidic lead arsenate, bismuth oxychloride.
  Further, a protective layer and a light stabilizer layer can be appropriately provided. Specifically, the light stabilizer layer is selected from an ultraviolet absorber, an antioxidant, an anti-aging agent, a singlet oxygen quencher, a superoxide anion quencher, an ozone decolorant, a visible light absorber, and an infrared absorber. This is a layer in which the light stabilizer is fixed in a dispersed state.
  In addition, an antistatic agent, a polarity imparting agent, a thixotropic imparting agent, an antifoaming agent, and the like can be added to the reversible thermochromic layer and the porous layer as necessary to improve the function.
[0016]
  In the structure of the present invention, the reversible thermochromic layer itself is a support, and in a system in which a porous layer is provided on the reversible thermochromic layer, a medium such as water in a temperature range where the reversible thermochromic layer does not discolor. When attached, the medium penetrates the porous layer and becomes transparent, and the color tone of the lower reversible thermochromic layer is visually recognized.
  On the other hand, when a medium such as water in a temperature range that changes the color of the reversible thermochromic layer is attached, the medium penetrates into the porous layer and becomes transparent, and the lower reversible thermochromic layer changes color.
  Further, as a specific example, a reversible thermochromic layer that changes color depending on body temperature is provided, and after the porous layer is made transparent by attaching a medium such as water in a temperature range where the reversible thermochromic layer does not change color, Thus, the reversible thermochromic layer can be discolored, and a variety of discoloration is exhibited by the combined use with the non-discoloring layer.
  Here, the reversible thermochromic layer in the above-described configuration may be either colored ← → colorless reversible color change or colored (1) ← → colored (2) reversible color change.
  In the configuration of the discolored body of the present invention, in order to visualize three or more different hues, the color tone of the lower layer of the porous layer must exhibit two or more color tones different from the color tone of the porous layer in the dry state. Don't be. In order to make the two or more different hues visible, the reversible thermochromic layer itself exhibits a different color tone, and the reversible thermochromic layer is a layer that reversibly discolors from colored to colorless. It is necessary to provide a support different from the color tone or to provide a colored layer.
  Since the porous layer is a layer containing a low-refractive index pigment such as silica, it can exhibit a high concealment property during drying and completely conceal the color tone of the lower layer, so even if the lower layer is dark, It can be configured such that a relatively bright color tone is visible.
  Furthermore, on the porous layerYesDesign changes can be diversified by providing a reverse heat discoloration pattern layer.
[0017]
  Next, a system in which a porous layer is provided on a support and a reversible thermochromic layer is provided on the porous layer will be described. In order for a medium such as water to penetrate into the porous layer, the reversible The thermochromic layer is also preferably a layer having a property that the aqueous medium can penetrate.
  When the reversible thermochromic layer reversibly discolors from colored to colorless and is in a colored state at ambient temperature, the reversible thermochromic layer is formed by attaching a medium such as water in the temperature range where the composition changes color to the discolored body. In addition to decoloring, the porous layer also becomes transparent and the color tone of the support is visually recognized.
  In addition, when heating or cooling without touching a medium such as water, such as touching or blowing warm air or cold air, the reversible thermochromic layer disappears and the color tone of the porous layer is visually recognized. The
  Furthermore, when the reversible thermochromic layer reversibly discolors from colored to colorless and is decolored at ambient temperature, the reversible thermochromic layer changes.ColorWhen a medium such as water in a non-temperature range is attached, the porous layer becomes transparent and the color tone of the support is visually recognized, and when the medium in the temperature range where the reversible thermochromic layer changes color is attached to the color change body, the thermochromic layer Is visible in a colored state.
  Note that the reversible thermochromic layer in the above-described configuration is preferably one that reversibly discolors from colored to colorless. In order to visualize three or more different hues, the lower layer of the reversible thermochromic layer is reversible. Two or more color tones different from the color tone of the thermochromic layer must be exhibited. As the configuration exhibiting two or more different color tones, the support and the dry porous layer each have a different color tone, or a colored layer having a different color tone from the dry porous layer and the porous layer. It is necessary to interpose between the supports.
  Furthermore, since the porous layer is a layer containing a low refractive index pigment such as silica, it exhibits high concealment when dried and can completely conceal the color tone of the lower layer. The reversible thermochromic layer provided in the upper layer is Bright colors can be exhibited.
  Further, on the reversible thermochromic layerManyA porous design layer can be provided to diversify design changes.
[0018]
  In the laminated structure described above, the reversible thermochromic layer and the porous layer may be symbol layers such as letters, symbols, and figures if necessary.
  In addition, a non-discoloring layer may be interposed between the layers, or may be provided in an upper layer. Similarly, a pattern layer such as a character, a symbol, or a figure may be used.
  The reversible thermochromic layer, porous layer, and non-color-changing layer may be formed by a conventionally known method, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, static coating. It can be formed by means such as electrocoating, electrocoating, flow coating, roller coating, and dip coating.
[0019]
  As described above, the present invention makes it possible to most effectively express a variety of discoloration in a laminated structure of a reversible thermochromic layer and a porous layer containing a low refractive index pigment.The
[0020]
DETAILED DESCRIPTION OF THE INVENTION
  The color changing body of the present invention is not limited to a planar shape, and various forms such as a linear shape, an uneven shape, and a three-dimensional shape are effective.
[0021]
【Example】
  Examples are shown below. In addition, the part in an Example shows a weight part.
  Example 1 (see FIG. 1)
  20 parts of microcapsule pigment (blue ← → colorless, blue at 15 ° C or lower, colorless at 30 ° C or higher) encapsulating a temperature-sensitive color-change color memory material, pink fluorescent pigment [trade name: Epocolor FP-10, Inc. ) Nippon Shokubai] 1 part, 2 parts of benzotriazole UV absorber, 1000 parts of polypropylene having a Vicat softening point of 100 ° C. were uniformly mixed, and then a reversible thermochromic pellet was obtained using an extruder. The pellet was formed into a reversible thermochromic layer 2 by forming a sheet by injection molding.
  When the reversible thermochromic layer 2 is cooled to 15 ° C. or lower, a bluish purple color is visually observed. This color tone is maintained in a temperature range below 30 ° C., and when heated to 30 ° C. or higher, it becomes pink. The color tone is a layer maintained in a temperature range exceeding 15 ° C.
  Next, fine powdered silica [trade name: Nipsil E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] 15 parts, acrylic ester emulsion (solid content 50%) 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 White screen printing ink obtained by uniformly mixing and stirring 3 parts of a thickener for water-based ink, 1 part of ethylene glycol and 3 parts of a block isocyanate-based cross-linking agent, using a 180 mesh screen plate, the reversible thermal discoloration The entire surface of the layer 2 was solid-printed and dried and cured at 130 ° C. for 5 minutes to form a white porous layer 3 in a dry state, whereby a discolored body 1 having a laminated structure was obtained.
  The porous layer 3 changes from a white state to a colorless and transparent state due to adhesion of water or an aqueous medium.
[0022]
  The discolored body 1 is white in a dry state and at a room temperature of 24 ° C., and remains white even when cooled or heated, but the porous layer 3 is transparent when cold water of 15 ° C. or less is attached. And instantly changed to bluish purple by the lower reversible thermochromic layer 2. When the blue-violet discoloration body 1 was allowed to stand at a room temperature of 24 ° C., it showed a bluish-purple color when water was attached, but gradually returned from blue-violet color to white as the water evaporated and became dry. When it returned, it turned white.
  Next, when hot water of 30 ° C. or higher is attached to the discolored body 1, the porous layer 3 becomes transparent due to the attachment of water, and the reversible thermochromic layer 2 changes from purple to fluorescent pink and becomes fluorescent pink. You can see the discoloration.
  When the blue-purple discoloration body 1 was left at room temperature of 24 ° C., it showed a fluorescent pink color when water was attached, but gradually returned from the fluorescent pink color to white as the water evaporated and dried. It returned to the original white color.
  Next, when warm water of 30 ° C. or higher is attached to a part of the discolored body 1 with cold water of 15 ° C. or less attached to the discolored body 1 in a dry state and discolored to bluish purple, the color changes from blue purple to pink This state maintained both the blue-purple and pink states until the water evaporated to dryness.
  In this way, the color changing body 1 can be changed from blue to purple or fluorescent pink by applying cold water or hot water from a white state on the entire surface, and returning to the original white state again by drying. The color change is reversibly reproducible.
[0023]
  Example 2 (see FIG. 2)
  10 parts of microcapsule pigment (blue ← → colorless, blue at 15 ° C or lower, colorless at 30 ° C or higher) 10 parts, acrylic acid on pink nylon taffeta fabric as support 4 Ester emulsion (solid content 50%) 10 parts, silicone antifoam 0.2 parts, water 1 part, ethylene glycol 0.5 parts, thickener 0.5 parts, isocyanate cross-linking agent 0.5 parts uniformly A reversible thermochromic screen ink obtained by mixing and stirring was solid-printed on the entire surface using a 109-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a reversible thermochromic layer 2.
  In the state where the support and the reversible thermochromic layer are laminated, when the temperature is lowered to 15 ° C. or lower, a purple color in which the pink color of the support and the blue color of the reversible thermochromic layer are mixed is visually recognized, and this color tone is less than 30 ° C. When maintained at a temperature range, and when heated to 30 ° C. or higher, the reversible thermochromic layer becomes colorless and the pink color of the support is visible, and this color tone is maintained at a temperature range exceeding 15 ° C. .
  Next, fine powdered silica [trade name: Nipsil E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] 15 parts, acrylic ester emulsion (solid content 50%) 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 White screen printing ink obtained by uniformly mixing and stirring 3 parts of a thickener for water-based ink, 1 part of ethylene glycol and 3 parts of a block isocyanate-based crosslinking agent, using a 180-mesh screen plate, the reversible thermal discoloration The entire surface of the layer 2 was solid-printed, dried and cured at 130 ° C. for 5 minutes, and the white porous layer 3 was formed in a dry state to obtain the color change body 1.
  The porous layer 3 changes from a white state to a colorless and transparent state due to adhesion of water or a water-soluble liquid.
[0024]
  The discolored body 1 is white in a dry state and at a room temperature of 24 ° C., and remains white even when cooled or heated. However, when cold water of 15 ° C. or less is attached, the porous layer 3 becomes water. It became transparent by the adhesion of and the color tone of the lower reversible thermochromic layer 2 and the support 4 instantly changed to a mixed purple color. When the purple discoloration body 1 was left at room temperature of 24 ° C., it was purple when water was attached, but gradually returned from purple to white as the water evaporated, It became the original white color.
  Next, when hot water of 30 ° C. or higher is attached to the discolored body 1, the porous layer 3 becomes transparent due to the attachment of water, and the reversible thermochromic layer 2 discolors from blue to colorless and pink by the support 4 Visualized as color change body 1.
  When the pink discoloration body 1 was left at room temperature of 24 ° C., it showed a pink color when water was attached, but gradually returned from pink to white as the water evaporated, and was in a dry state. Returning to, it became the original white color.
  Next, in a state where cold water of 15 ° C. or less is attached to the dried discolored body and the color is changed to purple, when warm water of 30 ° C. or more is attached to a part of the discolored body, the color changes from purple to pink, This state maintained both purple and pink states until the water evaporated to dryness.
  In this way, the color changing body 1 can be changed from a white state to a purple or pink color by applying cold water or hot water, and can be returned to the original white state by drying. Various color changes can be shown, and the above-mentioned change in appearance can be reversibly reproduced.
[0025]
  Example 3
  10 parts of microcapsule pigment (blue ← → colorless, blue at 15 ° C or lower, colorless at 30 ° C or higher) 10 parts, pink fluorescent on white nylon taffeta fabric as support 4 1 part of pigment [trade name: Epocolor FP-10, manufactured by Nippon Shokubai Co., Ltd.], 10 parts of acrylic ester emulsion (solid content 50%), 0.2 part of silicone antifoaming agent, 1 part of water, ethylene glycol 0 .5 parts, 0.5 parts thickener and 0.5 parts isocyanate cross-linking agent are mixed and stirred uniformly. Reversible thermochromic screen ink (blue purple ← → pink, blue purple at 15 ° C. or lower, 30 A reversible thermochromic layer 2 was formed by performing solid printing on the entire surface using a 109-mesh screen plate and drying and curing at 130 ° C. for 5 minutes.
  When the reversible thermochromic layer 2 is cooled to 15 ° C. or lower, a bluish purple color is visually observed. This color tone is maintained in a temperature range below 30 ° C., and when heated to 30 ° C. or higher, it becomes pink. The color tone is a layer maintained in a temperature range exceeding 15 ° C.
  Next, fine powdered silica [trade name: Nipsil E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] 15 parts, acrylic ester emulsion (solid content 50%) 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 White screen printing ink obtained by uniformly mixing and stirring 3 parts of a thickener for water-based ink, 1 part of ethylene glycol and 3 parts of a block isocyanate-based crosslinking agent, using a 180-mesh screen plate, the reversible thermal discoloration The entire surface of the layer 2 was solid-printed, dried and cured at 130 ° C. for 5 minutes, and the white porous layer 3 was formed in a dry state to obtain the color change body 1.
  The porous layer 3 changes from a white state to a colorless and transparent state due to adhesion of water or a water-soluble liquid.
[0026]
  The discolored body 1 is white in a dry state and at a room temperature of 24 ° C., and remains white even when cooled or heated. However, when cold water of 15 ° C. or less is attached, the porous layer 3 becomes water. It became transparent by the adhesion of and immediately changed to bluish purple by the lower reversible thermochromic layer 2. When the blue-violet discoloration 1 was allowed to stand at a room temperature of 24 ° C., it showed a bluish purple when water was attached, but gradually returned from blue-violet to white as the water evaporated and dried. Returning to, it became the original white color.
  Next, when hot water of 30 ° C. or higher is attached to the discolored body 1, the porous layer 3 becomes transparent due to the attachment of water, and the reversible thermochromic layer 2 changes from purple to fluorescent pink and becomes fluorescent pink. You can see the discoloration.
  When the blue-violet discoloration body 1 was left at room temperature of 24 ° C., it showed a fluorescent pink color when water adhered, but gradually returned from the fluorescent pink color to white as the water evaporated, When it returned to the dry state, it became the original white color.
  Next, when warm water of 30 ° C. or higher is attached to a part of the color change body with cold water of 15 ° C. or less attached to the color change body in a dry state and changed to blue purple, the color changes from blue purple to pink. In this state, both the blue-purple and pink states were maintained until the water evaporated to dryness.
  In this way, the color changing body 1 can be changed from blue to purple or fluorescent pink by applying cold water or hot water from a white state on the entire surface, and returning to the original white state again by drying. It is possible to obtain a color change body 1 that exhibits various color changes that can be reproduced, and to repeat and reproduce the above-described change in appearance.
[0027]
  Example 4 (see FIG. 3)
  10 parts of a yellow fluorescent pigment [trade name: Epocolor FP-117, manufactured by Nippon Shokubai Co., Ltd.], 50 parts of an acrylate emulsion (solid content: 50%), silicone-based extinguishing on a white nylon taffeta cloth as a support 4 This is a fluorescent yellow screen printing ink in which 0.2 parts of foaming agent, 5 parts of thickener, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy crosslinking agent are uniformly mixed and stirred. A solid capsule is printed on the entire surface using a screen plate, dried and cured at 130 ° C. for 5 minutes to form a non-color-changing layer 5, and a microcapsule pigment containing a temperature-sensitive color-changing color memory material on its upper surface ( Blue ← → colorless, blue at 15 ° C or lower, colorless at 30 ° C or higher) 10 parts, acrylic acid ester emulsion (solid content 50%) 10 parts, silicone antifoam 0.2 parts, water 1 part, ethylene glycol A reversible thermochromic screen ink obtained by uniformly mixing and stirring 0.5 part, 0.5 part of a thickener and 0.5 part of an isocyanate-based crosslinking agent is printed on the entire surface using a 109 mesh screen plate. The reversible thermochromic layer 2 was formed by drying and curing at 130 ° C. for 5 minutes.
  In the state where the non-color-changing layer 5 and the reversible thermochromic layer 2 are stacked, when cooled to 15 ° C. or lower, a green color in which the fluorescent yellow color of the non-color-changing layer 5 and the blue color of the reversible thermochromic layer 2 are mixed is visually recognized. The color tone is maintained in a temperature range of less than 30 ° C. Further, when the temperature was raised to 30 ° C. or higher, the reversible thermochromic layer 2 became colorless and the fluorescent yellow color of the non-color-changing layer 5 was visually recognized, and this color tone was maintained in a temperature range exceeding 15 ° C.
  On the upper surface of the reversible thermochromic layer 2, the entire surface was printed using the white screen printing ink prepared in Example 1, dried and cured to form the porous layer 3, and the discolored body 1 was obtained.
  The porous layer 3 changes from a white state to a colorless and transparent state due to adhesion of water or a water-soluble liquid.
[0028]
  The discolored body 1 is white in a dry state and at a room temperature of 24 ° C., and remains white even when cooled or heated, but the porous layer 3 is transparent when cold water of 15 ° C. or less is attached. As a result, the color tone of the reversible thermochromic layer 2 and the non-discoloring layer 5 in the lower layer instantly changed to a mixed green color. When the green discoloration body 1 was left at room temperature of 24 ° C., it was green when the water was attached, but as the water evaporated, it gradually returned from green to white and then returned to the dry state. It became the original white color.
  Next, when hot water of 30 ° C. or higher is attached to the discolored body 1, the porous layer 3 becomes transparent, and the reversible thermochromic layer 2 discolors from blue to colorless, and the fluorescent yellow discoloration by the non-discoloring layer 5 occurs. Body 1 is visible.
  When the fluorescent yellow discolorant 1 was allowed to stand at a room temperature of 24 ° C., it showed fluorescent yellow when wet with water, but gradually returned from fluorescent yellow to white as the water evaporated and dried. Returning to, it became the original white color.
  Next, when warm water of 30 ° C. or more is attached to a part of the discolored body 1 in a state in which cold water of 15 ° C. or less is adhered to the discolored body in a dry state and discolored to green, the color changes from green to yellow. The state remained both green and yellow until the water evaporated to dryness.
  As described above, the color changing body 1 can be changed from a white state to a green color or a fluorescent yellow color by applying cold water or hot water, and can be returned to the original white state again by drying. It was possible to obtain a discolored body showing various color changes, and to repeat and reproduce the above-mentioned change in appearance.
[0029]
  Example 5 (see FIG. 4)
  10 parts of a yellow fluorescent pigment (trade name: Epocolor FP-117, manufactured by Nippon Shokubai Co., Ltd.), 50 parts of an acrylic ester emulsion (solid content 50%), silicone-based extinction on a white polyester satin fabric as a support 4 This is a fluorescent yellow screen printing ink in which 0.2 parts of foaming agent, 5 parts of thickener, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy crosslinking agent are uniformly mixed and stirred. A solid printing is performed on the entire surface using a screen plate, and the non-discoloring layer 5 is formed by drying and curing at 130 ° C. for 5 minutes, and a microcapsule pigment containing a reversible thermochromic material on its upper surface (blue ← → Colorless, blue below 15 ° C., colorless at 15 ° C. or higher) 10 parts, acrylic ester emulsion (solid content 50%) 10 parts, silicone antifoam 0.2 parts, water 1 part, ethylene glycol .5 parts, 0.5 parts of thickener and 0.5 parts of isocyanate cross-linking agent were mixed and stirred uniformly, and a reversible thermochromic screen ink was printed using a 109 mesh screen plate. The reversible thermochromic pattern layer 21 was formed by drying and curing at 130 ° C. for 5 minutes.
  In the state where the non-discoloring layer 5 and the reversible thermochromic pattern layer 21 are laminated, the entire surface is fluorescent yellow by the non-discoloring layer 5 at a room temperature of 24 ° C., and when cooled to 15 ° C. or less, the reversible thermochromic design layer 21 Is colored blue and a green floral pattern is visible on the yellow background. When the temperature again exceeds 15 ° C., the reversible thermochromic pattern layer 21 is decolored and the entire surface becomes fluorescent yellow.
  On the upper surface of the reversible thermochromic pattern layer 21, solid printing was performed on the entire surface using the white screen printing ink prepared in Example 1, and the porous layer 3 was formed by drying and curing.
  The porous layer 3 changes from a white state to a colorless and transparent state due to adhesion of water or a water-soluble liquid.
[0030]
  The discolored body 1 exhibits a white color in a dry state and at a room temperature of 24 ° C., and remains white even when cooled or heated. However, when water of 15 ° C. or higher is attached, the porous layer 3 is formed. The entire surface turned yellow to be transparent, and when left at room temperature of 24 ° C., water evaporated and dried to return to white.
  Next, when cold water of 10 ° C. was attached, the porous layer 3 became transparent and the reversible thermochromic pattern layer 21 changed from colorless to blue, so that the appearance changed to a green floral pattern on a yellow background. . When left at a room temperature of 24 ° C., the reversible thermochromic pattern layer 21 was decolored when the temperature exceeded 15 ° C., and the entire surface turned yellow, showing this state for a while, but when it dried, it returned to white. It was.
  As described above, the color change body 1 can be changed from a white state to a yellow or green flower pattern by applying cold water or hot water from a white state. It was possible to obtain a color change body showing various color changes that can be returned to the white state, and to repeat and reproduce the above-described change in appearance.
[0031]
  Example 6 (see FIG. 5)
  On the white polyester satin fabric as the support 4, a floral pattern was printed with yellow, pink, purple, green, and red fluorescent general color inks to provide a non-discolored pattern layer 51.
  On the non-discoloring pattern layer 51, 10 parts of microcapsule pigment (black ← → colorless, black at less than 30 ° C., colorless at 30 ° C. or higher) containing a reversible thermochromic material, polyester stell urethane emulsion (solid content 30) %) 20 parts, 0.4 part of a silicone-based antifoaming agent, 1 part of water, 0.5 part of ethylene glycol, 1.0 part of a thickener, and 0.5 part of an isocyanate-based crosslinking agent are uniformly mixed and stirred. A reversible thermochromic screen ink was printed on the entire surface using a 109 mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a reversible thermochromic layer 2.
  In the state in which the reversible thermochromic layer 2 is laminated on the non-discoloring pattern layer 51, the reversible thermochromic layer 2 exhibits a black color at a room temperature of 24 ° C., and the reversible thermochromic layer 2 is discolored when heated to 30 ° C. or higher. A colorful floral pattern is visually recognized by the discolored pattern layer 51, and when the temperature is again lower than 30 ° C., the reversible thermochromic layer 2 is colored black and the floral pattern is concealed.
  Next, on the reversible thermochromic layer 2, 15 parts of fine powder silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Industry Co., Ltd.], 50 parts of a polyester urethane emulsion (solid content 30%), 30 parts of water A white mesh screen printing ink prepared by uniformly mixing and stirring 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 2 parts of a blocked isocyanate-based crosslinking agent A butterfly pattern was printed using a plate and dried and cured at 130 ° C. for 5 minutes to form a porous pattern layer 31 of the butterfly pattern to obtain a discolored body 1.
  The porous design layer 31 changes from a white state to a colorless and transparent state due to adhesion of water or a water-soluble liquid.
[0032]
  In the discolored body 1, a white butterfly pattern by the porous design layer 31 is visually recognized on the black reversible thermochromic layer 2 at a room temperature of 24 ° C. When the discolored body is heated to 30 ° C. or more, the reversible thermochromic layer 2 is discolored from black to colorless, a colorful floral pattern by the non-discolored graphic layer 51 appears, and a white butterfly pattern appears on the floral pattern. It looks like it was drawn. When the temperature again became lower than 30 ° C, it returned to the appearance of a white butterfly pattern drawn on a black background.
  Also, when water at 20 ° C. is attached to the discolored body 1, the porous design layer 31 becomes transparent, so the butterfly design disappears and the entire surface becomes black. If left at room temperature of 24 ° C., the water evaporates and dries. As a result, a white butterfly pattern appeared, and in a completely dry state, the white butterfly pattern was again visible on a black background.
  Next, when warm water of 40 ° C. is applied, the porous design layer 31 becomes transparent and the butterfly design disappears, and the reversible thermochromic layer 2 changes from black to colorless, so that the colorful floral design by the non-color changing design layer 51 However, when it was allowed to stand at a room temperature of 24 ° C., the reversible thermochromic layer 2 was colored when the temperature became less than 30 ° C., and the floral pattern was hidden in black, indicating the state for a while. As it dries, a white butterfly pattern gradually appears on the black ground, and when it completely dries, it returns to the appearance of a white butterfly pattern drawn on black.
  In this way, a white butterfly pattern was drawn on a black background, a black solid pattern, and a white butterfly pattern on a colorful floral pattern due to the temperature change of the fabric, immersion in hot water and cold water. It was possible to reveal four aspects of appearance, a colorful floral pattern only, and this could be repeated many times.
[0033]
  Example 7 (see FIG. 6)
  As a support 4, on a white polyester taffeta cloth, 15 parts of a fluorescent pink pigment [trade name: Epocolor FP-10, manufactured by Nippon Shokubai Co., Ltd.], 50 parts of an acrylate emulsion (solid content 50%), silicone type A fluorescent pink screen printing ink obtained by uniformly mixing and stirring 0.2 part of an antifoaming agent, 5 parts of a thickening agent, 1 part of a leveling agent, 10 parts of water and 2.5 parts of an epoxy crosslinking agent, A solid screen was printed on the entire surface using a mesh screen plate, dried and cured at 130 ° C. for 5 minutes to form a non-discolored layer 5, and fine powder silica [trade name: NIPSEAL E-1011, Nippon Silica] Manufactured by Kogyo Co., Ltd.] 15 parts, 45 parts of polycarbonate urethane emulsion (solid content: 30%), 20 parts of water, 0.2 parts of silicone antifoaming agent, 3 parts of ethylene glycol, aqueous thickener 1 part, 1.5 parts of the blocked isocyanate cross-linking agent are mixed with white stirring and printed with a white screen printing ink using a 180 mesh screen plate, dried and cured at 130 ° C. for 5 minutes, and white porous A quality layer 3 was provided.
  Furthermore, 10 parts of microcapsule pigment (blue ← → colorless, blue at 15 ° C or lower, colorless at 30 ° C or higher) containing polyester with a temperature-sensitive color-change color memory material on its upper surface, polyester urethane emulsion (solid content 30%) 10 parts, 0.2 part of silicone antifoam, 1 part of water, 0.5 part of ethylene glycol, 0.5 part of thickener, and 0.5 part of isocyanate crosslinking agent are mixed and stirred uniformly. A reversible thermochromic layer 2 was formed by solid-printing the entire surface of the color-changing screen ink using a 180-mesh screen plate and drying and curing at 130 ° C. for 5 minutes to obtain a color change body 1.
  The porous layer 3 changes from a white state to a colorless and transparent state due to adhesion of water or a water-soluble liquid.
[0034]
  When the discolored body 1 was cooled to 15 ° C. or lower, the reversible thermochromic layer 2 turned blue, and this state was maintained in a temperature range of less than 30 ° C. When the discolored body was heated to 30 ° C. or higher with a dryer, the reversible thermochromic layer 2 was decolored, and white color due to the lower porous layer 3 was visually recognized and maintained in a temperature range exceeding 15 ° C. When the white discolored material is cooled again to 15 ° C. or lower, it turns blue.
  Furthermore, when hot water of about 40 ° C. is attached to the blue color changing body 1, the reversible thermochromic layer 2 becomes colorless, and the porous layer 3 also becomes transparent, and the pink color due to the non-color changing layer 5 is visible. . This state was pink in the state where water was attached, but changed from pink to white as it dried, and became white again in the completely dried state.
  When the white color change body 1 is written with cold water of about 10 ° C. contained in the brush, the porous layer 3 in the handwriting portion becomes transparent and the reversible thermochromic layer 2 becomes blue, and the non-discoloration in the lower layer. A purple handwriting mixed with the pink color of layer 5 is obtained.
  This state was purple in a state where water was attached, but changed from purple to blue because the porous layer 3 became white as it dried, and it became blue again in the completely dried state.
  When cold water of about 5 ° C. is attached to the discolored body 1, the entire surface changes to purple, and when hot water of about 40 ° C. is included in the brush and written, the handwriting part changes from purple to pink, and 15 ° C. It was kept in a temperature range above, and it was in both purple and pink states when water was attached, but the porous layer turned white as the water evaporates and the water evaporates, so the purple part turns blue. In addition, the pink portion turned white, water completely evaporated, and in a completely dry state, both a blue portion and a white portion were visually observed.
  Next, when water at 20 ° C. is attached again to the blue and white color change bodies, the blue portion changes to purple and the white portion changes to pink. In addition, the purple and pink discoloration bodies were in this state when water was attached, but when cold water of about 10 ° C was applied, the entire surface became purple, or about 40 ° C. When warm water was applied, the entire surface changed to a pink fabric, and when it was taken out to room temperature of about 24 ° C. and completely dried, it changed from purple to blue and from pink to white.
  As described above, when the color-change body is in a dry state at room temperature, three states in which two colors of blue, white, blue and white are present can be arbitrarily selected, and in a state where water is attached, pink, purple, and Since three states in which two colors of pink and purple exist simultaneously can be selected, a discolored body showing six states in total can be obtained, and this can be repeated many times.
[0035]
  Example 8
  On a white polyester taffeta cloth as a support, 15 parts of a fluorescent pink pigment [trade name: Epocolor FP-10, manufactured by Nippon Shokubai Co., Ltd.], 50 parts of an acrylate emulsion (solid content 50%), silicone-based dye This is a fluorescent pink screen printing ink in which 0.2 parts of foaming agent, 5 parts of thickener, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy crosslinking agent are uniformly mixed and stirred. Using a screen plate, the entire surface was solid-printed and dried and cured at 130 ° C. for 5 minutes to form a non-discolored layer. Further, fine powder silica [trade name: NIPSEAL E-1011, Nippon Silica Kogyo Co., Ltd. )]] 15 parts, 45 parts of polycarbonate urethane emulsion (solid content: 30%), 20 parts of water, 0.2 part of silicone antifoam, 3 parts of ethylene glycol, 3 parts of aqueous thickener A white screen ink formed by uniformly mixing and stirring 1.5 parts of a block isocyanate-based crosslinking agent was printed using a 180 mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a white porous layer. Provided.
  Furthermore, 10 parts of microcapsule pigment (blue ← → colorless, blue below 30 ° C., colorless at 30 ° C. or higher) 10 parts polyester urethane emulsion (solid content 30%) 10 parts silicone encapsulating reversible thermochromic material on the upper surface Reversible thermochromic screen ink obtained by uniformly mixing and stirring 0.2 part of an antifoaming agent, 1 part of water, 0.5 part of ethylene glycol, 0.5 part of a thickener and 0.5 part of an isocyanate crosslinking agent Was printed on the entire surface using a 180 mesh screen and dried and cured at 130 ° C. for 5 minutes to form a reversible thermochromic layer to obtain a discolored body.
  The porous layer changes from a white state to a colorless and transparent state due to adhesion of water or a water-soluble liquid.
[0036]
  The discolored body had a blue color at a room temperature of 24 ° C., but when heated to 30 ° C. or higher with a dryer, the reversible thermochromic layer becomes colorless and white due to the lower porous layer is visible. Moreover, although the white state was exhibited at 30 degreeC or more, it will return to blue when the temperature again becomes less than 30 degreeC.
  Furthermore, when hot water of about 40 ° C. is attached to the discolored body exhibiting a blue state, the reversible thermochromic layer becomes colorless and the porous layer also becomes transparent, so that the pink color due to the non-discolored layer is visually recognized. The When the temperature is lower than 30 ° C. with water attached, the reversible thermochromic layer turns blue, so the color changes to purple which is a color mixture with the non-color-changing layer. Since it turned white, it changed from purple to blue, and when completely dried, it turned blue again.
  When water of about 20 ° C. is attached to this blue discolored body, the porous layer becomes transparent, and the blue color of the reversible thermochromic layer and the pink color of the non-discolored layer are instantly changed to purple, and the water changes. Although it was purple in the attached state, it changed from purple to blue as it dried, and it became blue again in the completely dried state.
  Thus, the discolored body was able to obtain four colors of blue, white, purple, and pink, and the aspect change could be reproduced repeatedly.
[0037]
[0038]
[0039]
  Example9(Figure7reference)
  10 parts of microcapsule pigment (blue ← → colorless, blue at 15 ° C or lower, colorless at 30 ° C or higher), acrylic ester on yellow nylon taffeta fabric as support 4 and containing temperature-sensitive color-changing color memory material Emulsions (50% solids) 10 parts, silicone antifoam 0.2 parts, water 1 part, ethylene glycol 0.5 parts, thickener 0.5 parts, isocyanate cross-linking agent 0.5 parts uniformly The reversible thermochromic screen ink obtained by mixing and stirring was solid-printed on the entire surface using a 109 mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form the reversible thermochromic layer 2.
  Next, fine powdered silica [trade name: Nipsil E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] 15 parts, acrylic ester emulsion (solid content 50%) 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 White screen printing ink obtained by uniformly mixing and stirring 3 parts of a thickener for water-based ink, 1 part of ethylene glycol and 3 parts of a block isocyanate-based crosslinking agent, using a 180-mesh screen plate, the reversible thermal discoloration The entire surface of the layer 2 was solid-printed and dried and cured at 130 ° C. for 5 minutes to form a white porous layer 3 in a dry state.
  Furthermore, 10 parts of a microcapsule pigment (pink ← → colorless, pink at 40 ° C. or lower, colorless at 40 ° C. or higher) encapsulating a temperature-sensitive color-change color memory material, acrylic ester emulsion (solid content 50%) 10 Part, silicone antifoaming agent 0.2 part, water 1 part, ethylene glycol 0.5 part, thickener 0.5 part, isocyanate crosslinking agent 0.5 part A reversible thermochromic pattern layer 21 was formed by printing a polka dot pattern using a 180 mesh screen plate and drying and curing at 130 ° C. for 5 minutes.
[0040]
  In the discolored body 1, a pink polka dot pattern by the reversible thermochromic pattern layer 21 was observed on a white background by the porous layer 3 in a dry state and at a room temperature of 24 ° C., but when heated to 40 ° C. or more, When the reversible thermochromic pattern layer 21 is decolored and the entire surface is in a white state, heating is stopped from that state and the temperature is lowered to 40 ° C. or lower, and a pink polka dot pattern by the reversible thermochromic pattern layer 21 appears again. This phenomenon could be repeated many times.
  Next, when warm water of 35 ° C. is attached to the color change body 1, the porous layer 3 becomes transparent due to the adhesion of water, and the reversible thermochromic layer 2 changes color from blue to colorless. On the ground, a red polka dot pattern in which the pink color of the reversible thermochromic pattern layer 21 and the yellow color of the support 4 were mixed was visually observed.
  Furthermore, when immersed in warm water of 40 ° C. or higher, the reversible thermochromic pattern layer 21 was decolored and the entire surface became yellow, but when left at 24 ° C. at room temperature, A red polka dot pattern appeared on the yellow ground, the yellow ground gradually became white as the water evaporated, and when it returned to the dry state, a pink polka dot pattern was visible on the original white ground.
  Next, when cold water of 15 ° C. or less is adhered to the dried discolored body, the green and reversible thermochromic pattern layer 21 is formed on a green background in which the yellow color of the support 4 and the blue color of the reversible thermochromic layer 2 are mixed. A brown polka dot pattern that is a mixture of the pink color of the color is visible, and this state is maintained in cold water of 15 ° C or lower or in a state where water adheres at room temperature of 24 ° C. Turned white, and when completely dry, pink polka dots were visible on the original white background.
  As described above, the color changing body 1 can change the design and the color change in various ways by the adhesion of the aqueous medium and the temperature change, and can reversibly reproduce the change in the appearance many times.
[0041]
  Example10(Figure8reference)
  10 parts of microcapsule pigment (pink ← → colorless, pink below 30 ° C, colorless above 30 ° C), oil-based, in a blue ABS minicar body as support 4 in a reversible thermochromic material Acrylic resin solution [trade name: Acridic A165, manufactured by Dainippon Ink & Chemicals, Inc.] 30 parts, vinyl chloride vinyl acetate copolymer resin 5 parts, xylene 30 parts, MIBK 40 partsThe averageFirst, a yellow oil-based spray ink mixed and stirred and dissolved was spray-coated and dried at room temperature to form a reversible thermochromic pattern layer 21 having a star pattern.
  Next, 10 parts of wet method fine particle silicic acid [trade name: Nipseal E-200A, manufactured by Nippon Silica Industry Co., Ltd.] as a low refractive index pigment, and aqueous urethane resin [trade name: Hydran APX101, Dainippon Ink & Chemicals, Inc. ) Made of 30 parts of water, 10 parts of water, 20 parts of isopropyl alcohol, 0.5 part of a silicone-based antifoaming agent, and a size capable of concealing the reversible thermochromic pattern layer 21 using an aqueous spray ink obtained by uniformly mixing and stirring. The round shape was spray-coated and dried at 40 ° C. for about 1 hour to form a porous design layer 31 to obtain a discolored body 1.
[0042]
  The discolored body 1 showed a state in which a white circular shape by the porous design layer 31 was coated on a blue body at room temperature of 24 ° C., but when immersed in warm water of 40 ° C., the porous design layer 31 is shown. Since the layer is transparent and the reversible thermochromic pattern layer 21 is decolored, the entire surface becomes a blue body and presents the state in warm water, but when it is taken out from warm water and left to stand, the reversible thermochromic pattern layer Since the color of 21 appears to give a pink color, a purple star pattern appears in which the blue and pink colors of the body are mixed, and this state is shown when water is attached. Returned to a circle.
  Next, when immersed in water at 20 ° C., the porous design layer 31 becomes transparent, so the shape changes from a white circle to a purple star pattern, and this state is shown in water. As a result, a white circle was drawn on the blue body again.
  As described above, the color tone changed due to temperature change, aqueous medium adhesion and drying, and this phenomenon could be repeated many times.
[0043]
  Example11(Figure9reference)
  As a support 4, a blue ABS minicar body, 10 parts of a wet process fine particle silicic acid [trade name: NIPSEAL E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.] as a low refractive index pigment, and an aqueous urethane resin as a binder [ Product name: Hydran APX101, manufactured by Dainippon Ink & Chemicals, Inc.] 30 parts of water, 10 parts of water, 20 parts of isopropyl alcohol, and 0.5 parts of a silicone-based antifoaming agent are mixed and stirred. The star pattern was spray-coated and dried at 40 ° C. for about 1 hour to form a porous pattern layer 31.
  Next, 25 parts of a microcapsule pigment containing a reversible thermochromic material (water content 50%, pink color ← → colorless, pink below 30 ° C., colorless at 30 ° C. or higher) on the porous design layer 31; Aqueous urethane resin [trade name: Hydran APX101, manufactured by Dainippon Ink & Chemicals, Inc.] 40 parts, water 10 parts, isopropyl alcohol 20 parts, silicone-based antifoaming agent 0.5 part uniformly mixed and stirred. Using a spray ink, a star pattern having the same shape and size as the porous pattern layer 31 was spray-coated to form a reversible thermochromic pattern layer 21 to obtain a discolored body 1.
[0044]
  The discoloration body 1 showed a state where a blue star was painted on the blue body at a room temperature of 24 ° C. by the reversible thermochromic pattern layer 21, but reversible thermochromic when heated with warm air from a dryer. The pattern layer 21 is decolored and a white star pattern by the porous pattern layer 31 is visually recognized, and this state is exhibited at 30 ° C. or higher. However, when the heating is stopped and left at room temperature, the reversible thermochromic pattern is again displayed. Layer 21 developed color and returned to a pink star.
  Next, when immersed in warm water at 40 ° C., the reversible thermochromic pattern layer 21 is decolored and the porous pattern layer 31 becomes transparent, so that the entire surface becomes a blue body and shows its state in warm water. However, when it is taken out from warm water and immersed in water at about 20 ° C., the reversible thermochromic pattern layer becomes colored and becomes pink, so the blue color of the support 4 and the pink color of the reversible thermochromic pattern layer 21 are changed. It changed into a mixed purple star shape, and it was in the water, but when it was taken out of the water and dried, a pink star shape was drawn on the blue body again.
  As described above, the color tone changed due to temperature change, aqueous medium adhesion and drying, and this phenomenon could be repeated many times.
[0045]
  Example12(Figure10reference)
  10 parts of orange fluorescent pigment (trade name: Epocolor FP-40, manufactured by Nippon Shokubai Co., Ltd.), aqueous acrylic emulsion (trade name: Polysol AP-50, Showa High) on 50 denier polyester tricot white fabric as support 4 Molecule Co., Ltd.] 60 parts, 10 parts of water, 5 parts of ethylene glycol, 0.5 part of defoamer for silicone-based aqueous ink, 3 parts of thickener for aqueous ink, 1 part of leveling agent, 2 parts of isocyanate-based crosslinking agent 10 parts of orange aqueous screen ink and yellow fluorescent pigment [trade name: Epocolor FP-117, manufactured by Nippon Shokubai Co., Ltd.], aqueous acrylic emulsion [trade name: Polysol AP- 50, manufactured by Showa Polymer Co., Ltd.] 60 parts, 10 parts of water, 5 parts of ethylene glycol, 0.5 part of antifoaming agent for silicone-based water-based ink, water-based ink Using a yellow aqueous screen ink obtained by uniformly mixing and stirring 3 parts of a thickener, 1 part of a leveling agent, and 2 parts of an epoxy crosslinking agent, a vertical stripe pattern is printed on a 150 mesh screen plate, 120 A non-discolored pattern layer 51 was formed by drying and curing at about 3 ° C. for about 3 minutes.
  Next, 20 parts of wet method fine particle silicic acid (trade name: Mizukasil P-527, manufactured by Mizusawa Chemical Co., Ltd.) as a low refractive index pigment, and aqueous urethane emulsion (trade name: Hydran HW930, Dainippon Ink Chemical Co., Ltd.) as a binder. )] 60 parts, 15 parts of water, 3 parts of propylene glycol, 0.5 parts of silicone-based antifoaming agent, 3 parts of thickener for water-based ink, 4.0 parts of crosslinking agent for block isocyanate-based water-based ink A porous layer 3 was formed by printing on the entire surface of the non-discoloring pattern layer 51 using a 150-mesh screen plate with a white aqueous screen ink obtained by stirring.
  Furthermore, 15 parts of a microcapsule pigment (water content 50% by weight, pink ← → colorless, pink at 15 ° C. or lower, colorless at 30 ° C. or higher) 15 parts as a binder on the upper surface thereof, containing a temperature-sensitive color-changing color memory material Aqueous urethane emulsion [trade name: Hydran HW930, manufactured by Dainippon Ink & Chemicals, Inc.] 30 parts, water 7 parts, propylene glycol 1 part, silicone-based antifoaming agent 0.2 part, aqueous ink thickener 2 parts In addition, a pink water-based screen ink obtained by uniformly mixing and stirring 2.0 parts of a crosslinking agent for a blocked isocyanate-based water-based ink, and a microcapsule pigment containing a temperature-sensitive color-change color memory material (water content: 50% by weight, Blue ← → colorless, blue at 15 ° C. or lower, colorless at 30 ° C. or higher) Blue aqueous screen ink (color-changing material) prepared in the same manner as above except that 15 parts were used She Is using Re respectively, by printing a horizontal stripe pattern perpendicular to the stripes of the non-color-changing layer 4 by a screen plate of 180 mesh to form a reversibly thermochromic pattern layer 21 to obtain a color change body 1.
[0046]
  In the discolored body 1, pink and blue horizontal stripes are visually observed by the reversible thermochromic pattern layer 21 at room temperature of 24 ° C., but the reversible thermochromic pattern layer 21 is decolored when heated to 30 ° C. or higher with a dryer. As a result, white color due to the porous layer 3 was visually recognized, and the state was maintained even when left at room temperature.
  When the discolored body was cooled with cold air of about 10 ° C., the reversible thermochromic pattern layer 21 developed color and changed again from a white state to a pink and blue horizontal stripe pattern, and this state was maintained at room temperature.
  Then, when the discolored body 1 is immersed in warm water of about 40 ° C., the reversible thermochromic pattern layer 21 is decolored and the porous layer 3 becomes transparent. However, when it was taken out from the warm water and immersed in ice water at about 10 ° C., the reversible discoloration pattern layer 21 developed a color, and therefore the non-discolored design. It changed to a grid pattern consisting of red, green, and brown mixed with layer 51, and this state was exhibited in water at about 10 ° C. However, when it was taken out from water and left at room temperature, it changed from a grid pattern as it dried. It gradually changed to a horizontal stripe pattern, and it became a pink and blue horizontal stripe pattern upon complete drying.
  As described above, the color tone and design changed due to temperature change, adhesion of the aqueous medium and drying, and this phenomenon could be repeated many times.
[0047]
  Example13(Figure11reference)
  As support 4, on the entire surface of 40 denier nylon tricot fluorescent pink fabric, 20 parts of wet-method fine particle silicic acid [trade name: Nipsil E-1011, manufactured by Nippon Silica Kogyo Co., Ltd.] as a low refractive index pigment, aqueous as binder Urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc.] 60 parts, water 15 parts, propylene glycol 3 parts, silicone-based antifoaming agent 0.5 part, thickener 3 for aqueous ink A porous layer 3 was formed by printing with a white mesh screen ink obtained by uniformly mixing and stirring 4.0 parts of a cross-linking agent for a blocked isocyanate water-based ink with a white mesh screen ink.
  Next, on the porous layer 3, 30 parts of a microcapsule pigment encapsulating a reversible thermochromic material (water content 50 wt%, yellow ← → colorless, yellow below 15 ° C., yellow above 15 ° C., colorless), as a binder Aqueous acrylic emulsion [trade name: Mobile 700, manufactured by Hoechst Synthesis Co., Ltd.] 35 parts, water 15 parts, propylene glycol 3 parts, silicone antifoam 0.5 parts, aqueous ink thickener 3 parts, blocked isocyanate Yellow water-based screen ink (color-changing material) obtained by uniformly mixing and stirring 3.5 parts of a cross-linking agent for water-based inks, and a microcapsule pigment containing a reversible thermochromic material (water content 50% by weight, blue ← (→ colorless, blue at less than 15 ° C., colorless at 15 ° C. or higher) 15 parts) The wave pattern was printed by Interview of screen plate, to form a reversible thermochromic design layer 21 is cured for 3 minutes drying at 100 ° C..
  Further, on the reversible thermochromic pattern layer 21, fluorescent pink pigment [trade name: Epocolor FP-1000N, manufactured by Nippon Shokubai Co., Ltd.] 10 parts, aqueous acrylic emulsion [trade name: Polysol AP-50, Showa Polymer] Manufactured by Co., Ltd.] 60 parts, water 10 parts, ethylene glycol 5 parts, silicone water-based ink defoaming agent 0.5 parts, water-based ink thickener 3 parts, leveling agent 1 part, isocyanate-based crosslinking agent 2 parts Using a pink water-based screen ink that is uniformly mixed and stirred, a polka dot pattern is printed on a 180-mesh screen plate and cured and dried at 130 ° C. for 3 minutes to form a non-discolored pattern layer 51 and discoloration. Body 1 was obtained.
[0048]
  The discolored body 1 showed a state in which a fluorescent pink polka dot pattern by the non-discolored pattern layer 51 was drawn on the white ground by the porous layer 3 at room temperature of about 24 ° C. When cooled, the reversible thermochromic pattern layer 21 develops color and the white background changes to a yellow and blue wave pattern, showing a state below 15 ° C, but turns white again when cooled and left at room temperature. changed.
  Next, when immersed in water at about 20 ° C., the porous layer 3 becomes transparent, so that the pink color of the non-discolored design layer 51 and the pink color of the support 4 are synchronized, and the entire surface becomes fluorescent pink, In that state. When the discolored body 1 is immersed in water at 10 ° C., the reversible thermochromic pattern layer 21 develops color, so that the purple color in which blue and fluorescent pink colors are mixed, and the red color in which yellow and fluorescent pink colors are mixed. It changed into the state where the fluorescent pink polka dot pattern by the non-discoloring pattern layer 51 was drawn on the wave pattern, and the state was maintained in water.
  When the discolored body 1 is taken out of water and left at room temperature, the reversible thermochromic pattern layer 21 is decolored. When the water is attached, the entire surface changes from pink to pink, and when completely dried, a white background is obtained. A fluorescent pink polka dot pattern was drawn.
  As described above, the color tone and design changed due to temperature change, adhesion of the aqueous medium and drying, and this phenomenon could be repeated many times.
[0049]
  Comparative Example 1
  10 parts of microcapsule pigment (blue ← → colorless, blue at 15 ° C or lower, colorless at 30 ° C or higher), acrylic ester on pink nylon taffeta fabric as support Emulsions (50% solids) 10 parts, silicone antifoam 0.2 parts, water 1 part, ethylene glycol 0.5 parts, thickener 0.5 parts, isocyanate crosslinker 0.5 parts uniformly A reversible thermochromic screen ink obtained by mixing and stirring was solid-printed on the entire surface using a 109-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a reversible thermochromic layer to obtain a color change body. .
[0050]
  When the discolored body is cooled to 15 ° C. or lower, the pink color of the support and the blue color of the reversible thermochromic layer are mixed to make purple visible, and this color tone is maintained in a temperature range of less than 30 ° C. Further, when heated to 30 ° C. or higher, the reversible thermochromic layer becomes colorless, and the pink color of the support is visually recognized. This color tone is maintained in a temperature range exceeding 15 ° C., but the color tone change is 2 There was only state and it was poor in changeability.
[0051]
  Comparative Example 2
  As a support, on a pink nylon taffeta fabric, 15 parts of fine powder silica [trade name: Nipseal E-1011, manufactured by Nippon Silica Kogyo Co., Ltd.], 45 parts of a polycarbonate urethane emulsion (solid content: 30%), water 180 mesh with white screen ink obtained by uniformly mixing and stirring 20 parts, 0.2 part of silicone-based antifoaming agent, 3 parts of ethylene glycol, 3 parts of aqueous thickener, and 1.5 parts of blocked isocyanate crosslinking agent A screen plate was printed and dried and cured at 130 ° C. for 5 minutes to provide a white porous layer to obtain a discolored body.
[0052]
  The discolored body is white in a dry state, and when the water is attached, the porous layer becomes transparent and the pink color of the support is visible. However, the color tone changes only in two states, and the variability is poor. It was a thing.
[0053]
【The invention's effect】
  The discolored body of the present invention comprises a reversible thermochromic layer, a porous layer that becomes transparent or translucent by liquid absorption containing a low refractive index pigment,LaminateThe appearance of various color changes can be visualized by the temperature change in the living environment temperature range and the medium such as water, and the changed appearance can be reproduced repeatedly and reversibly. It is possible to provide a discolored body that can be applied and developed in the decoration field.
[Brief description of the drawings]
FIG. 1 is an explanatory view of a longitudinal section of an embodiment of a color changing body of the present invention.
FIG. 2 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
FIG. 3 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
FIG. 4 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
FIG. 5 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
FIG. 6 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
FIG. 7 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
FIG. 8 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
FIG. 9 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
FIG. 10 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
FIG. 11 is an explanatory view of a longitudinal section of another embodiment of the color changing body of the present invention.
[Explanation of symbols]
  1 Discolored body
  2 Reversible thermochromic layer
  21 reversible thermochromic pattern layer
  3 Porous layer
  31 Porous pattern layer
  4 Support
  5 Non-discoloring layer
  51 Non-discolored pattern layer

Claims (8)

A discolored body in which a reversible thermochromic layer and a porous layer that becomes transparent or translucent by a liquid absorption containing a low refractive index pigment are laminated and discolored by heat or water. The discoloration body according to claim 1, wherein the reversible thermochromic layer is provided on a support, and the porous layer is provided on the reversible thermochromic layer. The discoloration body according to claim 3, wherein a reversible thermochromic pattern layer is disposed on the porous layer. The discoloration body according to claim 1, wherein the porous layer is provided on a support, and the reversible thermochromic layer is provided on the porous layer. The discoloration body according to claim 5, wherein a porous design layer is disposed on the reversible thermochromic layer. The discolorable body according to any one of claims 1 to 5, wherein the reversible thermochromic layer is a design layer. The discoloration body according to any one of claims 1 to 5, wherein the porous layer is a design layer. The discoloration body according to any one of claims 2 to 7, wherein the support is a fabric.

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