JP4950849B2 - Water discolorable laminate - Google Patents
Water discolorable laminate Download PDFInfo
- Publication number
- JP4950849B2 JP4950849B2 JP2007292672A JP2007292672A JP4950849B2 JP 4950849 B2 JP4950849 B2 JP 4950849B2 JP 2007292672 A JP2007292672 A JP 2007292672A JP 2007292672 A JP2007292672 A JP 2007292672A JP 4950849 B2 JP4950849 B2 JP 4950849B2
- Authority
- JP
- Japan
- Prior art keywords
- protective layer
- resin
- water
- parts
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Toys (AREA)
- Laminated Bodies (AREA)
Description
本発明は水変色性積層体に関する。更に詳細には、耐久性を向上させた水変色性積層体に関する。 The present invention relates to a water discolorable laminate. More specifically, the present invention relates to a water discolorable laminate having improved durability.
従来、支持体上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、吸液状態と非吸液状態で透明性が異なる多孔質層を設けた変色性積層体に関して幾つかの提案が開示されている(例えば、特許文献1参照)。
前記積層体は、多孔質層が乾燥状態(非吸液状態)においては下層が隠蔽され、多孔質層に水を吸液させると透明化して下層の色調を視認できるものであり、意外性と変化性を有するものである。
In the laminate, the lower layer is concealed when the porous layer is in a dry state (non-absorbing state), and when the porous layer absorbs water, it becomes transparent and the color tone of the lower layer can be visually recognized. It has variability.
本発明は、前記積層体の耐擦過性、即ち、多孔質層に傷が付いたり、多孔質層の厚みが擦過により薄くなったり、或いは、剥離して変色機能が低下することなく、繰り返しの実用性を満足させた水変色性積層体を提供しようとするものである。 The present invention is not repeatedly scratched on the laminate, i.e., the porous layer is scratched, the thickness of the porous layer is reduced by rubbing, or peeling and the discoloration function is not deteriorated. It is an object of the present invention to provide a water discolorable laminate that satisfies practicality.
本発明は、支持体上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、吸液状態と非吸液状態で透明性が異なる多孔質層を設け、前記多孔質層上に多孔質粒状体又は非球形粒状体をバインダー樹脂中に分散させた保護層を設けてなり、前記保護層の厚みA(μm)と、保護層中の単位面積当りの多孔質粒状体又は非球状粒状体の質量B(g/m 2 )が下記関係式(1)及び(2)を満たす水変色性積層体を要件とする。
1+2B≦A≦3.5+2B (1)
0.5≦B≦2.5 (2)
更には、前記保護層中の粒状体のうち、有機物からなる粒状体が10〜100体積%を占めること、前記保護層が、屈折率1.45〜1.65のバインダー樹脂と、平均粒子径0.1〜10μm、且つ、屈折率1.45〜1.65の粒状体とから構成されること等を要件とする。
The present invention provides a porous layer having a low refractive index pigment fixed on a support in a dispersed state in a binder resin and having different transparency in a liquid-absorbing state and a non-liquid-absorbing state, and the porous layer is formed on the porous layer. Ri particulate material or a non-spherical granules name a protective layer dispersed in a binder resin, and the thickness a of the protective layer ([mu] m), a porous granules or non-spherical particulate per unit area in the protective layer body mass B (g / m 2) is the requirement of water discoloration laminate satisfying the following relational expression (1) and (2).
1 + 2B ≦ A ≦ 3.5 + 2B (1)
0.5 ≦ B ≦ 2.5 (2)
Furthermore, among the granules before Symbol protective layer, the granules made of organic material occupies 10 to 100% by volume, the protective layer comprises a binder resin having a refractive index 1.45 to 1.65, an average particle It is required to be composed of a granular material having a diameter of 0.1 to 10 μm and a refractive index of 1.45 to 1.65.
本発明は、多孔質層の吸液状態と非吸液状態で透明性が異なる機能を損なうことなく、耐擦過性を満足させ、水の適用による変色を永続して発現可能な実用性に富む水変色性積層体を提供することができる。 INDUSTRIAL APPLICABILITY The present invention has excellent practicality that can satisfy scratch resistance and can permanently exhibit discoloration due to the application of water without impairing the function of transparency in the liquid absorption state and non-liquid absorption state of the porous layer. A water discolorable laminate can be provided.
前記支持体は印刷適性を備えた基材であれば全て有効であり、例えば、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。又、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。 The substrate is effective if it is a substrate having printability, for example, paper, synthetic paper, woven fabric, knitted fabric, braid, non-woven fabric, natural or synthetic leather, plastic, glass, ceramics, metal Wood, stone, etc. are used. The shape is preferably a planar shape, but may be an uneven shape.
前記支持体上に設けられる多孔質層は、低屈折率顔料をバインダー樹脂と共に分散状態に固着させた層であり、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。
又、前記低屈折率顔料は2種以上を併用することもできる。
前記低屈折率顔料の粒径は特に限定されるものではないが、0.03〜10.0μmのものが好適に用いられる。
尚、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。
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、よって、常態での隠蔽性が大きくなるものと推察される。
又、前記多孔質層においては、水を吸液させるものであるから、湿式法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。
尚、前記多孔質層の常態での隠蔽性と吸液状態での透明性を調整するために、湿式法珪酸と共に、他の汎用の低屈折率顔料を併用することもできる。
The porous layer provided on the support is a layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin, and is a layer having different transparency in a dry state and a liquid absorption state.
Examples of the low refractive index pigment include silicic acid and salts thereof, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, magnesium carbonate, and the like. It is in the range of 1.8, and shows good transparency when water is absorbed.
Examples of the silicic acid salts include aluminum silicate, aluminum potassium silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, calcium sodium silicate, sodium silicate, magnesium silicate, and magnesium potassium silicate.
Two or more of the low refractive index pigments can be used in combination.
The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
In addition, silicic acid is mentioned as a low refractive index pigment used suitably.
The silicic acid may be a silicic acid produced by a dry process, but a silicic acid produced by a wet process (hereinafter referred to as a wet process silicic acid) is particularly effective. To explain this point, silicic acid is amorphous. Amorphous silicic acid produced by a dry process using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as dry process silicic acid), and sodium silicate. It is roughly divided into those using a wet method using a liquid phase reaction such as decomposition by an acid such as a dry method, and the structure of a dry method silicic acid is different from that of a wet method silicic acid. In contrast, wet-process silicic acid has a so-called two-dimensional structure part in which silicic acid is condensed to form a long molecular arrangement.
Therefore, since the molecular structure becomes rough compared to the dry method silicic acid, when wet method silicic acid is applied to the porous layer, it is excellent in the diffused reflection of light in the dry state compared to the system using the dry method silicic acid, Therefore, it is guessed that the concealment property in a normal state becomes large.
Moreover, in the porous layer, since water is absorbed, the wet process silicic acid has more hydroxyl groups present as silanol groups on the particle surface than the dry process silicic acid, and the degree of hydrophilicity is large. Preferably used.
In addition, in order to adjust the concealability in the normal state of the porous layer and the transparency in the liquid absorption state, other general-purpose low-refractive-index pigments can be used in combination with the wet method silicic acid.
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1〜30g/m2であることが好ましく、より好ましくは、5〜20g/m2である。1g/m2未満では、常態で十分な隠蔽性を得ることが困難であり、又、30g/m2を越えると吸液時に十分な透明性を得ることが困難である。
前記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、透光性支持体に塗布した後、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これらの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悪くなる。
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、2種以上を併用することもできる。又、前記樹脂が水に乳化分散したウレタン系エマルジョン樹脂や、イオン性を有するウレタン樹脂(ウレタンアイオノマー)自体のイオン基により乳化剤を必要とすることなく自己乳化して、水中に溶解乃至分散したコロイド分散型(アイオノマー型)ウレタン樹脂を用いることもできる。
尚、前記ウレタン系樹脂は水性ウレタン系樹脂又は油性ウレタン系樹脂のいずれを用いることもできるが、本発明においては水性ウレタン系樹脂、殊に、ウレタン系エマルジョン樹脂やコロイド分散型ウレタン系樹脂が好適に用いられる。
前記ウレタン系樹脂は単独で用いることもできるが、透光性支持体の種類や皮膜に必要とされる性能に応じて、他のバインダー樹脂を併用することもできる。ウレタン系樹脂以外のバインダー樹脂を併用する場合、実用的な皮膜強度を得るためには、前記多孔質層のバインダー樹脂中にウレタン系樹脂を固形分質量比率で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 low refractive index pigment in the porous layer depends on properties such as particle diameter, specific surface area, oil absorption, etc., in order to satisfy both the concealability in the normal state and the transparency in the liquid absorption state, preferably the coating amount is 1 to 30 g / m 2, more preferably 5 to 20 g / m 2. If it is less than 1 g / m 2 , it is difficult to obtain sufficient concealability in a normal state, and if it exceeds 30 g / m 2 , it is difficult to obtain sufficient transparency during liquid absorption.
The low refractive index pigment is dispersed in a vehicle containing a binder resin as a binder, applied to a translucent support, and then the volatile matter is dried to form a porous layer.
Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic resin, polyester resin, styrene. Resin, styrene copolymer resin, polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and the above Each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like can be mentioned.
The mixing ratio of the low refractive index pigment and these binder resins depends on the type and properties of the low refractive index pigment, but preferably the binder resin solid content is 0.5 to 1 part by mass with respect to 1 part by mass of the low refractive index pigment. 2 parts by mass, and more preferably 0.8 to 1.5 parts by mass. When the binder resin solid content is less than 0.5 parts by mass with respect to 1 part by mass of the low refractive index pigment, it is difficult to obtain a practical film strength of the porous layer, and the content exceeds 2 parts by mass. In this case, the water permeability into the porous layer is deteriorated.
Since the porous layer has a smaller mixing ratio of the binder resin to the colorant than a general coating film, it is difficult to obtain sufficient film strength. Therefore, in order to increase the scratch resistance, it is effective to use a nylon resin or a urethane resin among the binder resins.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid in which the resin is self-emulsified without the need for an emulsifier by an ionic group of the ionic urethane resin (urethane ionomer) itself and dissolved or dispersed in water. A dispersion type (ionomer type) urethane resin can also be used.
The urethane-based resin may be either an aqueous urethane-based resin or an oil-based urethane-based resin. Used for.
The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of translucent support and the performance required for the film. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain 30% or more of the urethane resin in a solid mass ratio in the binder resin of the porous layer.
In the binder resin, the crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking.
The binder resin has a large or small affinity with water. By combining these, the penetration time into the porous layer, the degree of penetration, and the slow speed of drying after the penetration can be adjusted. Furthermore, the said adjustment can be controlled by adding a dispersing agent and surfactant suitably.
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、浸漬塗装等により支持体上に形成できる。 The porous layer is formed by screen printing, offset printing, gravure printing, coater, tampo printing, transfer printing, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc. It can be formed on a support.
前記多孔質層上に設けられる保護層は、該層を通して多孔質層が水を吸液したり、或いは、乾燥するための水透過性を有すると共に、保護層として十分な被膜強度及び透明性が必要である。
保護層が水透過性を有するためには、該層に連通孔を備えることが必要である。
また、十分な被膜強度を有するためには、保護層を厚くすることが好ましいが、該層を厚くすると層自体の透明性が低下して多孔質層の吸液状態と非吸液状態での明瞭な色変化を視認できなくなると共に、水透過性も損ない易くなる。
これらの問題点を解消すべく、一定以上の塗膜強度と透明性を保つ範囲で保護層中に非球形粒状体又は多孔質粒状体を含有させて連通孔を形成して保護層の水透過性を向上させる。
前記要件を満たすため、保護層中の単位面積当りの多孔質粒状体又は非球状粒状体の質量B(g/m2)は範囲があり、保護層の膜厚A(μm)との間に下記関係式(1)及び(2)が成り立つ。
1+2B≦A≦3.5+2B (1)
0.5≦B≦2.5 (2)
多孔質粒状体又は非球状粒状体の質量Bが0.5g/m2未満では多孔質層への水の通過を保護層が阻害し易くなるため、変色鋭敏性が低下したり、変色し難くなる。
一方、質量Bが2.5g/m2を超えると、保護層の塗膜強度が弱くなるため、多孔質層に対する保護層としての機能に乏しくなる。
また、保護層の膜厚A(μm)が1+2B未満の場合、保護層の塗膜強度が弱くなるため、多孔質層に対する保護層としての機能に乏しくなる。
一方、保護層の膜厚A(μm)が3.5+2Bを超える場合、多孔質層への水の通過を保護層が阻害し易くなるため、変色鋭敏性が低下したり、変色し難くなる。
また、保護層を形成するバインダー樹脂と、粒状体について、屈折率1.45〜1.65のバインダー樹脂と、平均粒子径0.1〜10μm、且つ、屈折率1.45〜1.65の粒状体を用いることにより、保護層の透明性が向上し、下層に設けた多孔質層の吸液時及び非吸液時の変化を損なうことなく観察できる。
バインダー樹脂の屈折率と粒状体の屈折率が大きく異なる場合、保護層が白濁し、下層の多孔質層の吸液時及び非吸液時の色変化を視認でき難くなる。
更に、保護層中の粒状体の粒子径が大きい場合、保護層の強度が低下し、粒子径が小さい場合、保護層の水透過性を阻害し易くなる。
The protective layer provided on the porous layer has water permeability for the porous layer to absorb water or dry through the layer, and has sufficient film strength and transparency as a protective layer. is necessary.
In order for the protective layer to have water permeability, it is necessary to provide a communication hole in the layer.
Further, in order to have a sufficient film strength, it is preferable to make the protective layer thicker, but if the layer is made thicker, the transparency of the layer itself is lowered, and the porous layer is in a liquid-absorbing state and a non-liquid-absorbing state. A clear color change cannot be visually recognized, and water permeability is easily lost.
In order to solve these problems, non-spherical granular material or porous granular material is included in the protective layer within a range that maintains the coating strength and transparency above a certain level, and water permeation of the protective layer is formed. Improve sexiness.
To meet the previous SL requirements, the mass B of the porous granules or non-spherical granules per unit area in the protective layer (g / m 2) for there is a range, between the thickness A ([mu] m) of the protective layer The following relational expressions (1) and (2) hold.
1 + 2B ≦ A ≦ 3.5 + 2B (1)
0.5 ≦ B ≦ 2.5 (2)
If the mass B of the porous granule or non-spherical granule is less than 0.5 g / m 2 , the protective layer tends to inhibit the passage of water to the porous layer, so that the color change sensitivity is reduced or the color change is difficult. Become.
On the other hand, when the mass B exceeds 2.5 g / m 2 , the coating layer strength of the protective layer becomes weak, so that the function as a protective layer for the porous layer becomes poor.
Moreover, since the coating film strength of a protective layer becomes weak when the film thickness A (micrometer) of a protective layer is less than 1 + 2B, it becomes poor in the function as a protective layer with respect to a porous layer.
On the other hand, when the thickness A (μm) of the protective layer exceeds 3.5 + 2B, the protective layer easily inhibits the passage of water into the porous layer, so that the color change sensitivity is reduced or the color change is difficult.
Moreover, about binder resin which forms a protective layer, and a granular material, binder resin with a refractive index of 1.45 to 1.65, an average particle diameter of 0.1 to 10 μm, and a refractive index of 1.45 to 1.65 By using the granular material, the transparency of the protective layer is improved, and the porous layer provided in the lower layer can be observed without impairing the change in liquid absorption and non-liquid absorption.
When the refractive index of the binder resin and the refractive index of the granular material are greatly different, the protective layer becomes cloudy, and it becomes difficult to visually recognize the color change when the lower porous layer absorbs liquid and when it does not absorb liquid.
Furthermore, when the particle size of the granular material in the protective layer is large, the strength of the protective layer is reduced, and when the particle size is small, the water permeability of the protective layer is easily inhibited.
前記非球形粒状体又は多孔質粒状体としては、偏平状粒状体やラズベリー状粒状体等の非球形粒状体、中空粒子等の多孔質粒状体が挙げられる。
なお、偏平状粒状体は球状粒子を押しつぶして偏平にした粒状体であってもよい。
前記偏平状粒状体は、円形や楕円形等の円板形状、中央部に貫通孔を有するドーナツ形状、一方の面の中央部が陥没した形状の合成樹脂製粒状体が挙げられる。
前記粒状体としては、三井化学(株)製、商品名:ミューティクルPP240D(スチレン樹脂、粒子径0.5μm、屈折率1.6)、ミューティクルPP2000TX(スチレンアクリル樹脂、粒子径0.5μm、屈折率1.6)を例示できる。
前記ラズベリー状粒状体としては、日本ゼオン(株)製、商品名:LX407BP(スチレンブタジエン樹脂、粒子径0.4μm、屈折率1.5)を例示できる。
前記中空粒子は、内部に空隙を有する粒子であり外壁に多孔性を備える。
形状は球状の他、偏平状であってもよい。
前記中空粒子としては、日本ゼオン(株)製、商品名:ローペイクHP−1055(スチレンアクリル樹脂、粒子径1μm、屈折率1.5)、ローペイクHP−91(スチレンアクリル樹脂、粒子径1μm、屈折率1.5)、ローペイクOP−84J(スチレンアクリル樹脂、粒子径0.6μm、屈折率1.5)、ローペイクHP−433J(スチレンアクリル樹脂、粒子径0.4μm、屈折率1.5)、
NIPOL MH5055(スチレンアクリル樹脂、粒子径0.5μm、屈折率1.5)、
JSR(株)製、商品名:SX866(スチレンアクリル樹脂、粒子径0.3μm、屈折率1.5)、SX8782(スチレンアクリル樹脂、粒子径1μm、屈折率1.5)を
例示できる。
Examples of the non-spherical granular material or porous granular material include non-spherical granular materials such as flat granular materials and raspberry granular materials, and porous granular materials such as hollow particles.
The flat granular material may be a granular material obtained by squashing spherical particles.
Examples of the flat granule include a disc shape such as a circle and an ellipse, a donut shape having a through hole in the center, and a synthetic resin granule having a shape in which the center of one surface is depressed.
As the granular material, Mitsui Chemicals, trade name: Muticle PP240D (styrene resin, particle diameter 0.5 μm, refractive index 1.6), Muticle PP2000TX (styrene acrylic resin, particle diameter 0.5 μm, A refractive index of 1.6) can be exemplified.
As the raspberry-like granular material, Nippon Zeon Co., Ltd., trade name: LX407BP (styrene butadiene resin, particle diameter 0.4 μm, refractive index 1.5) can be exemplified.
The hollow particles are particles having voids inside, and have a porous outer wall.
The shape may be spherical or flat.
As the hollow particles, trade names: Ropeke HP-1055 (styrene acrylic resin, particle diameter 1 μm, refractive index 1.5), Ropeke HP-91 (styrene acrylic resin, particle diameter 1 μm, refraction) manufactured by Nippon Zeon Co., Ltd. 1.5), Ropeke OP-84J (styrene acrylic resin, particle size 0.6 μm, refractive index 1.5), Ropeke HP-433J (styrene acrylic resin, particle size 0.4 μm, refractive index 1.5),
NIPOL MH5055 (styrene acrylic resin, particle size 0.5 μm, refractive index 1.5),
Examples include trade names: SX866 (styrene acrylic resin, particle diameter 0.3 μm, refractive index 1.5) and SX8782 (styrene acrylic resin, particle diameter 1 μm, refractive index 1.5) manufactured by JSR Corporation.
前記積層体に水を付着させる手段としては、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具又は塗布具、ローラー形態の塗布具、スタンプ具等の水付着具を用いることができる。
なお、好ましい水付着具としては、容器内に水を収容し、且つ、容器内の水を導出する連続気孔を有するプラスチック多孔体又は繊維加工体をペン先部材として適用した筆記具又は塗布具であり、筆跡を簡便に形成でき、実用性を高めることができる。
前記における連続気孔を有するプラスチック多孔体又は繊維加工体は、水を適宜量、吸収し、吐出させるものであればよく、ポリオレフィン系、ポリウレタン系、ポリエステル系、その他各種プラスチックの連続気孔体や繊維を集束させた毛筆状のもの、繊維の樹脂加工又は熱溶着加工によるもの、フェルト、不織布形態のものを挙げることができ、形状、寸法は目的に応じて任意に設定できる。
As means for adhering water to the laminate, a writing or applicator having a brush or a fiber pen at the tip, a fiber or brush that contains water in the container and derives the water in the container A water applicator such as a writing instrument or applicator provided with a roller, an applicator in the form of a roller, or a stamp tool can be used.
In addition, as a preferable water adhering tool, it is a writing instrument or applicator in which water is contained in a container and a plastic porous body or a fiber processed body having continuous pores for leading out the water in the container is applied as a pen tip member. The handwriting can be easily formed and the practicality can be enhanced.
The plastic porous body or fiber processed body having continuous pores in the above may be any one that absorbs and discharges water in an appropriate amount, such as polyolefin-based, polyurethane-based, polyester-based and other various plastic continuous pores and fibers. Examples include a focused brush-like one, a fiber-processed resin-processed or heat-welded one, a felt, and a non-woven fabric. The shape and dimensions can be arbitrarily set according to the purpose.
以下に実施例を示すが、本発明はこれらの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
支持体として白色の合成紙上に、ピンク色蛍光顔料〔商品名:エポカラーFP−10、旭成化学(株)製〕10部、アクリル酸エマルジョン(固形部50%)50部、シリコーン系消泡剤0.2部、水系インキ増粘剤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、攪拌してなる蛍光ピンク色スクリーンインキを用いて、180メッシュのスクリーン版にてベタ印刷し着色層を形成した。
次いで、前記着色層上に、湿式法珪酸〔商品名:ニップシールE−200A、日本シリカ工業(株)製〕15部、ウレタンエマルジョン〔商品名:ハイドランAP−10、大日本インキ化学工業(株)製、固形分30%〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、ブロックイソシアネート系架橋剤2部を均一に混合、攪拌してなる白色スクリーン印刷用インキを用いて、120メッシュのスクリーン版にて全面にベタ印刷し、70℃で5分間乾燥硬化させて多孔質層を形成した。
次いで、多孔質層上に、樹脂粒子〔ミューティクルPP240D、三井化学(株)製〕4.5部、湿式法珪酸〔商品名:サイシリア730、日本シリカ工業(株)製〕4.5部、アクリルエマルジョン〔商品名:NeoRez A−612、DSM社製、固形分32%〕60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、ブロックイソシアネート系架橋剤2部を均一に混合、攪拌してなるスクリーン印刷用インキを用いて、180メッシュのスクリーン版にてベタ印刷し、70℃で5分間乾燥硬化させて保護層(膜厚5μm、粒状物1.5g/m2含有)を形成して変色性積層体を得た。
前記変色性積層体は、乾燥状態では全面が白色の多孔質層が視認できた。保護層の上から水を付着させると多孔質層が吸液により無色透明に変化し着色層のピンク色が視認され、水が蒸発することにより全面が白色の状態に戻った。
Examples are shown below, but the present invention is not limited to these examples. In addition, the part in an Example shows a mass part.
Example 1
10 parts pink fluorescent pigment [trade name: Epocolor FP-10, manufactured by Asahi Chemical Co., Ltd.] on white synthetic paper as a support, 50 parts acrylic acid emulsion (solid part 50%), silicone-based antifoaming agent A fluorescent pink screen ink obtained by uniformly mixing and stirring 0.2 parts, 3 parts of a water-based ink thickener, 2 parts of a wetting agent, 1 part of a leveling agent, 10 parts of water, and 2.5 parts of an epoxy-based crosslinking agent. Using this, solid printing was performed with a 180 mesh screen plate to form a colored layer.
Next, 15 parts of wet-process silicic acid [trade name: Nipseal E-200A, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran AP-10, Dainippon Ink & Chemicals, Inc.] on the colored layer. Manufactured, solid content 30%] 50 parts, water 30 parts, silicone-based antifoaming agent 0.5 part, water-based ink thickener 3 parts, ethylene glycol 1 part, block isocyanate-based crosslinking agent 2 parts uniformly mixed and stirred Using the white screen printing ink thus formed, the entire surface was solid-printed with a 120-mesh screen plate and dried and cured at 70 ° C. for 5 minutes to form a porous layer.
Next, 4.5 parts of resin particles [Muticle PP240D, manufactured by Mitsui Chemicals, Inc.], 4.5 parts of wet method silicic acid [trade name: Cicilia 730, manufactured by Nippon Silica Industry Co., Ltd.] on the porous layer, Acrylic emulsion [trade name: NeoRez A-612, manufactured by DSM, solid content 32%] 60 parts, 0.5 part of silicone-based antifoaming agent, 3 parts of water-based ink thickener, 1 part of ethylene glycol, blocked isocyanate-based crosslinking Using a screen printing ink obtained by uniformly mixing and stirring 2 parts of the agent, solid-printed on a 180 mesh screen plate and dried and cured at 70 ° C. for 5 minutes to form a protective layer (film thickness 5 μm, granular material 1 0.5 g / m 2 inclusive) to form a discolorable laminate.
In the discolorable laminate, a white porous layer was visually recognized in the dry state. When water was allowed to adhere from above the protective layer, the porous layer changed to colorless and transparent due to liquid absorption, the pink color of the colored layer was visually recognized, and the entire surface returned to a white state as the water evaporated.
比較例1
実施例1と同様の支持体上に、実施例1と同様の着色層、多孔質層を形成して変色性積層体を得た。
前記変色性積層体は、乾燥状態では全面が白色の多孔質層が視認できた。水を付着させると多孔質層が吸液により無色透明に変化し着色層のピンク色が視認され、水が蒸発することにより全面が白色の状態に戻った。
Comparative Example 1
On the same support as in Example 1, the same colored layer and porous layer as in Example 1 were formed to obtain a discolorable laminate.
In the discolorable laminate, a white porous layer was visually recognized in the dry state. When water was attached, the porous layer changed to colorless and transparent due to liquid absorption, the pink color of the colored layer was visually recognized, and the entire surface returned to a white state as the water evaporated.
比較例2
実施例1と同様の支持体上に、実施例1と同様の着色層、多孔質層を形成した。
次いで、前記多孔質層上に、樹脂粒子〔ミューティクルPP240D、三井化学(株)製〕3部、湿式法珪酸〔商品名:サイシリア730、日本シリカ工業(株)製〕3部、アクリルエマルジョン〔商品名:NeoRez A−612、DSM社製、固形分32%〕60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、ブロックイソシアネート系架橋剤2部を均一に混合、攪拌してなるスクリーン印刷用インキを用いて、120メッシュのスクリーン版にてベタ印刷し、70℃で5分間乾燥硬化させて保護層(膜厚8μm、粒状物1.5g/m2含有)を形成して変色性積層体を得た。
前記変色性積層体は、乾燥状態では全面が白色の多孔質層が視認できた。保護層の上から水を付着させても多孔質層は、保護層により吸液が阻害されて色変化に乏しいものであった。
Comparative Example 2
On the same support as in Example 1, the same colored layer and porous layer as in Example 1 were formed.
Next, on the porous layer, 3 parts of resin particles [Muticle PP240D, manufactured by Mitsui Chemicals, Inc.], 3 parts of a wet process silicic acid [trade name: Cicilia 730, manufactured by Nippon Silica Kogyo Co., Ltd.], acrylic emulsion [ Product name: NeoRez A-612, DSM, solid content 32%] 60 parts, silicone antifoam 0.5 parts, aqueous ink thickener 3 parts, ethylene glycol 1 part, block isocyanate cross-linking agent 2 parts Using a screen printing ink that is uniformly mixed and stirred, a solid print is made on a 120-mesh screen plate and dried and cured at 70 ° C. for 5 minutes to form a protective layer (film thickness: 8 μm, granular material: 1.5 g / m 2 -containing) to form a discolorable laminate.
In the discolorable laminate, a white porous layer was visually recognized in the dry state. Even when water was allowed to adhere from above the protective layer, the porous layer was poor in color change due to inhibition of liquid absorption by the protective layer.
比較例3
実施例1と同様の支持体上に、実施例1と同様の着色層、多孔質層を形成した。
次いで、前記多孔質層上に、樹脂粒子〔ミューティクルPP240D、三井化学(株)製〕8部、湿式法珪酸〔商品名:サイシリア730、日本シリカ工業(株)製〕8部、アクリルエマルジョン〔商品名:NeoRez A−612、DSM社製、固形分32%〕60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、ブロックイソシアネート系架橋剤2部を均一に混合、攪拌してなるスクリーン印刷用インキを用いて、250メッシュのスクリーン版にてベタ印刷し、70℃で5分間乾燥硬化させて保護層(膜厚3μm、粒状物1.5g/m2含有)を形成して変色性積層体を得た。
前記変色性積層体は、乾燥状態では全面が白色の多孔質層が視認できた。保護層の上から水を付着させると多孔質層が吸液により無色透明に変化し着色層のピンク色が視認され、水が蒸発することにより全面が白色の状態に戻った。
Comparative Example 3
On the same support as in Example 1, the same colored layer and porous layer as in Example 1 were formed.
Next, on the porous layer, 8 parts of resin particles [Muticle PP240D, manufactured by Mitsui Chemicals, Inc.], 8 parts of wet process silicic acid [trade name: Cicilia 730, manufactured by Nippon Silica Industry Co., Ltd.], acrylic emulsion [ Product name: NeoRez A-612, DSM, solid content 32%] 60 parts, silicone antifoam 0.5 parts, aqueous ink thickener 3 parts, ethylene glycol 1 part, block isocyanate cross-linking agent 2 parts Using a screen printing ink that is uniformly mixed and stirred, a solid printing is performed on a 250 mesh screen plate, followed by drying and curing at 70 ° C. for 5 minutes to form a protective layer (film thickness 3 μm, granular material 1.5 g / m 2 -containing) to form a discolorable laminate.
In the discolorable laminate, a white porous layer was visually recognized in the dry state. When water was allowed to adhere from above the protective layer, the porous layer changed to colorless and transparent due to liquid absorption, the pink color of the colored layer was visually recognized, and the entire surface returned to a white state as the water evaporated.
比較例4
実施例1と同様の支持体上に、実施例1と同様の着色層、多孔質層を形成した。
次いで、前記多孔質層上に、樹脂粒子〔ミューティクルPP240D、三井化学(株)製〕2部、湿式法珪酸〔商品名:サイシリア730、日本シリカ工業(株)製〕2部、アクリルエマルジョン〔商品名:NeoRez A−612、DSM社製、固形分32%〕60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、ブロックイソシアネート系架橋剤2部を均一に混合、攪拌してなるスクリーン印刷用インキを用いて、250メッシュのスクリーン版にてベタ印刷し、70℃で5分間乾燥硬化させて保護層(膜厚3μm、粒状物0.4g/m2含有)を形成して変色性積層体を得た。
前記変色性積層体は、乾燥状態では全面が白色の多孔質層が視認できた。保護層の上から水を付着させても多孔質層は、保護層により吸液が阻害され色変化に乏しかった。
Comparative Example 4
On the same support as in Example 1, the same colored layer and porous layer as in Example 1 were formed.
Next, on the porous layer, 2 parts of resin particles [Muticle PP240D, manufactured by Mitsui Chemicals, Inc.], 2 parts of wet method silicic acid [trade name: Cicilia 730, manufactured by Nippon Silica Kogyo Co., Ltd.], acrylic emulsion [ Product name: NeoRez A-612, DSM, solid content 32%] 60 parts, silicone antifoam 0.5 parts, aqueous ink thickener 3 parts, ethylene glycol 1 part, block isocyanate cross-linking agent 2 parts Using a screen printing ink that is uniformly mixed and stirred, a solid print is made on a 250-mesh screen plate, followed by drying and curing at 70 ° C. for 5 minutes to form a protective layer (film thickness 3 μm, granular material 0.4 g / m 2 -containing) to form a discolorable laminate.
In the discolorable laminate, a white porous layer was visually recognized in the dry state. Even when water was allowed to adhere from above the protective layer, the porous layer was poor in color change due to inhibition of liquid absorption by the protective layer.
実施例2
支持体として白色の合成紙上に、ピンク色顔料10部、アクリル酸エマルジョン(固形部50%)50部、シリコーン系消泡剤0.2部、水系インキ増粘剤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、攪拌してなる蛍光ピンク色スクリーンインキを用いて、180メッシュのスクリーン版にて「A」の文字を印刷した。
次いで、前記文字上に、湿式法珪酸〔商品名:ニップシールE−200A、日本シリカ工業(株)製〕15部、ウレタンエマルジョン〔商品名:ハイドランAP−10、大日本インキ化学工業(株)製、固形分30%〕50部、水30部、シリコーン系消泡剤0.5部、水系インキ増粘剤3部、エチレングリコール1部、ブロックイソシアネート系架橋剤2部を均一に混合、攪拌してなる白色スクリーン印刷用インキを用いて、120メッシュのスクリーン版にて全面にベタ印刷し、70℃で5分間乾燥硬化させて多孔質層を形成した。
次いで、前記多孔質層上に、樹脂粒子〔ミューティクルPP240D、三井化学(株)製〕11部、アクリルエマルジョン〔商品名:NeoRez A−612、DSM社製、固形分32%〕60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、ブロックイソシアネート系架橋剤2部を均一に混合、攪拌してなるスクリーン印刷用インキを用いて、180メッシュのスクリーン版にてベタ印刷して保護層(膜厚5μm、粒状物1.8g/m2含有)を形成して変色性積層体を得た。
前記変色性積層体は、乾燥状態では全面が白色の多孔質層が視認できた。保護層の上から水を付着させると多孔質層が吸液により無色透明に変化し下層のピンクの文字Aが明確に視認され、水が蒸発することにより全面が白色の状態に戻った。
Example 2
On a white synthetic paper as a support, 10 parts of a pink pigment, 50 parts of an acrylic acid emulsion (solid part 50%), 0.2 part of a silicone-based antifoaming agent, 3 parts of a water-based ink thickener, 2 parts of a wetting agent, The letter “A” was printed on a 180-mesh screen plate using a fluorescent pink screen ink in which 1 part of a leveling agent, 10 parts of water, and 2.5 parts of an epoxy crosslinking agent were uniformly mixed and stirred. .
Next, 15 parts wet-type silicic acid [trade name: Nipseal E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc.] , Solid content 30%] 50 parts, water 30 parts, silicone-based defoamer 0.5 part, water-based ink thickener 3 parts, ethylene glycol 1 part, block isocyanate-based crosslinking agent 2 parts uniformly mixed and stirred Using the white screen printing ink, solid printing was performed on the entire surface with a 120 mesh screen plate, followed by drying and curing at 70 ° C. for 5 minutes to form a porous layer.
Next, on the porous layer, 11 parts of resin particles [Muticle PP240D, manufactured by Mitsui Chemicals, Inc.], acrylic emulsion [trade name: NeoRez A-612, manufactured by DSM, solid content 32%] 60 parts, silicone 180 mesh screen ink using screen printing ink prepared by uniformly mixing and stirring 0.5 part of antifoaming agent, 3 parts of water-based ink thickener, 1 part of ethylene glycol and 2 parts of blocked isocyanate crosslinking agent A solid printing was performed with a plate to form a protective layer (film thickness 5 μm, containing granular material 1.8 g / m 2 ) to obtain a discolorable laminate.
In the discolorable laminate, a white porous layer was visually recognized in the dry state. When water was allowed to adhere from above the protective layer, the porous layer changed to colorless and transparent due to liquid absorption, and the pink letter A in the lower layer was clearly visible, and the entire surface returned to a white state as the water evaporated.
比較例5
実施例2と同様の支持体上に、実施例2と同様の「A」の文字、多孔質層を形成して変色性積層体を得た。
前記変色性積層体は、乾燥状態では全面が白色の多孔質層が視認できた。水を付着させると多孔質層が吸液により無色透明に変化し下層のピンクの文字Aが明確に視認され、水が蒸発することにより全面が白色の状態に戻った。
Comparative Example 5
On the same support as in Example 2, the same letter “A” as in Example 2 and a porous layer were formed to obtain a discolorable laminate.
In the discolorable laminate, a white porous layer was visually recognized in the dry state. When water was attached, the porous layer changed to colorless and transparent due to liquid absorption, and the pink letter A in the lower layer was clearly visually recognized, and the entire surface returned to a white state as the water evaporated.
以下の表に実施例1及び2及び比較例1乃至4の各変色性積層体を水に濡らした時の目視による変色性試験の結果、摩擦試験機による耐擦過性試験の結果を示す。
なお、耐擦過性試験は、摩擦試験機2型(学振型)〔スガ試験機(株)製〕を用い、上部の摩擦子に綿布(かなきん3号、JIS L 0803準拠、JIS染色堅牢度試験用)を取り付け、前記摩擦子を700gの加重下で変色性積層体の試験片上に毎分30往復の速度で10cmの間を500回水平往復運動させることにより行った。
前記耐擦過性試験は、試験片を水に濡らした状態(吸液状態)で行った。
The table below shows the results of visual discoloration tests when each of the discolorable laminates of Examples 1 and 2 and Comparative Examples 1 to 4 is wetted with water, and the results of a scratch resistance test using a friction tester.
For the scratch resistance test, a friction tester type 2 (Gakushin Type) [manufactured by Suga Test Instruments Co., Ltd.] was used, and the upper friction piece was cotton cloth (Kanakin No. 3, JIS L 0803 compliant, JIS dyeing fastness) And the friction element was subjected to a horizontal reciprocating motion between 10 cm at a speed of 30 reciprocations per minute under a load of 700 g at a speed of 30 reciprocations per minute.
The scratch resistance test was performed in a state where the test piece was wet with water (liquid absorption state).
変色性試験
○:十分な透明性を有する。
△:下層の色調、模様が不鮮明に視認され実用的な透明性がない。
×:下層の色調、模様が視認されない。
耐擦過性試験
○:擦過による皮膜の劣化がない。
△:擦過による皮膜の劣化が大きく、実用的な皮膜強度を有さない。
×:擦過により多孔質層が消失する。
Discoloration test ○: Sufficient transparency.
(Triangle | delta): The color tone and pattern of a lower layer are visually recognized unclearly, and there is no practical transparency.
X: The color tone and pattern of a lower layer are not visually recognized.
Scratch resistance test ○: There is no deterioration of the film due to scratching.
(Triangle | delta): The deterioration of the film | membrane by abrasion is large and does not have practical film | membrane intensity | strength.
X: A porous layer lose | disappears by abrasion.
試験結果に見られるように本発明の変色性積層体は、比較例の積層体と比べ、水で濡らすことによる良好な変色性を維持したまま、耐擦過性の向上を示した。 As can be seen from the test results, the discolorable laminate of the present invention showed improved scratch resistance while maintaining good discoloration by wetting with water, as compared with the laminate of the comparative example.
Claims (3)
1+2B≦A≦3.5+2B (1)
0.5≦B≦2.5 (2) A porous layer having a low refractive index pigment fixed in a dispersed state in a binder resin and having different transparency in a liquid absorbing state and a non-liquid absorbing state is provided on the support, and the porous granular material or non-porous material is provided on the porous layer. Ri spherical granules name a protective layer dispersed in a binder resin, and the thickness a of the protective layer ([mu] m), the mass B of the porous granules or non-spherical granules per unit area in the protective layer A water discolorable laminate in which (g / m 2 ) satisfies the following relational expressions (1) and (2) .
1 + 2B ≦ A ≦ 3.5 + 2B (1)
0.5 ≦ B ≦ 2.5 (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007292672A JP4950849B2 (en) | 2007-11-12 | 2007-11-12 | Water discolorable laminate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007292672A JP4950849B2 (en) | 2007-11-12 | 2007-11-12 | Water discolorable laminate |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2009119611A JP2009119611A (en) | 2009-06-04 |
JP4950849B2 true JP4950849B2 (en) | 2012-06-13 |
Family
ID=40812333
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2007292672A Active JP4950849B2 (en) | 2007-11-12 | 2007-11-12 | Water discolorable laminate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4950849B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009087789A1 (en) * | 2008-01-04 | 2009-07-16 | Sakura Color Products Corporation | Fabric sheet changing in color with water |
JP5378263B2 (en) * | 2010-02-16 | 2013-12-25 | 株式会社サクラクレパス | Water discoloration sheet |
JP2014184656A (en) * | 2013-03-23 | 2014-10-02 | Mitsubishi Plastics Inc | Laminate polyester film roll for optical use |
WO2019004113A1 (en) * | 2017-06-29 | 2019-01-03 | パイロットインキ株式会社 | Discoloring body having glossiness |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006321244A (en) * | 1997-10-31 | 2006-11-30 | Pilot Ink Co Ltd | Discoloring body |
JP4160648B2 (en) * | 1998-02-13 | 2008-10-01 | パイロットインキ株式会社 | Discolorable laminate |
JP2000135386A (en) * | 1998-10-30 | 2000-05-16 | Pilot Ink Co Ltd | Target whose color is changed by water |
JP4172577B2 (en) * | 2001-10-30 | 2008-10-29 | パイロットインキ株式会社 | Thermocompression-bonding water-discoloring sheet material and water-discoloring processed body using the same |
JP2006117807A (en) * | 2004-10-22 | 2006-05-11 | Pilot Ink Co Ltd | Color-changing pressure-sensitive adhesive sheet |
JP4499539B2 (en) * | 2004-11-30 | 2010-07-07 | パイロットインキ株式会社 | Discolored body set |
JP2005271580A (en) * | 2005-02-04 | 2005-10-06 | Pilot Ink Co Ltd | Cloth sheet whose color is changeable with water and toy set employing it |
-
2007
- 2007-11-12 JP JP2007292672A patent/JP4950849B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2009119611A (en) | 2009-06-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4950849B2 (en) | Water discolorable laminate | |
CN1087694C (en) | Recording media | |
JP4786564B2 (en) | Water discoloration drawing toy and water discoloration drawing toy set using the same | |
JP2007322594A (en) | Color changeable self-adhesive label, and color changeable article using the same | |
JP2011005642A (en) | Water discolorable cloth sheet, and water discolorable drawing toy set using the same | |
JP2007118198A (en) | Discoloring laminate | |
JP6147724B2 (en) | Method for producing water-coloring laminate | |
JP3156569U (en) | Learning tool and learning tool set using the same | |
JP2011079253A (en) | Water discoloration see-through sheet and water discoloration see-through sheet set using the same | |
JP3157166U (en) | Water discoloration learning tool and water discoloration learning tool set using the same | |
JP2010094971A (en) | Water color-change fabric and water color-change plotting toy set using the same | |
JP2009271321A (en) | Allochroic geography teaching equipment and allochroic geography teaching equipment set using the same | |
JP2007050694A (en) | Reversible color change body and reversible color change body set using the same | |
JP6412792B2 (en) | Glittering discolorant and glittering discolorant set using the same | |
JP6615393B2 (en) | Color change body and color change body set using the same | |
JP2012236332A (en) | Water color-changeable laminate | |
JP3178550U (en) | Water discolorable fluoroscopic sheet and water discolorable fluoroscopic sheet set using the same | |
JP2022097408A (en) | Water discoloration body, and water discoloration body set | |
JP7018473B2 (en) | Water discoloration indicator | |
JP2009184209A (en) | Water discoloration printed matter | |
JPH0255185A (en) | Material to be recorded and ink jet recording method using the same | |
JP2008262009A (en) | Water-allochroic teaching tool and water-allochroic teaching tool set using same | |
JP6738638B2 (en) | Water discoloring cursive body and water discoloring cursive body set using the same | |
JP2022153279A (en) | Aqueous discoloration body, aqueous discoloration set | |
JP6938357B2 (en) | Water discoloration indicator |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100913 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111118 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120110 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120125 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120306 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120309 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150316 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4950849 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313121 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |