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JP7794658B2 - Water-colored body, Water-colored body set - Google Patents
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JP7794658B2 - Water-colored body, Water-colored body set - Google Patents

Water-colored body, Water-colored body set

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JP7794658B2
JP7794658B2 JP2022027049A JP2022027049A JP7794658B2 JP 7794658 B2 JP7794658 B2 JP 7794658B2 JP 2022027049 A JP2022027049 A JP 2022027049A JP 2022027049 A JP2022027049 A JP 2022027049A JP 7794658 B2 JP7794658 B2 JP 7794658B2
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water
cover member
sheet
transparent cover
discoloring
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JP2022153279A (en
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明雄 中島
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Pilot Ink Co Ltd
Pilot Corp
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Pilot Ink Co Ltd
Pilot Corp
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Description

本発明は水変色体、水変色体セットに関する。更に詳細には水変色シートと、前記水変色シートに形成した水変色像の消失を遅延させるカバー部材とを備えた水変色体、水変色体セットに関する。 The present invention relates to a water-discoloring body and a water-discoloring body set. More specifically, it relates to a water-discoloring body and a water-discoloring body set that includes a water-discoloring sheet and a cover member that delays the disappearance of the water-discoloring image formed on the water-discoloring sheet.

従来、非吸水状態で不透明であり、吸水状態で透明化する低屈折率顔料をバインダー樹脂に分散状態に固着させた多孔質層を着色層上に配した水変色体が開示されており、筆記又はスタンプ具や手指等によって水を付着させて水変色像を形成した直後に、前記水変色像をカバー部材で覆うことにより、水変色像の維持時間を延長化させる水変色材セットが開示されている(例えば、特許文献1参照)。
前記水変色材セットは水変色像の維持時間を延長でき、玩具、教習具への実用性を満足させることができる。
Conventionally, a water-discoloring body has been disclosed in which a porous layer in which a low refractive index pigment that is opaque in a non-water-absorbing state and becomes transparent in a water-absorbing state is dispersed and fixed in a binder resin is disposed on a colored layer. A water-discoloring material set has also been disclosed in which the water-discoloring image is formed by applying water with a writing or stamping tool or a finger, and then immediately after the water-discoloring image is formed, the water-discoloring image is covered with a cover member, thereby extending the maintenance time of the water-discoloring image (see, for example, Patent Document 1).
The water-color changing material set can prolong the time for which the water-color changing image is maintained, and can satisfy the practicality of toys and educational tools.

特開2002-254547号公報Japanese Patent Application Laid-Open No. 2002-254547

本発明は、この種の水変色材に形成された水変色像の維持時間を延長できると共に、水変色像がバランス良く形成されたかどうか確認することのできる水変色体、水変色体セットを提供しようとするものである。 The present invention aims to provide a hydrochromic material and a hydrochromic material set that can extend the retention time of the hydrochromic image formed on this type of hydrochromic material and also allows confirmation of whether the hydrochromic image has been formed in a balanced manner.

本発明は、低屈折率顔料をバインダー樹脂に分散状態に固着させた多孔質層を着色層の上層に備えた水変色シートと、前記多孔質層の表面に水の付着により形成される水変色像を覆い、水の乾燥を抑制して、水変色像の消失を遅延させる透明性カバー部材とを備えてなり、前記透明性カバー部材の下面には水変色シート表面と透明性カバー部材を非接触状態に保持し、水変色シート表面と接する点状の凸部を少なくとも三か所以上非直線状に配置してなり、前記凸部は0.4mm~12.0mmの高さを有し、前記透明性カバー部材上面から視認される凸部の表面積(s)と、凸部の高さ(h)が下記式(1)を満たし、前記透明性カバー部材上面の表面積に対して、透明性カバー部材上面から視認される凸部の占有面積が10%以下であり、前記透明性カバー部材には水変色シートに形成する文字の文字枠を設けてなる水変色体、或いは、低屈折率顔料をバインダー樹脂に分散状態に固着させた多孔質層を着色層の上層に備えた水変色シートと、前記多孔質層の表面に水の付着により形成される水変色像を覆い、水の乾燥を抑制して、水変色像の消失を遅延させる透明性カバー部材と、前記水変色シートに形成する文字の文字枠を設けてなる透明性枠シートとからなり、前記透明性カバー部材の下面には水変色シート表面と透明性カバー部材を非接触状態に保持し、水変色シート表面と接する点状の凸部を少なくとも三か所以上非直線状に配置してなり、前記凸部は0.4mm~12.0mmの高さを有し、前記透明性カバー部材上面から視認される凸部の表面積(s)と、凸部の高さ(h)が下記式(1)を満たし、前記透明性カバー部材上面の表面積に対して、透明性カバー部材上面から視認される凸部の占有面積が10%以下である水変色体を要件とする。
1.0≦s/h≦00 (1)
更には、前記凸部は透明性を有すること、前記凸部は白色を呈すること、前記凸部の先端が曲面形状であること、前記透明性カバー部材は可撓性を有し、且つ、前記凸部は100cmあたり3個以上有すること、前記透明性カバー部材は、一端部を水変色シートに取り付け、他端部を自由端となして、水変色シートに開閉自在に設けてなること、複数の前記水変色シートと、複数の前記透明性カバー部材とからなること、複数の前記水変色シートと、複数の前記透明性カバー部材と、複数の前記透明性枠シートとからなること、前記点状の凸部を碁盤目状に配置してなること等を要件とする。
更には、前記水変色体と、水変色像を形成させる水付着具を備えた水変色体セットを要件とする。
The present invention provides a water-discoloring sheet comprising, as an upper layer of a colored layer, a porous layer in which a low refractive index pigment is fixed in a dispersed state in a binder resin, and a transparent cover member that covers a water-discoloring image formed on the surface of the porous layer by adhesion of water, thereby suppressing drying of the water and delaying disappearance of the water-discoloring image, and the underside of the transparent cover member has at least three or more dot-like convex portions that contact the surface of the water-discoloring sheet and maintain a non-contact state between the surface of the water-discoloring sheet and the transparent cover member, and are arranged in a non-linear pattern, the convex portions having a height of 0.4 mm to 12.0 mm, the surface area (s) of the convex portions visible from the upper surface of the transparent cover member and the height (h) of the convex portions satisfy the following formula (1), the area occupied by the convex portions visible from the upper surface of the transparent cover member is 10% or less of the surface area of the upper surface of the transparent cover member, and the transparent cover member is provided with character frames for the characters to be formed on the water -discoloring sheet . Alternatively, the present invention is directed to a water-discoloring sheet comprising, as an upper layer of a colored layer, a porous layer in which a low-refractive index pigment is dispersed and fixed in a binder resin; a transparent cover member that covers the water-discoloring image formed on the surface of the porous layer by the adhesion of water, thereby inhibiting the drying of the water and delaying the disappearance of the water-discoloring image; and a transparent frame sheet provided with character frames for characters to be formed on the water-discoloring sheet, wherein the underside of the transparent cover member has at least three or more dot-like convex portions that contact the surface of the water-discoloring sheet and are arranged in a non-linear manner to keep the surface of the water-discoloring sheet and the transparent cover member out of contact, the convex portions having a height of 0.4 mm to 12.0 mm, the surface area (s) of the convex portions visible from the top surface of the transparent cover member and the height (h) of the convex portions satisfy the following formula (1), and the water-discoloring body is such that the area occupied by the convex portions visible from the top surface of the transparent cover member is 10% or less of the surface area of the top surface of the transparent cover member .
1.0≦s/h≦ 400 (1)
Further requirements include that the convex portions are transparent, that the convex portions are white, that the tips of the convex portions are curved, that the transparent cover member is flexible and that there are three or more convex portions per 100 cm2 , that the transparent cover member has one end attached to the water-discoloring sheet and the other end as a free end and is attached to the water-discoloring sheet so as to be able to be opened and closed freely, that it consists of a plurality of the water-discoloring sheets and a plurality of the transparent cover members, that it consists of a plurality of the water-discoloring sheets, a plurality of the transparent cover members and a plurality of the transparent frame sheets , and that the dot-like convex portions are arranged in a checkerboard pattern .
Furthermore, the present invention requires a water-discoloring body set including the water-discoloring body and a water-attaching tool for forming a water-discoloring image.

本発明は、筆記又はスタンプ具や手指等により、水を付着させて水変色像を形成した直後に、前記水変色像をカバー部材により覆うことにより、水変色像の維持時間を簡易に延長化させることができると共に、水変色像がバランス良く形成されたかどうか確認することのできる玩具、教習具としての商品性と実用性を満足させる水変色体、水変色体セットを提供できる。 The present invention provides a water-color changing object and water-color changing object set that satisfies marketability and practicality as a toy or educational tool by covering the water-color changing object with a cover member immediately after applying water to it using a writing or stamping tool, fingers, etc., and then easily extending the duration for which the water-color changing image remains. It also allows the user to check whether the water-color changing image has been formed in a balanced manner.

本発明の一実施例の水変色体を示す上面図である。1 is a top view showing a water-chromatic body according to an embodiment of the present invention; 図1の水変色体の縦断面図である。FIG. 2 is a longitudinal cross-sectional view of the water-changing body of FIG. 1. 本発明の他の実施例の水変色体を示す上面図である。FIG. 10 is a top view showing a water-chromatic body according to another embodiment of the present invention. 図3の水変色体の縦断面図である。FIG. 4 is a longitudinal cross-sectional view of the water-changing body of FIG. 3 . 参考例の水変色体を示す縦断面図である。FIG. 2 is a longitudinal cross-sectional view showing a water-chromatic body of a reference example . 他の参考例の水変色体を示す縦断面図である。FIG. 10 is a longitudinal cross-sectional view showing another reference example of a water-color changing body. 本発明の一実施例の水変色体セットの上面図である。1 is a top view of a water-changing body set according to an embodiment of the present invention. FIG.

前記水変色シートは、着色層の上層に低屈折率顔料をバインダー樹脂に分散状態に固着させた多孔質層を設けてなる。
着色層は、支持体自体が着色層を兼ねてもよいが、支持体表面に着色層(任意形状の像を含む)を設けることが好ましい。
前記支持体は、紙、合成紙、織物、編物、組物、不織布等の布帛、天然又は合成皮革、プラスチック、ガラス、陶磁器、金属、木材、石材等が用いられる。また、形状としては平面状のものが好ましいが、凹凸状の形態であってもよい。
前記支持体表面に設けられる着色層は、着色剤を含むバインダー樹脂により形成されてなる。
前記着色剤としては、一般染料、一般顔料、蛍光染料、蛍光顔料、金属光沢顔料等が挙げられる。
前記着色剤はバインダー樹脂を結合剤として含むビヒクル中に含有されたインキや塗料を支持体に塗布した後、揮発分を乾燥させて着色層を形成する。
前記バインダー樹脂としては、ウレタン系樹脂、ナイロン樹脂、酢酸ビニル樹脂、アクリル酸エステル樹脂、アクリル酸エステル共重合樹脂、アクリルポリオール樹脂、塩化ビニル-酢酸ビニル共重合樹脂、マレイン酸樹脂、ポリエステル樹脂、スチレン樹脂、スチレン共重合樹脂、ポリエチレン樹脂、ポリカーボネート樹脂、エポキシ樹脂、スチレン-ブタジエン共重合樹脂、アクリロニトリル-ブタジエン共重合樹脂、メタクリル酸メチル-ブタジエン共重合樹脂、ブタジエン樹脂、クロロプレン樹脂、メラミン樹脂、及び前記各樹脂エマルジョン、カゼイン、澱粉、セルロース誘導体、ポリビニルアルコール、尿素樹脂、フェノール樹脂等が挙げられる。
前記着色層は、プロセス印刷、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、インクジェット印刷、転写等の印刷手段、刷毛塗り、スプレー塗装、静電塗装、電着塗装、流し塗り、ローラー塗り、浸漬塗装等により支持体上に形成される。
また、予め別の基材上に着色剤とバインダー樹脂を結合剤として含むビヒクル中に含有されたインキや塗料を塗布して転写層を設け、前記転写層を支持体上に転写して着色層を設けることもできる。
更に、前記支持体が透明性を有する場合は、支持体の裏面(多孔質層を設けていない面)に着色層を設けることもできる。
The water-discoloring sheet has a porous layer formed on the colored layer, in which a low refractive index pigment is fixed in a dispersed state in a binder resin.
The support itself may also serve as the colored layer, but it is preferable to provide a colored layer (including an image of any shape) on the surface of the support.
The support may be made of paper, synthetic paper, fabric such as woven fabric, knitted fabric, braided fabric, or nonwoven fabric, natural or synthetic leather, plastic, glass, ceramics, metal, wood, stone, etc. The support is preferably flat, but may also be uneven.
The colored layer provided on the surface of the support is formed from a binder resin containing a colorant.
Examples of the colorant include general dyes, general pigments, fluorescent dyes, fluorescent pigments, and metallic luster pigments.
The colorant is contained in a vehicle containing a binder resin as a binder, and the ink or paint is applied to a support, and then the volatile components are dried to form a colored layer.
Examples of the binder resin include urethane resins, nylon resins, vinyl acetate resins, acrylic ester resins, acrylic ester copolymer resins, acrylic polyol resins, vinyl chloride-vinyl acetate copolymer resins, maleic acid resins, polyester resins, styrene resins, styrene copolymer resins, polyethylene resins, polycarbonate resins, epoxy resins, styrene-butadiene copolymer resins, acrylonitrile-butadiene copolymer resins, methyl methacrylate-butadiene copolymer resins, butadiene resins, chloroprene resins, melamine resins, and emulsions of each of the above resins, casein, starch, cellulose derivatives, polyvinyl alcohol, urea resins, and phenolic resins.
The colored layer is formed on the support by a printing means such as process printing, screen printing, offset printing, gravure printing, coater, pad printing, inkjet printing, or transfer printing, or by a brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, or dip coating.
Alternatively, a transfer layer can be formed by first applying an ink or paint contained in a vehicle containing a colorant and a binder resin as a binder onto another substrate, and then transferring the transfer layer onto the support to form a colored layer.
Furthermore, when the support has transparency, a colored layer can be provided on the back surface of the support (the surface on which the porous layer is not provided).

前記着色層上に低屈折率顔料をバインダー樹脂により分散状態に固着した多孔質層を積層して水変色シートを得ることができる。
前記多孔質層は、低屈折率顔料をバインダー樹脂と共に分散状態に固着させた層であり、乾燥状態と吸液状態で透明性が異なる層である。
前記低屈折率顔料としては、珪酸及びその塩、バライト粉、硫酸バリウム、炭酸バリウム、炭酸カルシウム、石膏、クレー、タルク、アルミナホワイト、炭酸マグネシウム等が挙げられ、これらは屈折率が1.4~1.8の範囲にあり、水を吸液すると良好な透明性を示すものである。
なお、前記珪酸の塩としては、珪酸アルミニウム、珪酸アルミニウムカリウム、珪酸アルミニウムナトリウム、珪酸アルミニウムカルシウム、珪酸カリウム、珪酸カルシウム、珪酸カルシウムナトリウム、珪酸ナトリウム、珪酸マグネシウム、珪酸マグネシウムカリウム等が挙げられる。
なお、好適に用いられる低屈折率顔料としては珪酸が挙げられる。
また、前記低屈折率顔料は二種以上を併用することもできる。
前記低屈折率顔料の粒子径は特に限定されるものではないが、0.03~10.0μmのものが好適に用いられる。
前記珪酸は、乾式法により製造させる珪酸であってもよいが、湿式法により製造される珪酸(以下、湿式法珪酸と称する)が特に効果的であり、この点を説明すると、珪酸は非晶質の無定形珪酸として製造され、その製造方法により、四塩化ケイ素等のハロゲン化ケイ素の熱分解等の気相反応を用いる乾式法によるもの(以下、乾式法珪酸と称する)と、ケイ酸ナトリウム等の酸による分解等の液相反応を用いる湿式法によるものとに大別され、乾式法珪酸と湿式法珪酸とでは構造が異なり、前記乾式法珪酸は珪酸が密に結合した三次元構造を形成するのに対して、湿式法珪酸は、珪酸が縮合して長い分子配列を形成した、所謂、二次元構造部分を有している。
従って、前記乾式法珪酸と比較して分子構造が粗になるため、湿式法珪酸を多孔質層に適用した場合、乾式法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、常態での隠蔽性が大きくなるものと推察される。
また、前記多孔質層は、水を吸液させるものであるから、湿式法珪酸は乾式法珪酸に比べて粒子表面にシラノール基として存在する水酸基が多く、親水性の度合いが大であり、好適に用いられる。
なお、前記多孔質層の常態での隠蔽性と吸液状態での透明性を調整するために、湿式法珪酸と共に、他の低屈折率顔料を併用することもできる。
A water-discoloring sheet can be obtained by laminating a porous layer on the colored layer, in which a low refractive index pigment is fixed in a dispersed state by a binder resin.
The porous layer is a layer in which a low refractive index pigment is fixed together with a binder resin in a dispersed state, and is a layer whose transparency differs between a dry state and a liquid-absorbing state.
Examples of the low refractive index pigment include silicic acid and its salts, baryte powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, and magnesium carbonate, which have a refractive index in the range of 1.4 to 1.8 and exhibit good transparency when absorbing water.
Examples of the salt of silicic acid include aluminum silicate, potassium aluminum silicate, sodium aluminum silicate, calcium aluminum silicate, potassium silicate, calcium silicate, sodium calcium silicate, sodium silicate, magnesium silicate, and potassium magnesium silicate.
A preferred example of a low refractive index pigment is silica.
Two or more of the low refractive index pigments can also be used in combination.
The particle size of the low refractive index pigment is not particularly limited, but is preferably 0.03 to 10.0 μm.
The silicic acid may be silicic acid produced by a dry method, but silicic acid produced by a wet method (hereinafter referred to as wet-method silicic acid) is particularly effective. In this regard, silicic acid is produced as amorphous silicic acid, and depending on the production method, it can be roughly divided into dry-method silicic acid (hereinafter referred to as dry-method silicic acid) which uses a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride, and wet-method silicic acid which uses a liquid phase reaction such as decomposition with an acid such as sodium silicate. The dry-method silicic acid and the wet-method silicic acid have different structures, and the dry-method silicic acid forms a three-dimensional structure in which silicic acid is tightly bonded, while the wet-method silicic acid has a so-called two-dimensional structure in which silicic acid is condensed to form a long molecular arrangement.
Therefore, since the molecular structure is coarser than that of the dry process silica, when wet process silica is applied to a porous layer, it is presumed that the system will have better diffused reflection of light in a dry state and greater hiding power in the normal state than a system using dry process silica.
Furthermore, since the porous layer is capable of absorbing water, wet-process silica has more hydroxyl groups present as silanol groups on the particle surface than dry-process silica, and is therefore more hydrophilic, and is therefore preferably used.
In order to adjust the hiding power of the porous layer in its normal state and the transparency in its liquid-absorbed state, other low refractive index pigments may be used in combination with the wet-process silica.

前記多孔質層中の低屈折率顔料は、粒子径、比表面積、吸油量等の性状に左右されるが、常態での隠蔽性と吸液状態での透明性を共に満足するためには、塗布量が1~50g/mであることが好ましく、より好ましくは、5~50g/mである。1g/m未満では、常態で十分な隠蔽性を得ることが困難であり、また、50g/mを越えると吸液時に十分な透明性を得ることが困難である。
前記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され、支持体上に塗布した後、揮発分を乾燥させて多孔質層を形成する。
前記バインダー樹脂としては、ウレタン系樹脂、ナイロン樹脂、酢酸ビニル樹脂、アクリル酸エステル樹脂、アクリル酸エステル共重合樹脂、アクリルポリオール樹脂、塩化ビニル-酢酸ビニル共重合樹脂、マレイン酸樹脂、ポリエステル樹脂、スチレン樹脂、スチレン共重合樹脂、ポリエチレン樹脂、ポリカーボネート樹脂、エポキシ樹脂、スチレン-ブタジエン共重合樹脂、アクリロニトリル-ブタジエン共重合樹脂、メタクリル酸メチル-ブタジエン共重合樹脂、ブタジエン樹脂、クロロプレン樹脂、メラミン樹脂、及び前記各樹脂エマルジョン、カゼイン、澱粉、セルロース誘導体、ポリビニルアルコール、尿素樹脂、フェノール樹脂等が挙げられる。
前記低屈折率顔料とバインダー樹脂の混合比率は、低屈折率顔料の種類及び性状に左右されるが、好ましくは、低屈折率顔料1質量部に対してバインダー樹脂固形分0.5~2質量部であり、より好ましくは、0.8~1.5質量部である。低屈折率顔料1質量部に対してバインダー樹脂固形分が0.5質量部未満の場合には、前記多孔質層の実用的な皮膜強度を得ることが困難であり、2質量部を越える場合には、前記多孔質層内部への水の浸透性が損なわれ易くなる。
前記多孔質層は、一般的な塗膜と比較して着色剤に対するバインダー樹脂の混合比率が小さいため、十分な皮膜強度が得られ難い。そこで、耐擦過強度を高めるために、前記のバインダー樹脂のうち、ナイロン樹脂又はウレタン系樹脂を用いると効果的である。
前記ウレタン系樹脂としては、ポリエステル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂、ポリエーテル系ウレタン樹脂等があり、二種以上を併用することもできる。また、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。
なお、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、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質量比率で30%以上含有させることが好ましい。
前記バインダー樹脂において、架橋性のものは任意の架橋剤を添加して架橋させることにより、さらに皮膜強度を向上させることができる。
前記バインダー樹脂には、水との親和性に大小が存在するが、これらを組み合わせることにより、多孔質層中への浸透時間、浸透度合い、浸透後の乾燥の遅速を調整することができる。更には、適宜分散剤や界面活性剤を添加して前記調整をコントロールすることができる。
The amount of the low refractive index pigment in the porous layer depends on properties such as particle size, specific surface area, and oil absorption, but in order to satisfy both hiding power in the normal state and transparency in the liquid-absorbed state, the coating amount is preferably 1 to 50 g/ m2 , and more preferably 5 to 50 g/ m2 . If it is less than 1 g/ m2 , it is difficult to obtain sufficient hiding power in the normal state, and if it exceeds 50 g/ m2 , it is difficult to obtain sufficient transparency when liquid is absorbed.
The low refractive index pigment is dispersed in a vehicle containing a binder resin as a binding agent, and after coating on a support, the volatile components are dried to form a porous layer.
Examples of the binder resin include urethane resins, nylon resins, vinyl acetate resins, acrylic ester resins, acrylic ester copolymer resins, acrylic polyol resins, vinyl chloride-vinyl acetate copolymer resins, maleic acid resins, polyester resins, styrene resins, styrene copolymer resins, polyethylene resins, polycarbonate resins, epoxy resins, styrene-butadiene copolymer resins, acrylonitrile-butadiene copolymer resins, methyl methacrylate-butadiene copolymer resins, butadiene resins, chloroprene resins, melamine resins, and emulsions of each of the above resins, casein, starch, cellulose derivatives, polyvinyl alcohol, urea resins, and phenolic resins.
The mixing ratio of the low refractive index pigment to the binder resin depends on the type and properties of the low refractive index pigment, but is preferably 0.5 to 2 parts by mass, more preferably 0.8 to 1.5 parts by mass, of binder resin solids per 1 part by mass of the low refractive index pigment. If the binder resin solids per 1 part by mass of the low refractive index pigment is less than 0.5 parts by mass, it is difficult to obtain a practical coating strength for the porous layer, and if it exceeds 2 parts by mass, water permeability into the porous layer is easily impaired.
The porous layer has a smaller binder resin to colorant ratio than a general coating film, making it difficult to obtain sufficient film strength. Therefore, in order to improve abrasion resistance, it is effective to use a nylon resin or a urethane-based resin among the binder resins.
The urethane resin may be a polyester urethane resin, a polycarbonate urethane resin, a polyether urethane resin, etc., and two or more of these may be used in combination. Alternatively, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloidal dispersion type (ionomer type) urethane resin in which the ionic urethane resin (urethane ionomer) itself emulsifies without the need for an emulsifier due to the ionic group of the urethane resin itself, and is dissolved or dispersed in water, may also be used.
The urethane resin may be either an aqueous urethane resin or an oil-based urethane resin, but an aqueous urethane resin, particularly an urethane emulsion resin or a colloidal dispersion type urethane resin, is preferably used.
The urethane-based resin can be used alone, or can be used in combination with other binder resins depending on the performance required for the film. When a binder resin other than a urethane-based resin is used in combination, in order to obtain practical film strength, it is preferable that the urethane-based resin be contained in the binder resin of the porous layer in an amount of 30% or more in terms of solid content mass ratio.
Among the binder resins, if the binder resin is crosslinkable, the strength of the film can be further improved by adding an optional crosslinking agent to crosslink the binder resin.
The binder resins have different affinities with water, and by combining these, it is possible to adjust the time and degree of penetration into the porous layer and the rate of drying after penetration. Furthermore, the adjustment can be controlled by adding a dispersant or surfactant as appropriate.

前記多孔質層は、スクリーン印刷、オフセット印刷、グラビヤ印刷、コーター、タンポ印刷、転写等の印刷手段、刷毛塗り、スプレー塗装、静電塗装、電着塗装、流し塗り、ローラー塗り、浸漬塗装等により着色層上に形成できる。 The porous layer can be formed on the colored layer by printing methods such as screen printing, offset printing, gravure printing, coater printing, pad printing, and transfer printing, as well as by brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating.

また、多孔質層中には、着色剤を添加して乾燥状態における多孔質層を着色することもできる。
前記着色剤としては、一般染料、一般顔料、蛍光染料、蛍光顔料、金属光沢顔料、可逆熱変色性組成物、可逆熱変色性組成物を内包した可逆熱変色性マイクロカプセル顔料、光変色性組成物、光変色性組成物を内包した光変色性マイクロカプセル顔料が挙げられ、蛍光染料、蛍光顔料等の蛍光性着色剤を用いると色変化の明瞭性に優れ、可逆熱変色性組成物、可逆熱変色性組成物を内包した可逆熱変色性マイクロカプセル顔料等の熱変色性着色剤、光変色性着色剤、光変色性組成物、光変色性組成物を内包した光変色性マイクロカプセル顔料等の光変色性着色剤を用いると多彩な変化性を付与することができる。
前記可逆熱変色性組成物としては、電子供与性呈色性有機化合物と電子受容性化合物と呈色反応を可逆的に生起させる有機化合物媒体の三成分を含む可逆熱変色性組成物が好適に用いられる。
前記光変色性組成物としては、スピロオキサジン系化合物、スピロピラン系化合物、ジアリールエテン系化合物等のフォトクロミック化合物が好適に用いられる。
Furthermore, a colorant may be added to the porous layer to color the porous layer in a dry state.
Examples of the colorant include general dyes, general pigments, fluorescent dyes, fluorescent pigments, metallic luster pigments, reversible thermochromic compositions, reversible thermochromic microcapsule pigments encapsulating a reversible thermochromic composition, photochromic compositions, and photochromic microcapsule pigments encapsulating a photochromic composition. When fluorescent colorants such as fluorescent dyes and fluorescent pigments are used, the clarity of the color change is excellent. When photochromic colorants such as thermochromic colorants such as reversible thermochromic compositions and reversible thermochromic microcapsule pigments encapsulating a reversible thermochromic composition are used, a variety of changes can be imparted.
The reversible thermochromic composition preferably contains three components: an electron-donating organic color-forming compound, an electron-accepting compound, and an organic compound medium that reversibly induces a color-forming reaction.
As the photochromic composition, photochromic compounds such as spirooxazine compounds, spiropyran compounds, diarylethene compounds, etc. are preferably used.

前記水変色シートの多孔質層の表面には、多孔質層の表面に水の付着により形成される水変色像を覆い、水の乾燥を抑制して、水変色像の消失を遅延させる透明性カバー部材を備えてなる。
前記透明性カバー部材を形成する透明性基材は、水変色像を透視できる程度の透明性を有していればよく、プラスチックシート材やプラスチック成形体、ガラスにより形成される。
なお、着色透明の透明性基材を用いることもできる。
透明性カバー部材(透明性基材)の下面には水変色シート表面と透明性カバー部材を非接触状態に保持し、水変色シート表面と接する凸部を少なくとも三か所以上非直線状に配置することができる。
前記凸部は、多孔質層と透明性カバー部材の間に空間を形成すると共に、透明性カバー部材が多孔質像と接触して像を形成していない箇所に像中の水が拡散することにより、水変色像の輪郭がぼやけて不明瞭になることを防止するものである。
凸部は少なくとも三か所以上非直線状に配置することにより透明性カバー部材と多孔質層の接触を防止できる。
また、凸部は0.4mm~12.0mmの高さ、好ましくは0.5mm~10.0mmの高さを有することにより、多孔質層と透明性カバー部材の間の空間が水の乾燥を抑制して、水変色像の消失を遅延させる機能を良好なものとすることができる。
前記凸部の高さが、0.4mm未満では水変色シートに形成した水変色像が透明性カバー部材と接触し易くなり、水変色像の著しい滲みや像の形状変形が発生し易くなる。また凸部の高さが12.0mmを超える場合は水の乾燥を抑制する効果を発現し難く、水変色像の維持時間を延長し難くなる。
なお、0.4mmから12.0mmまで高さを変えていくと、0.4mmが最も水変色像の維持時間を延長できることから、凸部の高さを設定することにより、水変色像を維持する時間を調整することができる。
更に、前記透明性カバー部材上面から視認される凸部の表面積(s)と、凸部の高さ(h)が下記式(1)を満たすことにより、透明性カバー部材を通して視認される水変色像が凸部によって視認を妨げることなく、且つ、水変色像の消失を遅延させる機能を満たすことができる。
1.0≦s/h≦00 (1)
s/hが1.0未満では凸部の形状が鋭角になり、多孔質層を損傷し易く、また、取り扱いに注意が必要となる。また、s/hが00を超えると前記透明性カバー部材上面から視認される凸部の表面積が大きくなり、水変色像の視認を妨げ易くなる。
更に、前記カバー部材上面の表面積に対して、カバー部材上面から視認される凸部の占有面積は10.0%以下であることにより、水変色像が凸部によって視認を妨げることを防止できる。
なお、凸部は透明性を有することが好ましく、多孔質層が白色の場合は白色を呈することが好ましく、水変色像が凸部によって視認を妨げることを防止できる。
前記凸部の先端が曲面形状であることにより、多孔質層を損傷し難く、多孔質層が剥離することを防止できると共に、幼児でも取り扱いが容易となる。
更に、前記透明性カバー部材が可撓性を有することにより、透明性カバー部材の被覆と剥離を容易なものとすることとができると共に、凸部を100cmあたり三個以上、好ましくは四個以上備えることにより、使用時に水変色像との接触を好適に回避することができる。
更に、透明性カバー部体は、一端部を水変色シートに取り付け、他端部を自由端となして、水変色シートに開閉自在に設けることにより、水変色像の形成後、速やかに簡便にカバーできる利便性を向上させることができる。
更に、複数の水変色シートと、複数の透明性カバー部材とからなる水変色体とすることにより、水変色像が乾燥する前に別の水変色シートに水変色像を形成することができるため、迅速に所望の像を形成することができる。
前記複数の水変色シートと、複数の透明性カバー部材は、同数であってもよいが、透明性カバー部材が少ない構成であってもよい。
更に、複数の水変色シートと、単一の透明性カバー部材とからなる水変色体であっても同様の効果を奏することができる。
更に、後述する複数の水変色シートと、複数の透明性カバー部材と、複数の透明性枠シートとからなる水変色体とすることにより、水変色像が乾燥する前に別の水変色シートに水変色像を形成することができるため、迅速に所望の像を形成することができる。
前記複数の水変色シートと、複数の透明性カバー部材と、複数の透明性枠シートは、同数であってもよいが、透明性カバー部材及び透明性枠シートが水変色シートよりも少ない構成であってもよい。
更に、複数の水変色シートと、単一の透明性カバー部材及び単一の透明性枠シートとからなる水変色体であっても同様の効果を奏することができる。
The surface of the porous layer of the water-discoloring sheet is provided with a transparent cover member that covers the water-discoloring image formed by the adhesion of water to the surface of the porous layer, inhibits the water from drying, and delays the disappearance of the water-discoloring image.
The transparent substrate forming the transparent cover member only needs to have a transparency sufficient to allow the water discoloration image to be seen through, and may be made of a plastic sheet material, a plastic molded body, or glass.
A transparent, colored substrate may also be used.
The underside of the transparent cover member (transparent base material) can be kept in a non-contact state between the surface of the water-color-changing sheet and the transparent cover member, and at least three or more convex portions that contact the surface of the water-color-changing sheet can be arranged in a non-linear pattern.
The convex portions form a space between the porous layer and the transparent cover member, and also prevent the contours of the water-discolored image from becoming blurred and unclear, which would occur if the transparent cover member came into contact with the porous image and water in the image diffused to areas where no image was formed.
By arranging the protrusions in a non-linear pattern at at least three locations, contact between the transparent cover member and the porous layer can be prevented.
Furthermore, by having the convex portions have a height of 0.4 mm to 12.0 mm, preferably 0.5 mm to 10.0 mm, the space between the porous layer and the transparent cover member can inhibit the drying of water, thereby improving the function of delaying the disappearance of the water-discolored image.
If the height of the convex portions is less than 0.4 mm, the water-discoloring image formed on the water-discoloring sheet is likely to come into contact with the transparent cover member, resulting in significant bleeding of the water-discoloring image and deformation of the image.If the height of the convex portions is more than 12.0 mm, the effect of suppressing water drying is difficult to exhibit, and it is difficult to extend the duration of the water-discoloring image.
Furthermore, when the height is changed from 0.4 mm to 12.0 mm, 0.4 mm is the longest length of time the water discoloration image is maintained, so by setting the height of the convex part, the time the water discoloration image is maintained can be adjusted.
Furthermore, by making the surface area (s) of the convex portions visible from the top surface of the transparent cover member and the height (h) of the convex portions satisfy the following formula (1), the visibility of the water-discolored image visible through the transparent cover member is not hindered by the convex portions, and the function of delaying the disappearance of the water-discolored image can be achieved.
1.0≦s/h≦ 400 (1)
If s/h is less than 1.0, the shape of the convex portions will be acute-angled, which will easily damage the porous layer and require careful handling.If s/h is more than 400 , the surface area of the convex portions visible from the top surface of the transparent cover member will be large, which will easily hinder the visibility of the water-discolored image.
Furthermore, the area occupied by the convex portions visible from the upper surface of the cover member is 10.0% or less of the surface area of the upper surface of the cover member, so that the visibility of the water discoloration image can be prevented from being obstructed by the convex portions.
The convex portions are preferably transparent, and when the porous layer is white, they preferably exhibit a white color, so that the convex portions can be prevented from interfering with the visibility of the water-discolored image.
The curved tip of the convex portion makes it difficult for the porous layer to be damaged, prevents the porous layer from peeling off, and makes it easy for even small children to handle.
Furthermore, since the transparent cover member is flexible, it can be easily covered and peeled off, and by providing three or more, preferably four or more, convex portions per 100 cm2, it is possible to suitably avoid contact with the water-discolored image during use.
Furthermore, by attaching one end of the transparent cover body to the water-discoloring sheet and leaving the other end as a free end so that it can be opened and closed freely on the water-discoloring sheet, convenience can be improved by allowing the water-discoloring image to be covered quickly and easily after it is formed.
Furthermore, by making the water-discoloring body consist of a plurality of water-discoloring sheets and a plurality of transparent cover members, a water-discoloring image can be formed on another water- discoloring sheet before the water-discoloring image dries, so that the desired image can be formed quickly.
The number of the water-coloring sheets and the number of the transparent cover members may be the same, or the number of the transparent cover members may be fewer.
Furthermore, a water-color changing body consisting of a plurality of water-color changing sheets and a single transparent cover member can also achieve the same effect.
Furthermore, by making the water-discoloring body consist of a plurality of water-discoloring sheets, a plurality of transparent cover members, and a plurality of transparent frame sheets, as described below, a water-discoloring image can be formed on another water -discoloring sheet before the water-discoloring image dries, thereby enabling the desired image to be formed quickly.
The number of the water-discoloring sheets, the number of transparent cover members, and the number of transparent frame sheets may be the same, or the number of transparent cover members and transparent frame sheets may be fewer than the number of water-discoloring sheets.
Furthermore, a water-color changing body consisting of a plurality of water-color changing sheets, a single transparent cover member, and a single transparent frame sheet can also achieve the same effect.

また、前記透明性カバー部材として、カバー部材下面の周縁部が水変色シート表面と密接し、周縁部内方は水変色シート表面と非接触状態に保持する空隙部を備えることにより、多孔質層の表面に水の付着により形成される水変色像を覆い、水の乾燥を抑制して、水変色像の消失を遅延させることもできる。
前記空隙部の高さは0.4mm~12.0mm、好ましくは0.5mm~10.0mmの高さを有することにより、多孔質層と透明性カバー部材の間の空間が水の乾燥を抑制して、水変色像の消失を遅延させる機能を良好なものとすることができる。
前記高さが、0.4mm未満では水変色シートに形成した水変色像が透明性カバー部材と接触し易くなり、水変色像の著しい滲みや像の形状変形が発生し易くなる。高さが12.0mmを超える場合は水の乾燥を抑制する効果を発現し難く、水変色像の維持時間を延長し難くなる。
Furthermore, the transparent cover member has a peripheral portion on the underside of the cover member that is in close contact with the surface of the water-discoloring sheet, and the inner peripheral portion has a void portion that keeps it out of contact with the surface of the water-discoloring sheet, thereby covering the water-discoloring image formed by the adhesion of water to the surface of the porous layer, preventing the water from drying, and delaying the disappearance of the water-discoloring image.
The height of the void portion is 0.4 mm to 12.0 mm, preferably 0.5 mm to 10.0 mm, so that the space between the porous layer and the transparent cover member can suppress drying of water, thereby improving the function of delaying disappearance of the water-discolored image.
If the height is less than 0.4 mm, the water-discoloring image formed on the water-discoloring sheet is likely to come into contact with the transparent cover member, resulting in significant bleeding of the water-discoloring image and deformation of the image.If the height is more than 12.0 mm, it is difficult to achieve the effect of suppressing the drying of water, and it is difficult to extend the duration of the water-discoloring image.

前記透明性カバー部材には水変色シートに形成する文字等の文字枠を設ける、或いは、前記透明性カバー部材上に、水変色シートに形成する文字等の文字枠を印刷等の手段により設けた透明性枠シートを備えることにより、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができる。
前記透明性カバー部材上に形成される文字枠の大きさ、形状、色、線幅、線種は特に限定されるものではない。
また、文字枠を設ける透明性枠シートは、プラスチックシート材やプラスチック成形体、ガラスにより形成され、文字枠を印刷等の手段により設けることができる。
前記文字とは、平仮名、片仮名、漢字の他、英数字、各種記号であってもよい。
前記透明性カバー部材表面又は透明性枠シート表面が微細な凹凸を有して非光沢であることにより、表面で光が反射して水変色像の視認性を妨げることを防止することができる。
また、拭き消し可能なインキを収容したホワイトボード用マーカー等の筆記具、水により消色するインキを収容した筆記具等の消去性筆記具を用いて、透明性カバー部材表面又は透明性枠シート表面に筆記して水変色像をなぞり書きしたり、別の文字や採点を記載することもできる。
By providing the transparent cover member with a frame for letters, etc. to be formed on the water -discoloring sheet , or by providing the transparent cover member with a transparent frame sheet on which the frame for letters, etc. to be formed on the water -discoloring sheet is formed by means of printing or the like, it is possible to visually confirm whether the water-discoloring image has been properly formed within the frame, and to confirm whether the water-discoloring image has been formed in a well-balanced manner.
The size, shape, color, line width and line type of the character frame formed on the transparent cover member are not particularly limited.
The transparent frame sheet on which the character frame is provided is made of a plastic sheet material, a plastic molded body, or glass, and the character frame can be provided by means of printing or the like.
The characters may be hiragana, katakana, kanji, alphanumeric characters, and various symbols.
The surface of the transparent cover member or the surface of the transparent frame sheet has minute irregularities and is non-glossy, so that it is possible to prevent light from being reflected on the surface and impairing the visibility of the water-discolored image.
In addition, erasable writing implements such as whiteboard markers containing wipeable ink or writing implements containing ink that fades with water can be used to write on the surface of the transparent cover member or the surface of the transparent frame sheet to trace the water-discolored image or write other letters or marks.

前記水変色シートに水を付着させる手段としては、手や指を水で濡らして接触させる他、水付着具を適用することもできる。
前記水付着具としては、水鉄砲、噴霧機、先端部に筆穂や繊維ペン体等を有する筆記又は塗布具、容器内に水を収容し、且つ、容器内の水を導出する繊維体や刷毛を設けた筆記又は塗布具、スタンプ具等が挙げられる。
前記水付着具として、連続気孔を有するプラスチック多孔体又は繊維加工体をペン先部材として適用した筆記具又は塗布具は、筆記像を簡便に形成でき、実用性を高めることができる。
なお、前記水付着具と、水変色体とを組み合わせて水変色体セットを構成することもでき、教習具セット、描画玩具セットとして用いることができる。
前記水付着具としては、筆記体、スタンプ具が挙げられ、前記筆記体は、毛筆、連続気孔プラスチック体、フェルト、繊維の樹脂加工乃至融着加工体、プラスチックの内部軸線方向に毛細間隙を設けたもの、等の部材を単体として使用することができるが、前記部材をペン先として軸胴に装着し、軸胴内に収容した水を導出可能に構成した筆記具形態のものが実用的である。
スタンプ具は、プラスチック多孔体、印面を粗面に形成して水濡れ性を付与したプラスチック成形体等を印材としたもの、或いは、前記部材を車輪状回転体外周部等に取り付けた回転スタンプ形態のものであってもよい。
As a means for applying water to the water-discoloring sheet, a hand or finger may be wetted with water and brought into contact with the sheet, or a water application tool may be used.
Examples of the water application tool include water guns, sprayers, writing or application tools with a brush tip or fiber pen body at the tip, writing or application tools that store water in a container and have a fiber body or brush that discharges the water from the container, stamping tools, etc.
A writing implement or applicator using a plastic porous body or processed fiber body having continuous pores as a pen tip member as the water adhesion implement can easily form a written image and has improved practicality.
In addition, a water-color changing object set can be constructed by combining the water-adhering tool and the water-color changing object, and can be used as a teaching tool set or a drawing toy set.
Examples of the water-adhering device include writing implements and stamping implements. The writing implements can be a writing brush, a continuous-pore plastic body, felt, a resin-processed or fused fiber body, a plastic body with capillary gaps in the internal axial direction, or other such components that can be used alone, but a more practical writing implement is one in which the component is attached to the barrel as a pen tip and is configured to be able to extract water contained in the barrel.
The stamping tool may be a stamping material made of a plastic porous body, a plastic molded body with a roughened stamping surface that is water-wettable, or a rotary stamp in which the above-mentioned component is attached to the outer periphery of a wheel-shaped rotating body.

以下に実施例を示すが、本発明は実施例に限定されない。なお、実施例中の部は質量部を示す。
実施例1(図1、2参照)
水変色体の作製
白色合成紙からなる支持体3上に、青色顔料5部、アクリル酸エステルエマルジョン(固形分50重量%)50部、シリコーン系消泡剤0.2部、増粘剤3部、湿潤剤2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、攪拌したスクリーン印刷用インキを用いて、180メッシュのスクリーン版によるスクリーン印刷を行って、着色層4を形成した。次いで、前記着色層上に、湿式法により製造される微粒子状珪酸〔商品名:ニップシールE-200A、日本シリカ工業(株)製〕15部、バインダー樹脂として水性ウレタン樹脂〔商品名:ハイドランAP-10、ポリエステル系ウレタン樹脂、固形分30重量%、大日本インキ化学工業(株)製〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、エポキシ系架橋剤2部を均一に混合、攪拌した白色スクリーン印刷用インキを用いて全面ベタ印刷を施して多孔質層5を形成し、220mm×320mmの大きさからなる水変色シート2を得た。
次いで、透明性基材7として厚さ1.0mm、200mm×300mmの大きさの透明性硬質ABS樹脂からなる板状成型物の下面に直径10mm、高さ1.0mmの先端が曲面の円錐形状の透明ABS樹脂からなる凸部8を二等辺三角形の頂点に相当する位置に3箇所設け、板状成型物の上面に黒色の印刷インキを用いて四つの四角形からなる文字枠9を設けて透明性カバー部材6を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は78.5mmであり、凸部の高さ(h)は1.0mmであり、凸部の表面積(s)/凸部の高さ(h)は78.5であった。
また、前記透明性カバー部材上面の表面積は600cmであり、透明性カバー部材の上面から視認される凸部の占有面積は2.36cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は0.39%であった。
前記水変色シート2と前記透明性カバー部材6とを備えた水変色体1を得た。
Examples are shown below, but the present invention is not limited to these examples. In the examples, "parts" refers to parts by mass.
Example 1 (see Figures 1 and 2)
Preparation of Water-Discoloring Material A colored layer 4 was formed on a support 3 made of white synthetic paper by screen printing using a 180-mesh screen stencil, using a screen printing ink prepared by uniformly mixing and stirring 5 parts of blue pigment, 50 parts of acrylic ester emulsion (solid content 50% by weight), 0.2 parts of silicone-based antifoaming agent, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy-based crosslinking agent. Next, on the colored layer, 15 parts of particulate silicic acid produced by a wet method [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], 50 parts of an aqueous urethane resin as a binder resin [trade name: Hydran AP-10, polyester-based urethane resin, solid content 30% by weight, manufactured by Dainippon Ink and Chemicals, Inc.], 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of an aqueous ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred to form a white screen printing ink, which was then solid printed over the entire surface to form a porous layer 5, and a water-discoloring sheet 2 measuring 220 mm x 320 mm was obtained.
Next, a transparent substrate 7 was formed on the underside of a plate-shaped molded article made of transparent hard ABS resin with a thickness of 1.0 mm and dimensions of 200 mm x 300 mm. Three convex portions 8 made of transparent ABS resin with a diameter of 10 mm and a height of 1.0 mm and a curved tip were provided at positions corresponding to the vertices of an isosceles triangle, and a character frame 9 consisting of four rectangles was formed on the upper surface of the plate-shaped molded article using black printing ink, thereby obtaining a transparent cover member 6.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 78.5 mm2 , the height (h) of the convex portion was 1.0 mm, and the surface area (s) of the convex portion/height (h) of the convex portion was 78.5.
Furthermore, the surface area of the upper surface of the transparent cover member was 600 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 2.36 cm2 , and the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 0.39%.
A water-coloring body 1 comprising the water-coloring sheet 2 and the transparent cover member 6 was obtained.

前記水変色シートは常態では白色を呈しているが、水を収容した筆記体で多孔質層上に筆記すると青色の水変色像を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シートに水を収容した筆記体で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
更に、透明性カバー部材には文字の文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
次いで、水変色シート上から透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
The water-discoloring sheet was normally white, but when a writing tool containing water was used to write on the porous layer, a blue water-discoloring image was formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discolored image was formed on the water-discolored sheet by writing with a writing pen containing water, and the transparent cover member was placed on the water-discolored sheet on which the water-discolored image had been formed so that the tips of the convex portions were in contact with the surface of the water-discolored sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, since the transparent cover member is provided with a frame for the letters, it is possible to visually confirm whether the water-discolored image is properly formed within the frame, and to confirm whether the water-discolored image is well-balanced.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Next, when the transparent cover member was removed from the water-discoloring sheet, the water-discoloring image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized and the sheet returned to its original state. This phenomenon could be repeated many times.

実施例2(図3、4参照)
水変色体の作製
白色合成紙上にポリエステル製不織布を設けた支持体3上に、黒色顔料5部、アクリル酸エステルエマルジョン(固形分50重量%)50部、シリコーン系消泡剤0.2部、増粘剤3部、湿潤剤2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、攪拌したスクリーン印刷用インキを用いて、180メッシュのスクリーン版によるスクリーン印刷を行って、着色層4を形成した。次いで、前記着色層上に、湿式法により製造される微粒子状珪酸〔商品名:ニップシールE-200A、日本シリカ工業(株)製〕15部、バインダー樹脂として水性ウレタン樹脂〔商品名:ハイドランAP-10、ポリエステル系ウレタン樹脂、固形分30重量%、大日本インキ化学工業(株)製〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、エポキシ系架橋剤2部を均一に混合、攪拌した白色スクリーン印刷用インキを用いて全面ベタ印刷を施して多孔質層5を形成し、280mm×380mmの大きさからなる水変色シート2を得た。
次いで、透明性基材7として厚さ50μm、253mm×353mmの大きさの可撓性を有するポリエステル製透明シートの下面に直径3mm、高さ1.2mmの先端が曲面の半球形状の白色ポリウレタン樹脂からなる凸部8を47mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材6を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は7.07mmであり、凸部の高さ(h)は1.2mmであり、凸部の表面積(s)/凸部の高さ(h)は5.89であった。
また、前記透明性カバー部材上面の表面積は893.09cmであり、透明性カバー部材の上面から視認される凸部の占有面積は3.39cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は0.38%であり、100cmあたりの凸部の数は、5.37個であった。
更に、透明性基材71として厚さ50μm、233mm×333mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠9を設けて透明性枠シート10を得た。
前記水変色シートと前記透明性カバー部材と透明性枠シートとを備えた水変色体を得た。
Example 2 (see Figures 3 and 4)
Preparation of Water-Discoloring Material A colored layer 4 was formed on a support 3 made of white synthetic paper with a polyester nonwoven fabric provided thereon by screen printing using a 180-mesh screen stencil, using a screen printing ink prepared by uniformly mixing and stirring 5 parts of black pigment, 50 parts of acrylic ester emulsion (solid content 50% by weight), 0.2 parts of silicone-based antifoaming agent, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy-based crosslinking agent. Next, on the colored layer, 15 parts of particulate silicic acid produced by a wet method [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], 50 parts of an aqueous urethane resin as a binder resin [trade name: Hydran AP-10, polyester-based urethane resin, solid content 30% by weight, manufactured by Dainippon Ink and Chemicals, Inc.], 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of an aqueous ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred to form a white screen printing ink, which was then solid-printed over the entire surface to form a porous layer 5, and a water-discoloring sheet 2 measuring 280 mm x 380 mm was obtained.
Next, 48 convex portions 8 made of white polyurethane resin, each having a diameter of 3 mm and a height of 1.2 mm and a curved hemispherical shape with a curved tip, were arranged in a checkerboard pattern at equal intervals of 47 mm on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 253 mm x 353 mm as the transparent substrate 7, to obtain a transparent cover member 6.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 7.07 mm2 , the height (h) of the convex portion was 1.2 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 5.89.
Furthermore, the surface area of the upper surface of the transparent cover member was 893.09 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 3.39 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 0.38%, and the number of convex portions per 100 cm2 was 5.37.
Furthermore, a transparent base material 71 was a flexible polyester transparent sheet having a thickness of 50 μm and a size of 233 mm x 333 mm, and a character frame 9 consisting of six rectangles was printed on the underside of the sheet using black printing ink to obtain a transparent frame sheet 10.
A water-coloring body comprising the water-coloring sheet, the transparent cover member, and the transparent frame sheet was obtained.

前記水変色シートは常態では白色を呈しているが、筆穂に水を含侵させた毛筆で多孔質層上に筆記すると黒色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
なお、前記透明性カバー部材と透明性枠シートは可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush whose tip was impregnated with water, black water-discolored images (letters) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member were removed from the water-discolored sheet, the water-discolored image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized, returning to a completely white water-discolored sheet. This phenomenon could be repeated many times.
Furthermore, since the transparent cover member and the transparent frame sheet are flexible, the water-discoloring body can be rolled up and carried around, and is therefore highly portable.

実施例3
水変色体の作製
実施例2と同様にして水変色シートを得た。
次いで、透明性基材として厚さ50μm、253mm×353mmの大きさの可撓性を有するポリエステル製の透明シートの下面に直径3mm、高さ0.6mmの先端が曲面の半球形状の白色ポリウレタン樹脂からなる凸部を47mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は7.07mmであり、凸部の高さ(h)は0.5mmであり、凸部の表面積(s)/凸部の高さ(h)は14.14であった。
また、前記透明性カバー部材上面の表面積は893.09cmであり、透明性カバー部材の上面から視認される凸部の占有面積は3.39cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は0.38%であり、100cmあたりの凸部の数は、5.37個であった。
更に、透明性基材として厚さ50μm、253mm×353mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠枠を設けて透明性枠シートを得た。
前記水変色シートと前記透明性カバー部材と透明性枠シートとを備えた水変色体を得た。
Example 3
Preparation of Water-Colored Material A water-colored sheet was obtained in the same manner as in Example 2.
Next, a transparent polyester sheet having a thickness of 50 μm and dimensions of 253 mm x 353 mm was used as a transparent substrate. On the underside of the sheet, 48 convex portions made of white polyurethane resin, each 3 mm in diameter and 0.6 mm in height and with a curved hemispherical tip, were provided at equal intervals of 47 mm in a checkerboard pattern to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 7.07 mm2 , the height (h) of the convex portion was 0.5 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 14.14.
Furthermore, the surface area of the upper surface of the transparent cover member was 893.09 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 3.39 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 0.38%, and the number of convex portions per 100 cm2 was 5.37.
Furthermore, a transparent frame sheet consisting of six squares was printed on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 253 mm x 353 mm as a transparent substrate using black printing ink to obtain a transparent frame sheet.
A water-coloring body comprising the water-coloring sheet, the transparent cover member, and the transparent frame sheet was obtained.

前記水変色シートは常態では白色を呈しているが、筆穂に水を浸した毛筆で多孔質層上に筆記すると黒色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
なお、前記透明性枠シートと透明性カバー部材は可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush whose tip was dipped in water, black water-discolored images (letters) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member were removed from the water-discoloring sheet, the water-discoloring image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized and returned to its original state. This phenomenon could be repeated many times.
Furthermore, since the transparent frame sheet and the transparent cover member are flexible, the water-color changing body can be rolled up and carried around, and is therefore highly portable.

実施例4
水変色体の作製
実施例2と同様にして水変色シートを得た。
次いで、透明性基材として厚さ50μm、262mm×362mmの大きさの可撓性を有するポリエステル製の透明シートの下面に直径12mm、高さ5.0mmの先端が曲面の半球形状の白色ポリウレタン樹脂からなる凸部を38mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は113.04mmであり、凸部の高さ(h)は5.0mmであり、凸部の表面積(s)/凸部の高さ(h)は22.61であった。
また、前記透明性カバー部材上面の表面積は948.44cmであり、透明性カバー部材の上面から視認される凸部の占有面積は54.26cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は5.72%であり、100cmあたりの凸部の数は、5.06個であった。
更に、透明性基材として厚さ50μm、262mm×362mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シートを得た。
前記水変色シートと前記透明性カバー部材と透明性枠シートとを備えた水変色体を得た。
Example 4
Preparation of Water-Colored Material A water-colored sheet was obtained in the same manner as in Example 2.
Next, a transparent polyester sheet having a thickness of 50 μm and dimensions of 262 mm x 362 mm was used as a transparent substrate. On the underside of the sheet, 48 convex portions made of white polyurethane resin, each 12 mm in diameter and 5.0 mm in height and having a curved hemispherical tip, were provided at equal intervals of 38 mm in a checkerboard pattern to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 113.04 mm2 , the height (h) of the convex portion was 5.0 mm, and the surface area (s) of the convex portion/height (h) of the convex portion was 22.61.
Furthermore, the surface area of the upper surface of the transparent cover member was 948.44 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 54.26 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 5.72%, and the number of convex portions per 100 cm2 was 5.06.
Furthermore, a transparent frame sheet consisting of six squares was printed on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 262 mm x 362 mm as a transparent substrate using black printing ink to obtain a transparent frame sheet.
A water-coloring body comprising the water-coloring sheet, the transparent cover member, and the transparent frame sheet was obtained.

前記水変色シートは常態では白色を呈しているが、筆穂に水を浸した毛筆で多孔質層上に筆記すると黒色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で20分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
なお、前記透明性枠シートと透明性カバー部材は可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush whose tip was dipped in water, black water-discolored images (letters) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 20 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member were removed from the water-discoloring sheet, the water-discoloring image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized and returned to its original state. This phenomenon could be repeated many times.
Furthermore, since the transparent frame sheet and the transparent cover member are flexible, the water-color changing body can be rolled up and carried around, and is therefore highly portable.

実施例5
水変色体の作製
実施例2と同様にして水変色シートを得た。
次いで、透明性基材として厚さ50μm、265mm×365mmの大きさの可撓性を有するポリエステル製の透明シートの下面に直径15mm、高さ7.0mmの先端が曲面の半球形状の白色ポリウレタン樹脂からなる凸部を35mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は176.63mmであり、凸部の高さ(h)は7.0mmであり、凸部の表面積(s)/凸部の高さ(h)は25.23であった。
また、前記透明性カバー部材上面の表面積は967.25cmであり、透明性カバー部材の上面から視認される凸部の占有面積は84.78cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は8.77%であり、100cmあたりの凸部の数は、4.96個であった。
更に、透明性基材として厚さ50μm、265mm×365mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シートを得た。
前記水変色シートと前記透明性カバー部材と透明性枠シートとを備えた水変色体を得た。
Example 5
Preparation of Water-Colored Material A water-colored sheet was obtained in the same manner as in Example 2.
Next, a transparent polyester sheet having a thickness of 50 μm and dimensions of 265 mm x 365 mm was used as a transparent substrate. On the underside of the sheet, 48 convex portions made of white polyurethane resin, each 15 mm in diameter and 7.0 mm in height and with a curved hemispherical tip, were provided at equal intervals of 35 mm in a checkerboard pattern to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 176.63 mm2 , the height (h) of the convex portion was 7.0 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 25.23.
Furthermore, the surface area of the upper surface of the transparent cover member was 967.25 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 84.78 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 8.77%, and the number of convex portions per 100 cm2 was 4.96.
Furthermore, a transparent frame sheet consisting of six squares was printed on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 265 mm x 365 mm as a transparent substrate using black printing ink to obtain a transparent frame sheet.
A water-coloring body comprising the water-coloring sheet, the transparent cover member, and the transparent frame sheet was obtained.

前記水変色シートは常態では白色を呈しているが、筆穂に水を浸した毛筆で多孔質層上に筆記すると黒色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で15分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
なお、前記透明性枠シートと透明性カバー部材は可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush whose tip was dipped in water, black water-discolored images (letters) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 15 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member were removed from the water-discoloring sheet, the water-discoloring image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized and returned to its original state. This phenomenon could be repeated many times.
Furthermore, since the transparent frame sheet and the transparent cover member are flexible, the water-color changing body can be rolled up and carried around, and is therefore highly portable.

実施例6
水変色体の作製
実施例2と同様にして水変色シートを得た。
次いで、透明性基材として厚さ50μm、265mm×365mmの大きさの可撓性を有するポリエステル製の透明シートの下面に直径15mm、高さ10.0mmの先端が曲面の半球形状の白色ポリウレタン樹脂からなる凸部を35mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は176.63mmであり、凸部の高さ(h)は10.0mmであり、凸部の表面積(s)/凸部の高さ(h)は17.66であった。
また、前記透明性カバー部材上面の表面積は967.25cmであり、透明性カバー部材の上面から視認される凸部の占有面積は84.78cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は8.77%であり、100cmあたりの凸部の数は、4.96個であった。
更に、透明性基材として厚さ50μm、265mm×365mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シートを得た。
前記水変色シートと前記透明性カバー部材と透明性枠シートを備えた水変色体を得た。
Example 6
Preparation of Water-Colored Material A water-colored sheet was obtained in the same manner as in Example 2.
Next, a transparent polyester sheet having a thickness of 50 μm and dimensions of 265 mm x 365 mm was used as a transparent substrate. On the underside of the sheet, 48 convex portions made of white polyurethane resin, each 15 mm in diameter and 10.0 mm in height and with a curved hemispherical tip, were provided at equal intervals of 35 mm in a checkerboard pattern to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 176.63 mm2 , the height (h) of the convex portion was 10.0 mm, and the surface area (s) of the convex portion/height (h) of the convex portion was 17.66.
Furthermore, the surface area of the upper surface of the transparent cover member was 967.25 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 84.78 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 8.77%, and the number of convex portions per 100 cm2 was 4.96.
Furthermore, a transparent frame sheet consisting of six squares was printed on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 265 mm x 365 mm as a transparent substrate using black printing ink to obtain a transparent frame sheet.
A water-coloring body comprising the water-coloring sheet, the transparent cover member, and the transparent frame sheet was obtained.

前記水変色シートは常態では白色を呈しているが、筆穂に水を浸した毛筆で多孔質層上に筆記すると黒色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視覚することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で10分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができる。
なお、前記透明性枠シートと透明性カバー部材は可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush whose tip was dipped in water, black water-discolored images (letters) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 10 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member are removed from the water-discoloring sheet, the water-discoloring image gradually disappears as the water evaporates, and after 10 minutes the image has completely disappeared and returned to its original state. This phenomenon can be repeated many times.
Furthermore, since the transparent frame sheet and the transparent cover member are flexible, the water-color changing body can be rolled up and carried around, and is therefore highly portable.

実施例7
水変色体の作製
実施例2と同様にして水変色シートを得た。
次いで、透明性基材として厚さ50μm、265mm×365mmの大きさの可撓性を有するポリエステル製の透明シートの下面に直径15mm、高さ0.5mmの先端が曲面の半球形状の白色ポリウレタン樹脂からなる凸部を35mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は176.63mmであり、凸部の高さ(h)は0.5mmであり、凸部の表面積(s)/凸部の高さ(h)は353.33であった。
また、前記透明性カバー部材上面の表面積は967.25cmであり、透明性カバー部材の上面から視認される凸部の占有面積は84.78cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は8.77%であり、100cmあたりの凸部の数は、4.96個であった。
更に、透明性基材として厚さ50μm、265mm×365mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シートを得た。
前記水変色シートの一端部に透明性カバー部材と透明性枠シートとを取り付け、他端部を自由端として水変色体を得た。
Example 7
Preparation of Water-Colored Material A water-colored sheet was obtained in the same manner as in Example 2.
Next, a transparent polyester sheet having a thickness of 50 μm and dimensions of 265 mm x 365 mm was used as a transparent substrate. On the underside of the sheet, 48 convex portions made of white polyurethane resin, each 15 mm in diameter and 0.5 mm in height and with a curved hemispherical tip, were provided at equal intervals of 35 mm in a checkerboard pattern to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 176.63 mm2 , the height (h) of the convex portion was 0.5 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 353.33.
Furthermore, the surface area of the upper surface of the transparent cover member was 967.25 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 84.78 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 8.77%, and the number of convex portions per 100 cm2 was 4.96.
Furthermore, a transparent frame sheet consisting of six squares was printed on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 265 mm x 365 mm as a transparent substrate using black printing ink to obtain a transparent frame sheet.
A transparent cover member and a transparent frame sheet were attached to one end of the water-coloring sheet, and the other end was left as a free end to obtain a water-coloring body.

前記水変色シートは常態では白色を呈しているが、筆穂に水を浸した毛筆で多孔質層上に筆記すると黒色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視覚することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができる。
なお、前記透明性枠シートと透明性カバー部材は可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush whose tip was dipped in water, black water-discolored images (letters) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member are removed from the water-discoloring sheet, the water-discoloring image gradually disappears as the water evaporates, and after 10 minutes the image has completely disappeared and returned to its original state. This phenomenon can be repeated many times.
Furthermore, since the transparent frame sheet and the transparent cover member are flexible, the water-color changing body can be rolled up and carried around, and is therefore highly portable.

実施例8
水変色体の作製
実施例2と同様にして水変色シートを得た。
次いで、透明性基材として厚さ50μm、255mm×355mmの大きさの可撓性を有するポリエステル製の透明シートの下面に直径5mm、高さ10.0mmの先端が曲面の円錐形状の白色の軟質SEBS樹脂からなる凸部を45mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は19.63mmであり、凸部の高さ(h)は10.0mmであり、凸部の表面積(s)/凸部の高さ(h)は1.96であった。
また、前記透明性カバー部材上面の表面積は905.25cmであり、透明性カバー部材の上面から視認される凸部の占有面積は9.42cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は1.04%であり、100cmあたりの凸部の数は、5.30個であった。
更に、透明性基材として厚さ50μm、265mm×365mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シートを得た。
前記水変色シートの一端部に透明性カバー部材と透明性枠シートとを取り付け、他端部を自由端として水変色体を得た。
Example 8
Preparation of Water-Colored Material A water-colored sheet was obtained in the same manner as in Example 2.
Next, 48 convex portions made of white soft SEBS resin, each having a diameter of 5 mm and a height of 10.0 mm and a curved tip, were provided in a grid pattern at equal intervals of 45 mm on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 255 mm x 355 mm as a transparent substrate, to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 19.63 mm2 , the height (h) of the convex portion was 10.0 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 1.96.
Furthermore, the surface area of the upper surface of the transparent cover member was 905.25 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 9.42 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 1.04%, and the number of convex portions per 100 cm2 was 5.30.
Furthermore, a transparent frame sheet consisting of six squares was printed on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 265 mm x 365 mm as a transparent substrate using black printing ink to obtain a transparent frame sheet.
A transparent cover member and a transparent frame sheet were attached to one end of the water-coloring sheet, and the other end was left as a free end to obtain a water-coloring body.

前記水変色シートは常態では白色を呈しているが、筆穂に水を浸した毛筆で多孔質層上に筆記すると黒色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視覚することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で10分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができる。
なお、前記透明性枠シートと透明性カバー部材は可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush whose tip was dipped in water, black water-discolored images (letters) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 10 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member are removed from the water-discoloring sheet, the water-discoloring image gradually disappears as the water evaporates, and after 10 minutes the image has completely disappeared and returned to its original state. This phenomenon can be repeated many times.
Furthermore, since the transparent frame sheet and the transparent cover member are flexible, the water-color changing body can be rolled up and carried around, and is therefore highly portable.

実施例9
目付量が130g/mの赤色ポリエステルサテン生地からなる支持体上に、湿式法により製造される微粒子状珪酸〔商品名:ニップシールE-200A、日本シリカ工業(株)製〕15部、バインダー樹脂として水性ウレタン樹脂〔商品名:ハイドランAP-10、ポリエステル系ウレタン樹脂、固形分30重量%、大日本インキ化学工業(株)製〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、エポキシ系架橋剤2部を均一に混合、攪拌した白色スクリーン印刷用インキを用いて全面ベタ印刷を施して多孔質層を形成し、310mm×410mmの大きさの水変色シートを得た。
次いで、透明性基材として厚さ200μm、310mm×410mmの大きさの可撓性を有する軟質PVC製の透明シートの下面に直径10mm、高さ3.0mmの先端が曲面の半球形状の透明な軟質PVC樹脂からなる凸部を40mmの間隔で63箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は78.5mmであり、凸部の高さ(h)は3.0mmであり、凸部の表面積(s)/凸部の高さ(h)は26.17であった。
また、前記透明性カバー部材上面の表面積は1271cmであり、透明性カバー部材の上面から視認される凸部の占有面積は49.46cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は3.9%であり、100cmあたりの凸部の数は、4.95個であった。
更に、透明性基材として厚さ100μm、300mm×400mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シートを得た。
前記水変色シートの一端部に透明性カバー部材と透明性枠シートとを取り付け、他端部を自由端として水変色体を得た。
Example 9
A porous layer was formed on a support made of red polyester satin fabric with a basis weight of 130 g/ by solid printing using a white screen printing ink prepared by uniformly mixing and stirring 15 parts of wet-processed fine particle silica (trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.), 50 parts of an aqueous urethane resin (trade name: Hydran AP-10, polyester-based urethane resin, solids content 30 wt%, manufactured by Dainippon Ink and Chemicals, Inc.) as a binder resin, 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of an aqueous ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent. A water-discoloring sheet measuring 310 mm x 410 mm was obtained by solid printing on the entire surface of the support.
Next, a transparent sheet made of flexible soft PVC, 200 μm thick and 310 mm x 410 mm in size, was used as a transparent substrate. On the underside of the sheet, 63 convex portions made of transparent soft PVC resin, each having a diameter of 10 mm and a height of 3.0 mm and a curved hemispherical tip, were provided at intervals of 40 mm to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 78.5 mm2 , the height (h) of the convex portion was 3.0 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 26.17.
Furthermore, the surface area of the upper surface of the transparent cover member was 1,271 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 49.46 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 3.9%, and the number of convex portions per 100 cm2 was 4.95.
Furthermore, a transparent frame sheet consisting of six squares was printed on the underside of a flexible polyester transparent sheet having a thickness of 100 μm and dimensions of 300 mm x 400 mm as a transparent substrate using black printing ink to obtain a transparent frame sheet.
A transparent cover member and a transparent frame sheet were attached to one end of the water-coloring sheet, and the other end was left as a free end to obtain a water-coloring body.

前記水変色シートは常態では白色を呈しているが、筆穂に水を収容した筆記体で多孔質層上に筆記すると赤色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、3分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を収容した筆記体で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視覚することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で20分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができる。
なお、前記透明性枠シートと透明性カバー部材は可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush containing water in the tip, red water-discolored images (letters) could be formed.
The water-discolored image was maintained for 3 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a writing brush containing water in the tip, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 20 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member are removed from the water-discoloring sheet, the water-discoloring image gradually disappears as the water evaporates, and after 10 minutes the image has completely disappeared and returned to its original state. This phenomenon can be repeated many times.
Furthermore, since the transparent frame sheet and the transparent cover member are flexible, the water-color changing body can be rolled up and carried around, and is therefore highly portable.

実施例10
水変色体の作製
実施例2と同様にして水変色シートを得た。
次いで、透明性基材として厚さ50μm、253mm×353mmの大きさの可撓性を有するポリエステル製の透明シートの下面に直径3mm、高さ0.4mmの先端が曲面の半球形状の白色ポリウレタン樹脂からなる凸部を47mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は7.07mmであり、凸部の高さ(h)は0.4mmであり、凸部の表面積(s)/凸部の高さ(h)は17.68であった。
また、前記透明性カバー部材上面の表面積は893.09cmであり、透明性カバー部材の上面から視認される凸部の占有面積は3.39cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は0.38%であり、100cmあたりの凸部の数は、5.37個であった。
更に、透明性基材として厚さ50μm、260mm×360mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シートを得た。
前記水変色シートの一端部に透明性カバー部材と透明性枠シートとを取り付け、他端部を自由端として水変色体を得た。
Example 10
Preparation of Water-Color Changing Material A water-color changing sheet was obtained in the same manner as in Example 2.
Next, a transparent polyester sheet having a thickness of 50 μm and dimensions of 253 mm x 353 mm was used as a transparent substrate. On the underside of the sheet, 48 convex portions made of white polyurethane resin, each 3 mm in diameter and 0.4 mm in height and with a curved hemispherical tip, were provided at equal intervals of 47 mm in a checkerboard pattern to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 7.07 mm2 , the height (h) of the convex portion was 0.4 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 17.68.
Furthermore, the surface area of the upper surface of the transparent cover member was 893.09 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 3.39 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 0.38%, and the number of convex portions per 100 cm2 was 5.37.
Furthermore, a transparent frame sheet consisting of six squares was printed on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 260 mm x 360 mm as a transparent substrate using black printing ink to obtain a transparent frame sheet.
A transparent cover member and a transparent frame sheet were attached to one end of the water-coloring sheet, and the other end was left as a free end to obtain a water-coloring body.

前記水変色シートは常態では白色を呈しているが、筆穂に水を浸した毛筆で多孔質層上に筆記すると黒色の水変色像(数字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視認することができた。また、水変色像は一部が透明カバー部材と接触して若干の滲みを生じるものの、実用上は問題なく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
なお、前記透明性枠シートと透明性カバー部材は可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when a writing brush with the tip dipped in water was used to write on the porous layer, black water-discolored images (numbers) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member. Although a portion of the water-discolored image came into contact with the transparent cover member and caused slight bleeding, this did not pose a practical problem and the clear water-discolored image was maintained.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member were removed from the water-discoloring sheet, the water-discoloring image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized and returned to its original state. This phenomenon could be repeated many times.
Furthermore, since the transparent frame sheet and the transparent cover member are flexible, the water-color changing body can be rolled up and carried around, and is therefore highly portable.

実施例11
水変色体の作製
実施例2と同様にして水変色シートを得た。
次いで、透明性基材として厚さ50μm、265mm×365mmの大きさの可撓性を有するポリエステル製の透明シートの下面に直径15mm、高さ12.0mmの先端が曲面の円錐形状の白色ポリウレタン樹脂からなる凸部を35mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は176.63mmであり、凸部の高さ(h)は12.0mmであり、凸部の表面積(s)/凸部の高さ(h)は14.72であった。
また、前記透明性カバー部材上面の表面積は967.25cmであり、透明性カバー部材の上面から視認される凸部の占有面積は84.78cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は8.77%であり、100cmあたりの凸部の数は、4.96個であった。
更に、透明性基材として厚さ50μm、265mm×365mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シートを得た。
前記水変色シートと透明性カバー部材と透明性枠シートとを備えた水変色体を得た。
Example 11
Preparation of Water-Color Changing Material A water-color changing sheet was obtained in the same manner as in Example 2.
Next, a transparent polyester sheet having a thickness of 50 μm and dimensions of 265 mm x 365 mm was used as a transparent substrate. On the underside of the sheet, 48 convex portions made of white polyurethane resin with a diameter of 15 mm, a height of 12.0 mm and a curved tip were provided in a checkerboard pattern at equal intervals of 35 mm to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 176.63 mm2 , the height (h) of the convex portion was 12.0 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 14.72.
Furthermore, the surface area of the upper surface of the transparent cover member was 967.25 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 84.78 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 8.77%, and the number of convex portions per 100 cm2 was 4.96.
Furthermore, a transparent frame sheet consisting of six squares was printed on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 265 mm x 365 mm as a transparent substrate using black printing ink to obtain a transparent frame sheet.
A water-coloring body comprising the water-coloring sheet, a transparent cover member, and a transparent frame sheet was obtained.

前記水変色シートは常態では白色を呈しているが、筆穂に水を浸した毛筆で多孔質層上に筆記すると黒色の水変色像(記号)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視覚することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を25℃、65%RHの環境下で7分間像を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
前記水変色像は水分の蒸発にともない徐々に消失し、15分経過した段階では全面白色の水変色シートに戻った。
この現象は繰り返し何度も行うことができる。
なお、前記透明性枠シートと透明性カバー部材は可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discoloring sheet was normally white, but when a writing brush with the tip dipped in water was used to write on the porous layer, a black water-discoloring image (symbol) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, so the clear water-discolored image was maintained for 7 minutes in an environment of 25°C and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
The water-discolored image gradually disappeared as the water evaporated, and after 15 minutes the entire sheet returned to a white color.
This phenomenon can be repeated many times.
Since the transparent frame sheet and the transparent cover member are flexible, the water-color changing body can be rolled up and carried around, and is therefore highly portable.

参考例1(図5参照)
水変色体の作製
白色合成紙からなる支持体3上に、青色顔料5部、アクリル酸エステルエマルジョン(固形分50重量%)50部、シリコーン系消泡剤0.2部、増粘剤3部、湿潤剤2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、攪拌したスクリーン印刷用インキを用いて、180メッシュのスクリーン版によるスクリーン印刷を行って、着色層4を形成した。次いで、前記着色層上に、湿式法により製造される微粒子状珪酸〔商品名:ニップシールE-200A、日本シリカ工業(株)製〕15部、バインダー樹脂として水性ウレタン樹脂〔商品名:ハイドランAP-10、ポリエステル系ウレタン樹脂、固形分30重量%、大日本インキ化学工業(株)製〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、エポキシ系架橋剤2部を均一に混合、攪拌した白色スクリーン印刷用インキを用いて全面ベタ印刷を施して多孔質層5を形成し、220mm×320mmの大きさからなる水変色シートを得た。
次いで、透明性基材7として厚さ1.0mm、200mm×300mmの大きさの下面の周縁部が水変色シート表面と密接し、周縁部内方は水変色シート表面と非接触状態に保持する高さ5mmの空隙部を有し、上面に四つの四角形からなる文字枠を設けた透明性硬質ABS樹脂からなる透明性カバー部材を得た。
前記水変色シートと前記透明性カバー部材とを備えた水変色体を得た。
Reference Example 1 (see Figure 5)
Preparation of Water-Discoloring Material A colored layer 4 was formed on a support 3 made of white synthetic paper by screen printing using a 180-mesh screen stencil, using a screen printing ink prepared by uniformly mixing and stirring 5 parts of blue pigment, 50 parts of acrylic ester emulsion (solid content 50% by weight), 0.2 parts of silicone-based antifoaming agent, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy-based crosslinking agent. Next, on the colored layer, 15 parts of particulate silicic acid produced by a wet method [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], 50 parts of an aqueous urethane resin as a binder resin [trade name: Hydran AP-10, polyester-based urethane resin, solid content 30 wt%, manufactured by Dainippon Ink and Chemicals, Inc.], 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of an aqueous ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred to form a porous layer 5, which was solid-printed over the entire surface using a white screen printing ink, and a water-discoloring sheet measuring 220 mm x 320 mm was obtained.
Next, a transparent cover member was obtained as a transparent substrate 7, made of a transparent hard ABS resin with a thickness of 1.0 mm and dimensions of 200 mm x 300 mm, the peripheral edge of the lower surface being in close contact with the surface of the water-discoloring sheet, and the inner peripheral edge having a 5 mm high gap that keeps it out of contact with the surface of the water-discoloring sheet, and having a letter frame consisting of four rectangles on the upper surface.
A water-coloring body comprising the water-coloring sheet and the transparent cover member was obtained.

前記水変色シートは常態では白色を呈しているが、水を収容した筆記体で多孔質層上に筆記すると青色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シートに水を収容した筆記体で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭な水変色像を維持することができた。
更に、透明性カバー部材には文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
次いで、水変色シート上から透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
The water-discoloring sheet was normally white, but when a writing tool containing water was used to write on the porous layer, blue water-discoloring images (letters) were formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a writing implement filled with water, and a transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed.
The water discoloration image could be clearly maintained through the transparent cover member.
Furthermore, since the transparent cover member is provided with a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Next, when the transparent cover member was removed from the water-discoloring sheet, the water-discoloring image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized and the sheet returned to its original state. This phenomenon could be repeated many times.

参考例2(図6参照)
水変色体の作製
白色合成紙からなる支持体3上に、青色顔料5部、アクリル酸エステルエマルジョン(固形分50重量%)50部、シリコーン系消泡剤0.2部、増粘剤3部、湿潤剤2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、攪拌したスクリーン印刷用インキを用いて、180メッシュのスクリーン版によるスクリーン印刷を行って、着色層4を形成した。次いで、前記着色層上に、湿式法により製造される微粒子状珪酸〔商品名:ニップシールE-200A、日本シリカ工業(株)製〕15部、バインダー樹脂として水性ウレタン樹脂〔商品名:ハイドランAP-10、ポリエステル系ウレタン樹脂、固形分30重量%、大日本インキ化学工業(株)製〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、エポキシ系架橋剤2部を均一に混合、攪拌した白色スクリーン印刷用インキを用いて全面ベタ印刷を施して多孔質層5を形成し、220mm×320mmの大きさからなる水変色シートを得た。
更に、透明性基材7として厚さ1.0mm、200mm×300mmの大きさの下面の周縁部が水変色シート表面と密接し、周縁部内方は水変色シート表面と非接触状態に保持する高さ10mmの空隙部を有する透明性硬質ABS樹脂からなる透明性カバー部材を得た。
更に、透明性基材71として厚さ50μm、200mm×300mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて四つの四角形からなる文字枠9を設けて透明性枠シートを得た。
前記水変色シートと前記透明性カバー部材と透明性枠シートとを備えた水変色体を得た。
Reference Example 2 (see Figure 6)
Preparation of Water-Discoloring Material A colored layer 4 was formed on a support 3 made of white synthetic paper by screen printing using a 180-mesh screen stencil, using a screen printing ink prepared by uniformly mixing and stirring 5 parts of blue pigment, 50 parts of acrylic ester emulsion (solid content 50% by weight), 0.2 parts of silicone-based antifoaming agent, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy-based crosslinking agent. Next, on the colored layer, 15 parts of particulate silicic acid produced by a wet method [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], 50 parts of an aqueous urethane resin as a binder resin [trade name: Hydran AP-10, polyester-based urethane resin, solid content 30 wt%, manufactured by Dainippon Ink and Chemicals, Inc.], 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of an aqueous ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred to form a porous layer 5, which was solid-printed over the entire surface using a white screen printing ink, and a water-discoloring sheet measuring 220 mm x 320 mm was obtained.
Furthermore, a transparent cover member was obtained as a transparent substrate 7, made of a transparent hard ABS resin with a thickness of 1.0 mm and dimensions of 200 mm x 300 mm, the peripheral edge of the underside of which is in close contact with the surface of the water-discoloring sheet, and the inner peripheral edge has a 10 mm high gap that keeps it out of contact with the surface of the water-discoloring sheet.
Furthermore, a transparent base material 71 was prepared by forming a character frame 9 consisting of four rectangles on the underside of a flexible polyester transparent sheet having a thickness of 50 μm and a size of 200 mm x 300 mm using black printing ink, thereby obtaining a transparent frame sheet.
A water-coloring body comprising the water-coloring sheet, the transparent cover member, and the transparent frame sheet was obtained.

前記水変色シートは常態では白色を呈しているが、水を収容した筆記体で多孔質層上に筆記すると青色の水変色像(数字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シートに水を収容した筆記体で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭な水変色像を維持することができた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
The water-discoloring sheet was normally white, but when a writing tool containing water was used to write on the porous layer, blue water-discoloring images (numbers) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a writing implement filled with water, and a transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed.
The water discoloration image could be clearly maintained through the transparent cover member.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Next, when the transparent frame sheet and transparent cover member were removed from the water-discoloring sheet, the water-discoloring image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized and returned to its original state. This phenomenon could be repeated many times.

実施例14
水変色体セットの作製(図7参照)
実施例1の水変色体1と、水付着具11(水を収容した筆記体)とを組み合わせて水変色体セット12を得た。
前記水変色体セットは、水付着具を用いて水変色シートに水変色像を形成することができ、実施例1と同様に透明性カバー部材を載置することにより水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を長時間維持することができた。
更に、透明性カバー部材には文字の文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
また、実施例2乃至11の各水変色体と、水付着具(水を収容した筆記体)とをそれぞれ組み合わせて水変色体セットを得た。
前記水変色体セットは、水付着具を用いて水変色シートに水変色像を形成することができ、実施例2乃至11と同様に透明性カバー部材を載置することにより水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を長時間維持することができた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
また、実施例12の水変色体と、水付着具(水を収容した筆記体)とをそれぞれ組み合わせて水変色体セットを得た。
前記水変色体セットは、水付着具を用いて水変色シートに水変色像を形成することができ、実施例12と同様に透明性カバー部材を載置することにより水変色像は透明性カバー部材を介して明瞭に視認することができ、空隙部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を長時間維持することができた。
更に、透明性カバー部材には文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
また、実施例13の水変色体と、水付着具(水を収容した筆記体)とをそれぞれ組み合わせて水変色体セットを得た。
前記水変色体セットは、水付着具を用いて水変色シートに水変色像を形成することができ、実施例13と同様に透明性カバー部材を載置することにより水変色像は透明性カバー部材を介して明瞭に視認することができ、空隙部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を長時間維持することができた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
Example 14
Preparation of a hydrochromic body set (see Figure 7)
A water-coloring object set 12 was obtained by combining the water-coloring object 1 of Example 1 with a water-adhering tool 11 (a writing element containing water).
The water-discoloring body set can form a water-discoloring image on the water-discoloring sheet using a water-adhering tool, and by placing a transparent cover member on it as in Example 1, the water-discoloring image can be clearly seen through the transparent cover member, and the convex portion prevents the transparent cover member from coming into contact with the water-discoloring image, allowing the clear water-discoloring image to be maintained for a long time.
Furthermore, since the transparent cover member is provided with a frame for the letters, it is possible to visually confirm whether the water-discolored image is properly formed within the frame, and to confirm whether the water-discolored image is well-balanced.
Furthermore, each of the water-coloring products of Examples 2 to 11 was combined with a water-adhering tool (a writing tool containing water) to obtain a water-coloring product set.
The water-discoloring body set can be used to form a water-discoloring image on the water-discoloring sheet using a water-adhering tool, and by placing a transparent cover member on it as in Examples 2 to 11, the water-discoloring image can be clearly seen through the transparent cover member, and the convex portion prevents the transparent cover member from coming into contact with the water-discoloring image, allowing the clear water-discoloring image to be maintained for a long time.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
In addition, the water-coloring product of Example 12 was combined with a water-adhering tool (a writing tool containing water) to obtain a water-coloring product set.
The water-discoloring body set can be used to form a water-discoloring image on the water-discoloring sheet using a water-adhering tool, and by placing a transparent cover member on it as in Example 12, the water-discoloring image can be clearly seen through the transparent cover member, and the gap prevents the transparent cover member from coming into contact with the water-discoloring image, allowing the clear water-discoloring image to be maintained for a long time.
Furthermore, since the transparent cover member is provided with a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
In addition, the water-coloring product of Example 13 was combined with a water-adhering tool (a writing tool containing water) to obtain a water-coloring product set.
The water-discoloring body set can be used to form a water-discoloring image on the water-discoloring sheet using a water-adhering tool, and by placing a transparent cover member on it as in Example 13, the water-discoloring image can be clearly seen through the transparent cover member, and the gap prevents the transparent cover member from coming into contact with the water-discoloring image, allowing the clear water-discoloring image to be maintained for a long time.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.

実施例15
水変色体の作製
白色合成紙からなる支持体上に、青色顔料5部、アクリル酸エステルエマルジョン(固形分50重量%)50部、シリコーン系消泡剤0.2部、増粘剤3部、湿潤剤2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、攪拌したスクリーン印刷用インキを用いて、180メッシュのスクリーン版によるスクリーン印刷を行って、着色層を形成した。次いで、前記着色層上に、湿式法により製造される微粒子状珪酸〔商品名:ニップシールE-200A、日本シリカ工業(株)製〕15部、バインダー樹脂として水性ウレタン樹脂〔商品名:ハイドランAP-10、ポリエステル系ウレタン樹脂、固形分30重量%、大日本インキ化学工業(株)製〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、エポキシ系架橋剤2部を均一に混合、攪拌した白色スクリーン印刷用インキを用いて全面ベタ印刷を施して多孔質層を形成し、220mm×320mmの大きさからなる水変色シートを得た。
次いで、透明性基材として厚さ1.0mm、200mm×300mmの大きさの上面が微細な凹凸を有して非光沢性を有する透明性硬質アクリロニトリル樹脂からなる板状成型物の下面に直径10mm、高さ1.0mmの先端が曲面の円錐形状の透明ABS樹脂からなる凸部を二等辺三角形の頂点に相当する位置に3箇所設け、板状成型物の上面に黒色の印刷インキを用いて四つの四角形からなる文字枠を設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は78.5mmであり、凸部の高さ(h)は1.0mmであり、凸部の表面積(s)/凸部の高さ(h)は78.5であった。
また、前記透明性カバー部材上面の表面積は600cmであり、透明性カバー部材の上面から視認される凸部の占有面積は2.36cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は0.39%であった。
前記水変色シートと前記透明性カバー部材とを備えた水変色体を得た。
Example 15
Preparation of Water-Discoloring Material A colored layer was formed on a support made of white synthetic paper by screen printing using a 180-mesh screen stencil, using a screen printing ink prepared by uniformly mixing and stirring 5 parts of blue pigment, 50 parts of acrylic ester emulsion (solid content 50% by weight), 0.2 parts of silicone-based antifoaming agent, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy-based crosslinking agent. Next, on the colored layer, 15 parts of particulate silicic acid produced by a wet method [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], 50 parts of an aqueous urethane resin as a binder resin [trade name: Hydran AP-10, polyester-based urethane resin, solid content 30% by weight, manufactured by Dainippon Ink and Chemicals, Inc.], 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of an aqueous ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred to form a white screen printing ink, which was then solid printed over the entire surface to form a porous layer, and a water-discoloring sheet measuring 220 mm x 320 mm was obtained.
Next, a transparent substrate was prepared by forming three convex portions made of transparent ABS resin with a diameter of 10 mm and a height of 1.0 mm at positions corresponding to the vertices of an isosceles triangle on the underside of a plate-shaped molded article made of transparent rigid acrylonitrile resin, the upper surface of which had a thickness of 1.0 mm and dimensions of 200 mm x 300 mm and had fine irregularities and was non-glossy. Four rectangular letter frames were then formed on the upper surface of the plate-shaped molded article using black printing ink to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 78.5 mm2 , the height (h) of the convex portion was 1.0 mm, and the surface area (s) of the convex portion/height (h) of the convex portion was 78.5.
Furthermore, the surface area of the upper surface of the transparent cover member was 600 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 2.36 cm2 , and the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 0.39%.
A water-coloring body comprising the water-coloring sheet and the transparent cover member was obtained.

前記水変色シートは常態では白色を呈しているが、水を収容した筆記体で多孔質層上に筆記すると青色の水変色像を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シートに水を収容した筆記体で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材表面で光が反射して視認性を妨げることなく、透明性カバー部材を介していっそう明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
更に、室内で透明カバー部材を載置した状態で写真撮影を行なったところ、照明器具の移り込みは無く、明瞭な水変色像を撮影することができた。
更に、透明性カバー部材には文字の文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
次いで、水変色シート上から透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
更に、前記水変色体と消去性筆記具(ホワイトボード用マーカー)をセットにすることにより、前記透明性カバー部材表面にホワイトボード用マーカーを用いて筆記して水変色像の未習熟な箇所を指摘し、採点することができた。また、乾燥した布やホワイトボード用イレイザーで透明カバー部材の表面を擦ることでマーカーの筆跡を簡易に除去することができた。
The water-discoloring sheet was normally white, but when a writing tool containing water was used to write on the porous layer, a blue water-discoloring image was formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discolored image was formed on the water-discolored sheet by writing with a writing pen containing water, and the transparent cover member was placed on the water-discolored sheet on which the water-discolored image had been formed so that the tips of the convex portions were in contact with the surface of the water-discolored sheet.
The water-discolored image could be seen more clearly through the transparent cover member without light being reflected on the surface of the transparent cover member to hinder visibility, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, allowing the clear water-discolored image to be maintained.
Furthermore, when a photograph was taken indoors with the transparent cover member in place, the lighting fixture was not reflected in the photograph, and a clear image of the discolored water was captured.
Furthermore, since the transparent cover member is provided with a frame for the letters, it is possible to visually confirm whether the water-discolored image is properly formed within the frame, and to confirm whether the water-discolored image is well-balanced.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Next, when the transparent cover member was removed from the water-discoloring sheet, the water-discoloring image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized and the sheet returned to its original state. This phenomenon could be repeated many times.
Furthermore, by combining the water-discoloring body with an erasable writing implement (whiteboard marker), it was possible to write on the surface of the transparent cover member with the whiteboard marker to point out and grade the unskilled areas of the water-discoloring image. Also, the marker marks could be easily removed by rubbing the surface of the transparent cover member with a dry cloth or whiteboard eraser.

実施例16
水変色体の作製
白色合成紙からなる支持体上に、青色顔料5部、アクリル酸エステルエマルジョン(固形分50重量%)50部、シリコーン系消泡剤0.2部、増粘剤3部、湿潤剤2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、攪拌したスクリーン印刷用インキを用いて、180メッシュのスクリーン版によるスクリーン印刷を行って、着色層を形成した。次いで、前記着色層上に、湿式法により製造される微粒子状珪酸〔商品名:ニップシールE-200A、日本シリカ工業(株)製〕15部、バインダー樹脂として水性ウレタン樹脂〔商品名:ハイドランAP-10、ポリエステル系ウレタン樹脂、固形分30重量%、大日本インキ化学工業(株)製〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、エポキシ系架橋剤2部を均一に混合、攪拌した白色スクリーン印刷用インキを用いて全面ベタ印刷を施して多孔質層を形成し、220mm×320mmの大きさからなる水変色シート(3枚)を得た。
次いで、透明性基材として厚さ1.0mm、200mm×300mmの大きさの透明性硬質ABS樹脂からなる板状成型物の下面に直径10mm、高さ1.0mmの先端が曲面の円錐形状の透明ABS樹脂からなる凸部を二等辺三角形の頂点に相当する位置に3箇所設け、板状成型物の上面に黒色の印刷インキを用いて四つの四角形からなる文字枠を設けて透明性カバー部材(2枚)を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は78.5mmであり、凸部の高さ(h)は1.0mmであり、凸部の表面積(s)/凸部の高さ(h)は78.5であった。
また、前記透明性カバー部材上面の表面積は600cmであり、透明性カバー部材の上面から視認される凸部の占有面積は2.36cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は0.39%であった。
前記水変色シート(3枚)と前記透明性カバー部材(2枚)とを備えた水変色体を得た。
Example 16
Preparation of Water-Discoloring Material A colored layer was formed on a support made of white synthetic paper by screen printing using a 180-mesh screen stencil, using a screen printing ink prepared by uniformly mixing and stirring 5 parts of blue pigment, 50 parts of acrylic ester emulsion (solid content 50% by weight), 0.2 parts of silicone-based antifoaming agent, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy-based crosslinking agent. Next, on the colored layer, 15 parts of particulate silicic acid produced by a wet method [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], 50 parts of an aqueous urethane resin as a binder resin [trade name: Hydran AP-10, polyester-based urethane resin, solid content 30 wt%, manufactured by Dainippon Ink and Chemicals, Inc.], 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of an aqueous ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred to form a white screen printing ink, which was then solid printed over the entire surface to form a porous layer, and three water-discoloring sheets each measuring 220 mm x 320 mm were obtained.
Next, a plate-shaped molded article made of transparent hard ABS resin with a thickness of 1.0 mm and dimensions of 200 mm x 300 mm was used as the transparent substrate. On the underside of the molded article, three convex portions made of transparent ABS resin with a diameter of 10 mm and a height of 1.0 mm and a curved tip were provided at positions corresponding to the vertices of an isosceles triangle. On the upper surface of the molded article, four rectangular letter frames were provided using black printing ink to obtain transparent cover members (2 sheets).
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 78.5 mm2 , the height (h) of the convex portion was 1.0 mm, and the surface area (s) of the convex portion/height (h) of the convex portion was 78.5.
Furthermore, the surface area of the upper surface of the transparent cover member was 600 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 2.36 cm2 , and the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 0.39%.
A water-coloring body comprising the water-coloring sheets (3 sheets) and the transparent cover members (2 sheets) was obtained.

前記水変色シートは常態では白色を呈しているが、水を収容した筆記体で多孔質層上に筆記すると青色の水変色像を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シートに水を収容した筆記体で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
更に、透明性カバー部材には文字の文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
次いで、水変色シート上から透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して元の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
また、水変色シート上から透明性カバー部材を取り除いた後、完全消色して元の水変色シートに戻る前に別の水変色シートに水変色像を形成して透明性カバー部材を載置することにより、迅速に像の形成を行うことができた。
The water-discoloring sheet was normally white, but when a writing tool containing water was used to write on the porous layer, a blue water-discoloring image was formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discolored image was formed on the water-discolored sheet by writing with a writing pen containing water, and the transparent cover member was placed on the water-discolored sheet on which the water-discolored image had been formed so that the tips of the convex portions were in contact with the surface of the water-discolored sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, since the transparent cover member is provided with a frame for the letters, it is possible to visually confirm whether the water-discolored image is properly formed within the frame, and to confirm whether the water-discolored image is well-balanced.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Next, when the transparent cover member was removed from the water-discoloring sheet, the water-discoloring image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized and the sheet returned to its original state. This phenomenon could be repeated many times.
Furthermore, after removing the transparent cover member from the water-discoloring sheet, a water-discoloring image was formed on another water-discoloring sheet and the transparent cover member was placed on it before the sheet completely faded and returned to its original state, thereby enabling rapid image formation.

実施例17
水変色体の作製
白色合成紙上にポリエステル製不織布を設けた支持体上に、黒色顔料5部、アクリル酸エステルエマルジョン(固形分50重量%)50部、シリコーン系消泡剤0.2部、増粘剤3部、湿潤剤2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、攪拌したスクリーン印刷用インキを用いて、180メッシュのスクリーン版によるスクリーン印刷を行って、着色層を形成した。次いで、前記着色層上に、湿式法により製造される微粒子状珪酸〔商品名:ニップシールE-200A、日本シリカ工業(株)製〕15部、バインダー樹脂として水性ウレタン樹脂〔商品名:ハイドランAP-10、ポリエステル系ウレタン樹脂、固形分30重量%、大日本インキ化学工業(株)製〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、エポキシ系架橋剤2部を均一に混合、攪拌した白色スクリーン印刷用インキを用いて全面ベタ印刷を施して多孔質層を形成し、280mm×380mmの大きさからなる水変色シートを得た。
次いで、透明性基材として厚さ50μm、253mm×353mmの大きさの可撓性を有するポリエステル製透明シートの下面に直径3mm、高さ1.2mmの先端が曲面の半球形状の白色ポリウレタン樹脂からなる凸部を47mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は7.07mmであり、凸部の高さ(h)は1.2mmであり、凸部の表面積(s)/凸部の高さ(h)は5.89であった。
また、前記透明性カバー部材上面の表面積は893.09cmであり、透明性カバー部材の上面から視認される凸部の占有面積は3.39cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は0.38%であり、100cmあたりの凸部の数は、5.37個であった。
更に、透明性基材として厚さ50μm、233mm×333mmの大きさの上面が微細な凹凸を有して非光沢性を有すると共に可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シートを得た。
前記水変色シートと前記透明性カバー部材と透明性枠シートとを備えた水変色体を得た。
Example 17
Preparation of Water-Discoloring Material A colored layer was formed on a support consisting of white synthetic paper with a polyester nonwoven fabric provided thereon by screen printing using a 180-mesh screen stencil, using a screen printing ink prepared by uniformly mixing and stirring 5 parts of black pigment, 50 parts of acrylic ester emulsion (solid content 50% by weight), 0.2 parts of silicone-based antifoaming agent, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy-based crosslinking agent. Next, on the colored layer, 15 parts of particulate silicic acid produced by a wet method [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], 50 parts of an aqueous urethane resin as a binder resin [trade name: Hydran AP-10, polyester-based urethane resin, solid content 30% by weight, manufactured by Dainippon Ink and Chemicals, Inc.], 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of an aqueous ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred to form a white screen printing ink, which was then solid-printed over the entire surface to form a porous layer, and a water-discoloring sheet measuring 280 mm x 380 mm was obtained.
Next, a transparent polyester transparent sheet having a thickness of 50 μm and dimensions of 253 mm x 353 mm was used as a transparent substrate, and 48 convex portions made of white polyurethane resin, each 3 mm in diameter and 1.2 mm in height, and having a curved hemispherical tip, were arranged in a checkerboard pattern at equal intervals of 47 mm to obtain a transparent cover member.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 7.07 mm2 , the height (h) of the convex portion was 1.2 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 5.89.
Furthermore, the surface area of the upper surface of the transparent cover member was 893.09 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 3.39 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 0.38%, and the number of convex portions per 100 cm2 was 5.37.
Furthermore, a transparent substrate was prepared by forming a letter frame consisting of six rectangles on the underside of a polyester transparent sheet having a thickness of 50 μm, a size of 233 mm x 333 mm, and a top surface with fine irregularities, making it non-glossy and flexible, using black printing ink, to obtain a transparent frame sheet.
A water-coloring body comprising the water-coloring sheet, the transparent cover member, and the transparent frame sheet was obtained.

前記水変色シートは常態では白色を呈しているが、筆穂に水を含侵させた毛筆で多孔質層上に筆記すると黒色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、前記水変色像は透明性枠シート表面で光が反射して視認性を妨げることなく、透明性枠シートを介していっそう明瞭に視認することができると共に、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
更に、室内で透明性枠シートを載置した状態で写真撮影を行なったところ、照明器具の移り込みは無く、明瞭な水変色像を撮影することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
なお、前記透明性カバー部材と透明性枠シートは可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush whose tip was impregnated with water, black water-discolored images (letters) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, the water-discolored image can be seen more clearly through the transparent frame sheet without light being reflected on the surface of the transparent frame sheet, which would hinder visibility.In addition, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image has been properly formed within the character frame, and to confirm whether the water-discolored image has been formed in a well-balanced manner.
Furthermore, when a photograph was taken indoors with a transparent frame sheet placed on top, no light fixtures were reflected in the photograph, and a clear image of the discolored water could be captured.
Next, when the transparent frame sheet and transparent cover member were removed from the water-discolored sheet, the water-discolored image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized, returning to a completely white water-discolored sheet. This phenomenon could be repeated many times.
Furthermore, since the transparent cover member and the transparent frame sheet are flexible, the water-discoloring body can be rolled up and carried around, and is therefore highly portable.

実施例18
水変色体の作製
白色合成紙上にポリエステル製不織布を設けた支持体上に、黒色顔料5部、アクリル酸エステルエマルジョン(固形分50重量%)50部、シリコーン系消泡剤0.2部、増粘剤3部、湿潤剤2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、攪拌したスクリーン印刷用インキを用いて、180メッシュのスクリーン版によるスクリーン印刷を行って、着色層を形成した。次いで、前記着色層上に、湿式法により製造される微粒子状珪酸〔商品名:ニップシールE-200A、日本シリカ工業(株)製〕15部、バインダー樹脂として水性ウレタン樹脂〔商品名:ハイドランAP-10、ポリエステル系ウレタン樹脂、固形分30重量%、大日本インキ化学工業(株)製〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、エポキシ系架橋剤2部を均一に混合、攪拌した白色スクリーン印刷用インキを用いて全面ベタ印刷を施して多孔質層を形成し、280mm×380mmの大きさからなる水変色シート(3枚)を得た。
次いで、透明性基材として厚さ50μm、253mm×353mmの大きさの可撓性を有するポリエステル製透明シートの下面に直径3mm、高さ1.2mmの先端が曲面の半球形状の白色ポリウレタン樹脂からなる凸部を47mmの等間隔で碁盤目状に48箇所設けて透明性カバー部材(2枚)を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は7.07mmであり、凸部の高さ(h)は1.2mmであり、凸部の表面積(s)/凸部の高さ(h)は5.89であった。
また、前記透明性カバー部材上面の表面積は893.09cmであり、透明性カバー部材の上面から視認される凸部の占有面積は3.39cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は0.38%であり、100cmあたりの凸部の数は、5.37個であった。
更に、透明性基材として厚さ50μm、233mm×333mmの大きさの可撓性を有するポリエステル製透明シートの下面に黒色の印刷インキを用いて六つの四角形からなる文字枠を設けて透明性枠シート(2枚)を得た。
前記水変色シート(3枚)と前記透明性カバー部材(2枚)と透明性枠シート(2枚)とを備えた水変色体を得た。
Example 18
Preparation of Water-Discoloring Material A colored layer was formed on a support consisting of white synthetic paper with a polyester nonwoven fabric provided thereon by screen printing using a 180-mesh screen stencil, using a screen printing ink prepared by uniformly mixing and stirring 5 parts of black pigment, 50 parts of acrylic ester emulsion (solid content 50% by weight), 0.2 parts of silicone-based antifoaming agent, 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, and 2.5 parts of epoxy-based crosslinking agent. Next, on the colored layer, 15 parts of particulate silicic acid produced by a wet method [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], 50 parts of an aqueous urethane resin as a binder resin [trade name: Hydran AP-10, polyester-based urethane resin, solid content 30 wt%, manufactured by Dainippon Ink and Chemicals, Inc.], 30 parts of water, 0.5 parts of a silicone-based antifoaming agent, 3 parts of an aqueous ink thickener, 1 part of ethylene glycol, and 2 parts of an epoxy-based crosslinking agent were uniformly mixed and stirred to form a white screen printing ink, which was then solid printed over the entire surface to form a porous layer, and three water-discoloring sheets measuring 280 mm x 380 mm were obtained.
Next, 48 convex portions made of white polyurethane resin, each 3 mm in diameter and 1.2 mm in height and with a curved hemispherical tip, were arranged in a checkerboard pattern at equal intervals of 47 mm on the underside of a flexible polyester transparent sheet 50 μm thick and 253 mm x 353 mm in size as a transparent substrate, to obtain transparent cover members (2 sheets).
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 7.07 mm2 , the height (h) of the convex portion was 1.2 mm, and the ratio of the surface area (s) of the convex portion to the height (h) of the convex portion was 5.89.
Furthermore, the surface area of the upper surface of the transparent cover member was 893.09 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 3.39 cm2 , the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 0.38%, and the number of convex portions per 100 cm2 was 5.37.
Furthermore, a flexible polyester transparent sheet having a thickness of 50 μm and dimensions of 233 mm x 333 mm was used as a transparent substrate, and six rectangular letter frames were printed on the underside of the sheet using black printing ink to obtain two transparent frame sheets.
A water-coloring body was obtained comprising the water-coloring sheets (3 sheets), the transparent cover members (2 sheets), and the transparent frame sheets (2 sheets).

前記水変色シートは常態では白色を呈しているが、筆穂に水を含侵させた毛筆で多孔質層上に筆記すると黒色の水変色像(文字)を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シート上に筆穂に水を浸した毛筆で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して明瞭に視認することができ、凸部によって透明性カバー部材が水変色像と接触することなく、明瞭な水変色像を維持することができた。
また、前記水変色像は、25℃、65%RHの環境下で30分間放置しても筆記直後の水変色像と同じ形状を維持していた。
更に、透明性枠シートを透明性カバー部材上に載置すると、透明性枠シートには文字枠を設けているため、水変色像が文字枠内に適正に形成されたか視認することができ、水変色像のバランスを良く形成されたかどうか確認することができた。
次いで、水変色シート上から透明性枠シートと透明性カバー部材を取り除くと前記水変色像は水分の蒸発にともない徐々に消失し、10分間経過した段階では完全消色して全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
なお、前記透明性カバー部材と透明性枠シートは可撓性を有するため、水変色体を丸めて持ち運びすることができ、携帯性に優れていた。
また、水変色シート上から透明性カバー部材と透明性枠シートを取り除いた後、完全消色して元の水変色シートに戻る前に別の水変色シートに水変色像を形成して透明性カバー部材と透明性枠シートを載置することにより、迅速に像の形成を行うことができた。
The water-discolored sheet was normally white, but when writing was done on the porous layer with a writing brush whose tip was impregnated with water, black water-discolored images (letters) could be formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discoloring image was formed on the water-discoloring sheet by writing with a brush whose tip was dipped in water, and the transparent cover member was placed on the water-discoloring sheet on which the water-discoloring image had been formed so that the tip of the convex portion was in contact with the surface of the water-discoloring sheet.
The water-discolored image was clearly visible through the transparent cover member, and the convex portions prevented the transparent cover member from coming into contact with the water-discolored image, thereby enabling the water-discolored image to be maintained clearly.
Furthermore, the water discoloration image maintained the same shape as the water discoloration image immediately after writing even after being left to stand for 30 minutes in an environment of 25° C. and 65% RH.
Furthermore, when the transparent frame sheet is placed on the transparent cover member, since the transparent frame sheet has a character frame, it is possible to visually confirm whether the water-discolored image is properly formed within the character frame, and to confirm whether the water-discolored image is well-balanced.
Next, when the transparent frame sheet and transparent cover member were removed from the water-discolored sheet, the water-discolored image gradually disappeared as the water evaporated, and after 10 minutes the image was completely decolorized, returning to a completely white water-discolored sheet. This phenomenon could be repeated many times.
Furthermore, since the transparent cover member and the transparent frame sheet are flexible, the water-discoloring body can be rolled up and carried around, and is therefore highly portable.
Furthermore, after removing the transparent cover member and transparent frame sheet from the water-discoloring sheet, a water-discoloring image was formed on another water-discoloring sheet and the transparent cover member and transparent frame sheet were placed on top before the sheet completely faded and returned to its original state, allowing for rapid image formation.

比較例1
水変色体の作製
実施例1と同様にして水変色シートを得た。
次いで、透明性基材として厚さ1.0mm、200mm×300mmの大きさの透明性硬質ABS樹脂からなる板状成型物の下面に直径10mm、高さ1.0mmの先端が曲面の円錐形状の透明ABS樹脂からなる凸部を板状成型物に2箇所設けて透明性カバー部材を得た。
前記透明性カバー部材の上面から視認される凸部の表面積(s)は78.5mmであり、凸部の高さ(h)は1.0mmであり、凸部の表面積(s)/凸部の高さ(h)は78.5であった。
また、前記透明性カバー部材上面の表面積は600cmであり、透明性カバー部材の上面から視認される凸部の占有面積は2.36cmであり、透明性カバー部材上面の表面積に対する透明性カバー部材の上面から視認される凸部の占有面積比率は0.39%であった。
前記水変色シートと前記透明性カバー部材とを備えた水変色体を得た。
Comparative Example 1
Preparation of Water-Colored Material A water -colored sheet was obtained in the same manner as in Example 1.
Next, a transparent cover member was obtained by providing two conical convex portions made of transparent ABS resin with a diameter of 10 mm and a height of 1.0 mm and a curved tip on the underside of a plate-shaped molded product made of transparent hard ABS resin with a thickness of 1.0 mm and a size of 200 mm x 300 mm as a transparent substrate.
The surface area (s) of the convex portion visible from the top surface of the transparent cover member was 78.5 mm2 , the height (h) of the convex portion was 1.0 mm, and the surface area (s) of the convex portion/height (h) of the convex portion was 78.5.
Furthermore, the surface area of the upper surface of the transparent cover member was 600 cm2 , the area occupied by the convex portions visible from the upper surface of the transparent cover member was 2.36 cm2 , and the ratio of the area occupied by the convex portions visible from the upper surface of the transparent cover member to the surface area of the upper surface of the transparent cover member was 0.39%.
A water-coloring body comprising the water-coloring sheet and the transparent cover member was obtained.

前記水変色シートは常態では白色を呈しているが、水を収容した筆記体で多孔質層上に筆記すると青色の水変色像を形成できた。
前記水変色像は、25℃、65%RHの環境下では、5分間像を維持していたが、水分の蒸発にともない徐々に消失し、10分間経過した段階では全面白色の水変色シートに戻った。この現象は繰り返し何度も行うことができた。
次いで、前記水変色シートに水を収容した筆記体で筆記して水変色像を形成し、前記水変色像が形成された水変色シート上に凸部先端が水変色シート表面に接触するように前記透明性カバー部材を載置した。
前記水変色像は透明性カバー部材を介して視認することはできたが、透明性カバー部材と水変色像が接触する箇所が発生し、水変色像に滲みを生じた。
また、前記水変色像は、25℃、65%RHの環境下で放置すると透明カバー部材と水変色像との距離に差異が生じるため、水変色像の消色時間にも差異が生じて均一な水変色像を維持することはできなかった。
The water-discoloring sheet was normally white, but when a writing tool containing water was used to write on the porous layer, a blue water-discoloring image was formed.
The water-discolored image was maintained for 5 minutes in an environment of 25°C and 65% RH, but gradually disappeared as the water evaporated, and after 10 minutes the entire sheet returned to a white water-discolored sheet. This phenomenon could be repeated many times.
Next, a water-discolored image was formed on the water-discolored sheet by writing with a writing pen containing water, and the transparent cover member was placed on the water-discolored sheet on which the water-discolored image had been formed so that the tips of the convex portions were in contact with the surface of the water-discolored sheet.
The water-discolored image could be seen through the transparent cover member, but there were some areas where the transparent cover member and the water-discolored image came into contact with each other, causing bleeding of the water-discolored image.
Furthermore, when the water-discolored image is left in an environment of 25°C and 65% RH, differences arise in the distance between the transparent cover member and the water-discolored image, which results in differences in the time it takes for the water-discolored image to fade, making it impossible to maintain a uniform water-discolored image.

1 水変色体
2 水変色シート
3 支持体
4 着色層
5 多孔質層
6 透明性カバー部材
7,71 透明性基材
8 凸部
9 文字枠
10 透明性枠シート
11 空隙部
12 水付着具
13 水変色体セット
DESCRIPTION OF SYMBOLS 1 Water-color changing body 2 Water-color changing sheet 3 Support 4 Colored layer 5 Porous layer 6 Transparent cover member 7, 71 Transparent substrate 8 Convex portion 9 Letter frame 10 Transparent frame sheet 11 Void portion 12 Water-adhering tool 13 Water-color changing body set

Claims (11)

低屈折率顔料をバインダー樹脂に分散状態に固着させた多孔質層を着色層の上層に備えた水変色シートと、前記多孔質層の表面に水の付着により形成される水変色像を覆い、水の乾燥を抑制して、水変色像の消失を遅延させる透明性カバー部材とを備えてなり、前記透明性カバー部材の下面には水変色シート表面と透明性カバー部材を非接触状態に保持し、水変色シート表面と接する点状の凸部を少なくとも三か所以上非直線状に配置してなり、前記凸部は0.4mm~12.0mmの高さを有し、前記透明性カバー部材上面から視認される凸部の表面積(s)と、凸部の高さ(h)が下記式(1)を満たし、前記透明性カバー部材上面の表面積に対して、透明性カバー部材上面から視認される凸部の占有面積が10%以下であり、前記透明性カバー部材には水変色シートに形成する文字の文字枠を設けてなる水変色体。
1.0≦s/h≦400 (1)
The water-discoloring sheet comprises a porous layer, formed on an upper layer of a colored layer, in which a low-refractive index pigment is dispersed and fixed in a binder resin; and a transparent cover member that covers the water-discoloring image formed on the surface of the porous layer by the adhesion of water, thereby inhibiting the drying of the water and delaying the disappearance of the water-discoloring image. The underside of the transparent cover member has at least three or more dot-like protrusions that contact the water-discoloring sheet surface and maintain the water-discoloring sheet surface in a non-linear arrangement, and the protrusions have a height of 0.4 mm to 12.0 mm. The surface area (s) of the protrusions visible from the top surface of the transparent cover member and the height (h) of the protrusions satisfy the following formula (1): the surface area (s) of the protrusions visible from the top surface of the transparent cover member and the height (h) of the protrusions occupy 10% or less of the surface area of the top surface of the transparent cover member. The transparent cover member is provided with character frames for the characters to be formed on the water- discoloring sheet .
1.0≦s/h≦400 (1)
低屈折率顔料をバインダー樹脂に分散状態に固着させた多孔質層を着色層の上層に備えた水変色シートと、前記多孔質層の表面に水の付着により形成される水変色像を覆い、水の乾燥を抑制して、水変色像の消失を遅延させる透明性カバー部材と、前記水変色シートに形成する文字の文字枠を設けてなる透明性枠シートとからなり、前記透明性カバー部材の下面には水変色シート表面と透明性カバー部材を非接触状態に保持し、水変色シート表面と接する点状の凸部を少なくとも三か所以上非直線状に配置してなり、前記凸部は0.4mm~12.0mmの高さを有し、前記透明性カバー部材上面から視認される凸部の表面積(s)と、凸部の高さ(h)が下記式(1)を満たし、前記透明性カバー部材上面の表面積に対して、透明性カバー部材上面から視認される凸部の占有面積が10%以下である水変色体。
1.0≦s/h≦400 (1)
The water-discoloring body comprises a water-discoloring sheet provided with a porous layer on top of a colored layer, in which a low-refractive index pigment is dispersed and fixed in a binder resin; a transparent cover member that covers the water-discoloring image formed on the surface of the porous layer by the adhesion of water, thereby suppressing the drying of the water and delaying the disappearance of the water-discoloring image; and a transparent frame sheet provided with character frames for characters to be formed on the water -discoloring sheet . The underside of the transparent cover member has at least three or more dot-like protrusions that contact the surface of the water-discoloring sheet and are arranged in a non-linear manner, maintaining the surface of the water-discoloring sheet and the transparent cover member in a non-contact state. The protrusions have a height of 0.4 mm to 12.0 mm, and the surface area (s) of the protrusions as viewed from the top surface of the transparent cover member and the height (h) of the protrusions satisfy the following formula (1), and the area occupied by the protrusions as viewed from the top surface of the transparent cover member is 10% or less of the surface area of the top surface of the transparent cover member .
1.0≦s/h≦400 (1)
前記凸部は透明性を有する請求項1又は2記載の水変色体。3. The water-chromatic body according to claim 1, wherein the convex portions are transparent. 前記凸部は白色を呈する請求項1又は2記載の水変色体。3. The water-chromatic body according to claim 1, wherein the convex portions are white. 前記凸部の先端が曲面形状である請求項1乃至4のいずれか一項に記載の水変色体。The water-chromatic body according to any one of claims 1 to 4, wherein the tips of the convex portions are curved. 前記透明性カバー部材は可撓性を有し、且つ、前記凸部は100cmThe transparent cover member is flexible, and the protrusion is 100 cm 2 あたり3個以上有する請求項1乃至5のいずれか一項に記載の水変色体。The hydrochromic body according to any one of claims 1 to 5, having three or more per molecule. 前記透明性カバー部材は、一端部を水変色シートに取り付け、他端部を自由端となして、水変色シートに開閉自在に設けてなる請求項1乃至6のいずれか一項に記載の水変色体。7. The water-coloring body according to claim 1, wherein the transparent cover member has one end attached to the water-coloring sheet and the other end left as a free end, and is provided on the water-coloring sheet so as to be openable and closable. 複数の前記水変色シートと、複数の前記透明性カバー部材とからなる請求項1乃至7のいずれか一項に記載の水変色体。The water-coloring object according to any one of claims 1 to 7, comprising a plurality of the water-coloring sheets and a plurality of the transparent cover members. 複数の前記水変色シートと、複数の前記透明性カバー部材と、複数の前記透明性枠シートとからなる請求項2記載の水変色体。3. The water-coloring body according to claim 2, comprising a plurality of said water-coloring sheets, a plurality of said transparent cover members, and a plurality of said transparent frame sheets. 前記点状の凸部を碁盤目状に配置してなる請求項1又は2記載の水変色体。3. The hydrochromic material according to claim 1, wherein the dot-like protrusions are arranged in a grid pattern. 請求項1乃至10のいずれか一項に記載の水変色体と、水変色像を形成させる水付着具を備えた水変色体セット。A water-chromatic object set comprising the water-chromatic object according to any one of claims 1 to 10 and a water-attaching tool for forming a water-chromatic image.
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JP2010284250A (en) 2009-06-10 2010-12-24 Pilot Ink Co Ltd Color change table cloth and color change table cloth set using the same
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JP2022169437A (en) * 2021-04-27 2022-11-09 株式会社パイロットコーポレーション water discoloration body, water discoloration body set

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