JPH09309174A - Thermal discoloring laminated body - Google Patents
Thermal discoloring laminated bodyInfo
- Publication number
- JPH09309174A JPH09309174A JP8151734A JP15173496A JPH09309174A JP H09309174 A JPH09309174 A JP H09309174A JP 8151734 A JP8151734 A JP 8151734A JP 15173496 A JP15173496 A JP 15173496A JP H09309174 A JPH09309174 A JP H09309174A
- Authority
- JP
- Japan
- Prior art keywords
- color
- layer
- temperature
- thermochromic
- colored
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は熱変色性積層体に関
する。更に詳細には、可逆熱変色性隠蔽層が発消色する
ことにより、図柄を隠顕させる熱変色性積層体に関す
る。TECHNICAL FIELD The present invention relates to a thermochromic laminate. More specifically, the invention relates to a thermochromic laminate that reveals a pattern by developing and erasing the reversible thermochromic hiding layer.
【０００２】[0002]
【従来の技術】従来、図柄層を隠顕させる可逆熱変色性
隠蔽層を設けた熱変色性積層体が開示されている（実公
平４−１４７８７号公報）。前記した熱変色性積層体
は、可逆熱変色性隠蔽層が発消色することにより図柄層
が隠顕されるとしても、図柄層が明度の高い色調からな
る多彩な図柄である場合、或いは濃い色調の図柄である
場合、隠蔽層は前記図柄を十分に隠蔽可能な発色濃度を
有する必要があり、層中の熱変色性材料の含有率を増加
したり、層を厚くする等の手段がとられてきた。しかし
ながら、前記した手段では、図柄層を十分に隠蔽するこ
とができたとしても、前記隠蔽層の消色状態にあって図
柄層が不明瞭になったり、或いは隠蔽層の色残りによっ
て図柄層の色調に影響を与え、本来の色調の図柄を視覚
できないといった欠点を有していた。2. Description of the Related Art Conventionally, a thermochromic laminate having a reversible thermochromic concealing layer for concealing a pattern layer has been disclosed (Japanese Utility Model Publication No. 4-14787). The thermochromic laminate described above, when the reversible thermochromic hiding layer develops and disappears to reveal the pattern layer, when the pattern layer is a colorful pattern having a high lightness, or is dark. In the case of a color tone pattern, the hiding layer needs to have a coloring density capable of hiding the pattern sufficiently, and means such as increasing the content of the thermochromic material in the layer or thickening the layer is used. Has been. However, in the means described above, even if the pattern layer can be sufficiently hidden, the pattern layer becomes unclear in the decoloring state of the hiding layer, or the color layer of the hiding layer causes the pattern layer to become unclear. It had a drawback that it affected the color tone and that the pattern of the original color tone could not be seen.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前記した従
来の不具合を解消し、支持体上に設けた図柄層の視覚性
が殆ど妨害を受けることなく、鮮明な色調を呈して視覚
されると共に、前記図柄層の可逆熱変色性隠蔽層による
隠蔽性が十分に満足される熱変色性積層体を提供するも
のである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides a clear color tone with almost no obstruction to the visibility of the design layer provided on the support. At the same time, the invention provides a thermochromic laminate in which the masking property of the pattern layer by the reversible thermochromic masking layer is sufficiently satisfied.
【０００４】[0004]
【課題を解決するための手段】本発明は、支持体上に設
けた図柄層と、前記図柄層を隠蔽する可逆熱変色性隠蔽
層よりなる熱変色性積層体であって、前記図柄層は少な
くとも一部が温度変化により有色（１）と有色（２）の
可逆的互変性を有し、いずれか一方が他方より視覚濃度
が大である色調を呈する可逆熱変色層であり、前記可逆
熱変色性隠蔽層は、前記可逆熱変色層の視覚濃度が大で
ある色調に対して、発色時の色調が同等以上の視覚濃度
であるか又は同一乃至近似色である熱変色性積層体を要
件とする。更には、前記可逆熱変色層が、温度変化によ
る着色濃度の変化をプロットした曲線の形状が、温度を
変色温度域より低温側から温度を上昇させていく場合
と、逆に変色温度より高温側から下降させていく場合と
で大きく異なる経路を辿って変色し、低温側変色点と高
温側変色点の間の温度域において、有色（１）と有色
（２）間の互変性を呈し、前記有色（１）と有色（２）
の両相が共存できる二相保持領域が常温域にあり、低温
側変色点以下又は高温側変色点以上の温度で変化させた
状態を記憶保持できる熱変色性材料により形成されてな
る熱変色性積層体を要件とする。ここで、前記視覚濃度
は、目視による濃淡の感覚濃度であり、同一系統の色調
における濃淡に限らず、寒色、暖色の関係にあっては、
寒色の色調が視覚濃度が大であるといった目安を示す。The present invention is a thermochromic laminate comprising a pattern layer provided on a support and a reversible thermochromic masking layer for masking the pattern layer, wherein the pattern layer is At least a part of the reversible thermochromic layer has a reversible tautomerism of colored (1) and colored (2) due to temperature change, and one of them is a reversible thermochromic layer exhibiting a color tone having a higher visual density than the other. The color-changing concealing layer requires a color-changing laminate in which the reversible thermochromic layer has a high visual density, and the color tone at the time of color development is equal to or higher than the visual density, or the same or an approximate color. And Furthermore, the reversible thermochromic layer has a shape of a curve plotting a change in coloring density due to a temperature change, and when the temperature is increased from a temperature lower than the color changing temperature range to a temperature higher than the color changing temperature. The color changes according to a path that is significantly different between the case where the color is lowered from the above, and in the temperature range between the low temperature side color change point and the high temperature side color change point, it exhibits the inversion between the colored (1) and the colored (2), Colored (1) and colored (2)
There is a two-phase holding region where both phases can coexist in the room temperature range, and the thermochromic property is formed by a thermochromic material that can retain and retain the state changed at a temperature below the low-temperature side discoloration point or above the high-temperature side discoloration point. It requires a laminate. Here, the visual density is a visual density density, and is not limited to the density in the color tone of the same system, but in the relationship of cold color and warm color,
An indication that a cold color tone has a high visual density is shown.
【０００５】前記支持体は紙、合成紙、編織布等の布
帛、植毛或いは起毛布、不織布、合成皮革、レザー、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、形態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。As the support, paper, synthetic paper, cloth such as woven cloth, flocked or raised cloth, non-woven fabric, synthetic leather, leather, plastic, glass, ceramics, metal, wood, stone material, etc. are used. Further, the shape is preferably a flat shape, but may be an uneven shape.
【０００６】前記図柄層は、少なくとも適宜の文字、数
字、図形等の像を一種の有色（１）から有色（２）に可
逆的に変色する可逆熱変色性材料を含む熱変色性インキ
により形成された可逆熱変色層、或いは、複数の互いに
異なる色調を呈する熱変色性インキにより形成した混成
の可逆熱変色層によって形成される。更に、一般有色染
顔料による非変色層を併設或いは積層して図柄層を形成
してもよい。The pattern layer is formed by a thermochromic ink containing a reversible thermochromic material that reversibly discolors an image of at least appropriate characters, numbers, figures, etc. from a kind of colored (1) to colored (2). Or a mixed reversible thermochromic layer formed from a plurality of thermochromic inks having different color tones. Furthermore, a non-discoloring layer of general colored dyes and pigments may be provided together or laminated to form a pattern layer.
【０００７】本発明では、図柄層に有色（１）から有色
（２）に可逆的に変色する可逆熱変色性材料を用いて発
色時の色調を互いに同一乃至近似色となるよう設定し、
図柄層全体の色調が可逆熱変色性隠蔽層による隠蔽を補
助するように調整する。よって、膜厚の薄い可逆熱変色
性隠蔽層を積層しても隠蔽が可能となり、より鮮明な図
柄層を視覚することができ、しかも安定した量産性を満
たす熱変色性積層体を得ることができる。In the present invention, a reversible thermochromic material that reversibly changes from colored (1) to colored (2) is used in the pattern layer, and the color tones during color development are set to be the same or similar to each other.
The color tone of the entire design layer is adjusted so as to assist the hiding by the reversible thermochromic hiding layer. Therefore, even if a reversible thermochromic hiding layer having a small film thickness is laminated, it is possible to conceal, a clearer pattern layer can be visually recognized, and a thermochromic laminated body satisfying stable mass productivity can be obtained. it can.
【０００８】非変色性材料として染料、顔料等の可視光
線吸収体からなる着色材を用いる場合、減法混色によっ
て、各種の色が実現されるが、前記可逆熱変色層或いは
非変色層を可逆熱変色性隠蔽層で効果的に隠蔽するため
には、可逆熱変色層或いは非変色層に可逆熱変色性隠蔽
層の色調の減法混色における構成色を使用することが好
ましい。When a coloring material composed of a visible light absorber such as a dye or a pigment is used as the non-color-changing material, various colors can be realized by subtractive color mixing. In order to effectively conceal the color-changing masking layer, it is preferable to use the constituent colors in the subtractive color mixture of the color tone of the reversible thermochromic masking layer for the reversible thermochromic layer or the non-color-changing layer.
【０００９】又、図柄層の白色部分には、有色←→無色
に可逆的に変色する熱変色性材料を用いて図柄層全体の
色調を均一化することにより、より効果的な隠蔽が可能
となる。Further, in the white portion of the design layer, a thermochromic material that reversibly changes color ← → colorlessly is used to make the color tone of the entire design layer uniform, thereby enabling more effective concealment. Become.
【００１０】前記可逆熱変色層及び可逆熱変色性隠蔽層
を形成するために用いられる可逆熱変色性材料は、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熱
変色性材料が好適に用いられる。具体的には、特公昭５
１−３５４１４号公報、特公昭５１−４４７０６号公
報、特公平１−１７１５４号公報等に記載されている熱
変色性材料、即ち、 （１）（イ）電子供与性呈色性有機化合物と（ロ）フェ
ノール性水酸基を有する化合物と（ハ）鎖式脂肪族１価
アルコールの三成分を必須成分とした熱変色性材料。ま
たは、 （２）（イ）電子供与性呈色性有機化合物と（ロ）フェ
ノール性水酸基を有する化合物と（ハ）脂肪族１価アル
コールと脂肪族モノカルボン酸から得たエステルより選
んだ化合物の三成分を必須成分とした熱変色性材料。ま
たは、 （３）（イ）電子供与性呈色性有機化合物と（ロ）フェ
ノール性水酸基を有する化合物と（ハ）高級脂肪族１価
アルコールと、脂肪族モノカルボン酸と鎖式脂肪族１価
アルコールから得たエステルのいずれかより選んだ化合
物の三成分を必須成分とし、これを微小カプセルに内包
した熱変色性材料。又は、 （４）（イ）電子供与性呈色性有機化合物と（ロ）フェ
ノール性水酸基を有する化合物と（ハ）高級脂肪族１価
アルコールと、脂肪族モノカルボン酸と鎖式脂肪族１価
アルコールとから得たエステルより選んだ化合物の三成
分を必須成分とし、これをビヒクル中に溶解又は分散し
てなる熱変色性材料。或いは、特開平７−１８６５４６
号公報に記載されている、発色時には蛍光性を有する黄
色、黄橙色、橙色、赤橙色、赤色等の高発色濃度且つ明
るさに富む色を呈し、消色時には、色残りがなく無色を
呈する、（イ）ピリジン系、キナゾリン系、及びビスキ
ナゾリン系から選ばれる電子供与性呈色性有機化合物、
（ロ前記電子供与性呈色性有機化合物に対して電子受容
性である化合物、（ハ）前記（イ）、（ロ）成分による
電子授受反応を特定温度域において可逆的に生起させる
反応媒体である化合物の３成分を必須成分とする相溶体
からなる熱変色性材料。又、本出願人が提案した特公平
１−２９３９８号公報に記載した如き、温度変化による
色濃度−温度曲線に関し、３℃以下のヒステリシス幅を
もつ、高感度の熱変色性材料が挙げられる。前記は所定
の温度（変色点）を境としてその前後で変色し、変化前
後の両状態のうち常温域では特定の一方の状態しか存在
しえない。即ち、もう一方の状態は、その状態が発現す
るのに要する熱又は冷熱が適用されている間は維持され
るが、前記熱又は冷熱の適用がなくなれば常温域で呈す
る状態に戻る、所謂、温度変化による温度−色濃度につ
いて小さいヒステリシス幅（ΔＨ）を示して変色するタ
イプである。The reversible thermochromic material used for forming the reversible thermochromic layer and the reversible thermochromic masking layer reversibly causes a color reaction between an electron-donating color-changing organic compound and an electron-accepting compound. A thermochromic material containing three components of an organic compound medium to be generated is preferably used. Specifically, Japanese Patent Publication Sho 5
Thermochromic materials described in JP-A No. 1-354414, JP-B No. 51-44706, JP-B No. 1-17154, and the like, that is, (1) (a) an electron-donating color-forming organic compound and ( (B) A thermochromic material containing three components, a compound having a phenolic hydroxyl group and (c) a chain aliphatic monohydric alcohol as essential components. Or (2) a compound selected from an electron-donating color-developing organic compound, (b) a compound having a phenolic hydroxyl group, and (c) an ester obtained from an aliphatic monohydric alcohol and an aliphatic monocarboxylic acid. Thermochromic material with three essential components. Alternatively, (3) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol, an aliphatic monocarboxylic acid, and a chain aliphatic monohydric compound. A thermochromic material in which three components of a compound selected from any one of esters obtained from alcohol are contained as essential components in microcapsules. Alternatively, (4) (a) an electron-donating color-developing organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol, an aliphatic monocarboxylic acid, and a chain aliphatic monohydric compound. A thermochromic material obtained by dissolving or dispersing three components of a compound selected from an ester obtained from alcohol and an essential component in a vehicle. Alternatively, JP-A-7-186546
As described in Japanese Patent Publication, it exhibits a high color density and abundant colors such as yellow, yellow-orange, orange, red-orange, and red, which have fluorescence at the time of color development, and exhibits a colorless color without residual color at the time of color erasure. , (A) an electron-donating color-forming organic compound selected from pyridine type, quinazoline type, and bisquinazoline type,
(B) A compound that is electron-accepting to the electron-donating color-forming organic compound, (c) a reaction medium that reversibly causes an electron-accepting reaction by the components (a) and (b) in a specific temperature range. A thermochromic material composed of a compatible solution containing three components of a certain compound as essential components, and a color density-temperature curve due to temperature change as described in Japanese Patent Publication No. 1-29398 proposed by the applicant of the present invention. A highly sensitive thermochromic material having a hysteresis width of ℃ or less can be mentioned.The above is a color that changes before and after a predetermined temperature (color change point) as a boundary, and one of the specified ones in the normal temperature range before and after the change. That is, the other state is maintained as long as the heat or cold required for the development of that state is applied, but if the heat or cold is no longer applied, it will be in the normal temperature range. To return to the condition Temperature due to the temperature change - the type of discoloration indicates the color density for small hysteresis width ([Delta] H).
【００１１】又、特公平４−１７１５４号公報に記載さ
れている、大きなヒステリシス特性を示して変色する感
温変色性色彩記憶性材料、即ち、温度変化による着色濃
度の変化をプロットした曲線の形状が、温度を変色温度
域より低温側から温度を上昇させていく場合と、逆に変
色温度より高温側から下降させていく場合とで大きく異
なる経路を辿って変色するタイプの変色性材料であり、
低温側変色点と高温側変色点の間の温度域において、着
色状態と無色状態間の互変性或いは有色（１）と有色
（２）間の互変性を呈し、着色状態と無色状態或いは有
色（１）と有色（２）の両相が共存できる二相保持領域
が常温域にあり、低温側変色点以下又は高温側変色点以
上の温度で変化させた状態を記憶保持できる熱変色性材
料も有効である。Further, as disclosed in Japanese Patent Publication No. 4-17154, a thermosensitive color-changing color memory material exhibiting a large hysteresis characteristic and changing color, that is, a shape of a curve in which a change in color density due to a temperature change is plotted. However, it is a type of discoloring material that discolors by following a significantly different path when the temperature is raised from the lower temperature side than the discoloration temperature range and when it is lowered from the higher temperature side than the discoloration temperature range. ,
In the temperature range between the low-temperature side discoloration point and the high-temperature side discoloration point, it exhibits tautomerism between the colored state and the colorless state or between the colored (1) and the colored (2), and the colored state and the colorless state or the colored ( A thermochromic material that has a two-phase holding region where both 1) and colored (2) phases can coexist in the normal temperature range and can store and retain the state changed at a temperature below the low temperature side discoloration point or above the high temperature side discoloration point It is valid.
【００１２】前記した可逆熱変色性材料は、そのままの
適用でも有効であるが、微小カプセルに内包して使用す
るのが好ましい。即ち、種々の使用条件において可逆熱
変色性材料は同一の組成に保たれ、同一の作用効果を奏
することができるからである。前記微小カプセルに内包
させることにより、化学的、物理的に安定な顔料を構成
でき、粒子径０．１〜１００μｍ、好ましくは３〜３０
μｍの範囲が実用性を満たす。尚、微小カプセル化は、
従来より公知の界面重合法、ｉｎ Ｓｉｔｕ重合法、液
中硬化被覆法、水溶液からの相分離法、有機溶媒からの
相分離法、融解分散冷却法、気中懸濁被覆法、スプレー
ドライング法等があり、用途に応じて適宜選択される。
更に微小カプセルの表面には、目的に応じて更に二次的
な樹脂皮膜を設けて耐久性を付与させたり、表面特性を
改質させて実用に供することもできる。The above-mentioned reversible thermochromic material is effective as it is, but it is preferable to use it by encapsulating it in microcapsules. That is, under various use conditions, the reversible thermochromic materials are maintained in the same composition and can exert the same function and effect. By encapsulating in the microcapsules, a chemically and physically stable pigment can be formed, and the particle diameter is 0.1 to 100 μm, preferably 3 to 30.
The range of μm satisfies the practicality. In addition, microencapsulation is
Conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air suspension coating method, spray drying method, etc. , And is appropriately selected according to the application.
Further, the surface of the microcapsules may be provided with a secondary resin film for imparting durability depending on the purpose, or the surface characteristics may be modified for practical use.
【００１３】又、可逆熱変色性材料として、特開平８─
３４１６８号公報に記載の温度変化によりヒステリシス
特性を示して変色し、白色不透明状態と無色透明状態の
両状態の互変性を有する熱変色性遮光−透光性マイクロ
カプセル顔料を挙げることもできる。前記熱変色性遮光
−透光性マイクロカプセル顔料は、融点が−４０℃〜＋
９０℃の範囲にある結晶性の、エステル類、エーテル
類、ケトン類から選ばれる化合物の一種又は二種以上を
内包させた粒子径が０．１〜５０μｍのマイクロカプセ
ル顔料である熱変色性遮光−透光性マイクロカプセル顔
料である。Further, as a reversible thermochromic material, JP-A-8-
Further, a thermochromic light-shielding / light-transmitting microcapsule pigment which exhibits a hysteresis characteristic and changes in color due to a temperature change and has a mutual change of both white opaque state and colorless transparent state is described in JP-A-34168. The thermochromic shading-translucent microcapsule pigment has a melting point of -40 ° C to +
Thermochromic light-shielding, which is a crystalline microcapsule pigment having a particle size of 0.1 to 50 μm and containing one or more compounds selected from esters, ethers, and ketones in the range of 90 ° C. A translucent microcapsule pigment.
【００１４】前記可逆熱変色性材料は固着剤を含む媒体
中に分散した熱変色性インキにより、支持体上に可逆熱
変色層及び可逆熱変色性隠蔽層を形成する。可逆熱変色
層を形成する可逆熱変色性材料は、媒体中に０．５〜４
０重量％、好ましくは１〜３０重量％含有させることが
できる。０．５重量％未満の配合量では鮮明な熱変色効
果を視覚させ難いし、４０重量％を越えると、過剰であ
り、消色状態にあって残色を生じることもある。可逆熱
変色性隠蔽層を形成する可逆熱変色性材料は、媒体中に
１０〜８０重量％、好ましくは３０〜６０重量％含有さ
せることができる。１０重量％未満の配合量では隠蔽が
困難となり、８０重量％を越えると、被膜強度が不十分
となることもある。The reversible thermochromic material forms a reversible thermochromic layer and a reversible thermochromic hiding layer on the support by the thermochromic ink dispersed in a medium containing a fixing agent. The reversible thermochromic material forming the reversible thermochromic layer is 0.5 to 4 in the medium.
It may be contained in an amount of 0% by weight, preferably 1 to 30% by weight. If the amount is less than 0.5% by weight, a clear thermochromic effect is hard to be visually recognized, and if it exceeds 40% by weight, the color is excessive and may be in a decolored state to cause a residual color. The reversible thermochromic material forming the reversible thermochromic hiding layer can be contained in the medium in an amount of 10 to 80% by weight, preferably 30 to 60% by weight. When the content is less than 10% by weight, hiding is difficult, and when it exceeds 80% by weight, the film strength may be insufficient.
【００１５】更に、電子供与性呈色性有機化合物、フェ
ノール性水酸基を有する化合物及び前記両者の呈色反応
の生起温度を決める反応媒体の三者の均質相溶体を塩化
ビニル−酢酸ビニル共重合樹脂等に微粒子状に分散させ
て得られる、特開平６−１３５１４４号公報に記載の可
逆熱変色性材料により可逆熱変色層及び可逆熱変色性隠
蔽層を形成することもでき、又、塩化ビニル−酢酸ビニ
ル共重合樹脂に、透明性向上剤として塩化ビニル−酢酸
ビニル−ビニルアルコール共重合体及び／又は塩化ビニ
ル−塩化ビニリデン共重合体が配合された、着色時と消
色時の両状態において透明性を有する可逆熱変色性材料
により可逆熱変色層を形成することもできる。Further, a vinyl chloride-vinyl acetate copolymer resin is used as an electron-donating color-developing organic compound, a compound having a phenolic hydroxyl group, and a three-way homogenous solution of a reaction medium which determines the temperature at which the color reaction of both of them occurs. It is also possible to form a reversible thermochromic layer and a reversible thermochromic masking layer from the reversible thermochromic material described in JP-A-6-135144, which is obtained by dispersing them in a fine particle form into a vinyl chloride- A vinyl acetate copolymer resin blended with a vinyl chloride-vinyl acetate-vinyl alcohol copolymer and / or a vinyl chloride-vinylidene chloride copolymer as a transparency improver, transparent in both colored and decolored states The reversible thermochromic layer can be formed of a reversible thermochromic material having properties.
【００１６】尚、有色（１）から有色（２）に可逆的に
変色する可逆熱変色性材料は、前述した有色から無色に
可逆的に変色する前記した可逆熱変色性材料に一般有色
染顔料を添加して得ることができる。The reversible thermochromic material that reversibly changes from colored (1) to colored (2) is a general colored dye / pigment to the above-mentioned reversible thermochromic material that reversibly changes from colored to colorless. Can be added to obtain.
【００１７】前記図柄層及び可逆熱変色性隠蔽層は、従
来より公知の方法、例えば、スクリーン印刷、オフセッ
ト印刷、グラビヤ印刷、コーター、タンポ印刷、転写等
の印刷手段、刷毛塗り、スプレー塗装、静電塗装、電着
塗装、流し塗り、ローラー塗り、浸漬塗装等の手段によ
り形成することができる。The pattern layer and the reversible thermochromic hiding layer are conventionally known methods, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brushing, spray coating, and static coating. It can be formed by means of electrocoating, electrodeposition coating, flow coating, roller coating, dip coating and the like.
【００１８】尚、前記可逆熱変色層の厚みは５乃至４０
０μｍ、好ましくは１０乃至５０μｍの厚みであること
により、前記した熱変色効果を十分に機能させる。厚み
が４００μｍを越えると伝熱性の面で変色温度設定の自
由度に欠け、５μｍ未満の層では繰り返しの使用による
持久性を満足させ難い。可逆熱変色性隠蔽層の厚みは５
０乃至４００μｍ、好ましくは７０乃至２００μｍの厚
みであることが好ましい。厚みが４００μｍを越えると
図柄層が不鮮明になり、５０μｍ未満の層では十分な隠
蔽性を付与し難い。The thickness of the reversible thermochromic layer is 5 to 40.
When the thickness is 0 μm, preferably 10 to 50 μm, the above-described thermochromic effect is sufficiently performed. When the thickness exceeds 400 μm, the degree of freedom in setting the discoloration temperature is insufficient in terms of heat conductivity, and it is difficult to satisfy the durability due to repeated use in the layer having a thickness of less than 5 μm. The thickness of the reversible thermochromic hiding layer is 5
The thickness is preferably 0 to 400 μm, and more preferably 70 to 200 μm. If the thickness exceeds 400 μm, the pattern layer becomes unclear, and if it is less than 50 μm, it is difficult to provide sufficient hiding power.
【００１９】更に、前記図柄層及び可逆熱変色性隠蔽層
に光安定剤を添加したり、或いはその上層に光安定剤層
を設けることもできる。具体的には、前記光安定剤層は
紫外線吸収剤、酸化防止剤、老化防止剤、一重項酸素消
光剤、スーパーオキシドアニオン消光剤、オゾン消光
剤、可視光線吸収剤、赤外線吸収剤から選ばれる光安定
剤を分散状態に固着した層である。更には老化防止剤、
帯電防止剤、極性付与剤、揺変性付与剤、消泡剤、蛍光
増白剤等を必要に応じて添加して耐久性等の機能を向上
させることができる。Further, a light stabilizer may be added to the pattern layer and the reversible thermochromic hiding layer, or a light stabilizer layer may be provided as an upper layer. Specifically, the light stabilizer layer is selected from an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, a visible light absorber, and an infrared absorber. This is a layer in which the light stabilizer is fixed in a dispersed state. Furthermore, anti-aging agent,
An antistatic agent, a polarity imparting agent, a thixotropic agent, an antifoaming agent, a fluorescent whitening agent and the like may be added as necessary to improve the functions such as durability.
【００２０】又、前記可逆熱変色性隠蔽層の上面には、
保護層として、透明樹脂によるトップコート層を設けた
り、ラミネート処理を施すこともできる。Further, on the upper surface of the reversible thermochromic hiding layer,
As the protective layer, a top coat layer made of a transparent resin may be provided or a laminating process may be performed.
【００２１】[0021]
【発明の実施の形態】以下の実施例における部は重量部
を示す。 実施例１（図１参照） 可逆熱変色性材料として、感温変色性色彩記憶性顔料
〔黒色←→無色、着色温度（低温側変色点）１５℃、消
色温度（高温側変色点）３０℃〕３０部、青色顔料の水
性分散体からなる非変色性顔料０．５部をエチレン−酢
酸ビニル共重合体樹脂エマルジョンを主成分とするスク
リーンインキ用ビヒクル６０部中に均一に分散し、熱変
色性インキＡ〔黒色←→青色、着色温度（低温側変色
点）１５℃、消色温度（高温側変色点）３０℃〕を調製
した。BEST MODE FOR CARRYING OUT THE INVENTION The parts in the following examples indicate parts by weight. Example 1 (see FIG. 1) As a reversible thermochromic material, a thermochromic color memorizing pigment [black ← → colorless, coloring temperature (low temperature side color changing point) 15 ° C., decoloring temperature (high temperature side color changing point) 30 C.] 30 parts, 0.5 part of a non-discoloring pigment consisting of an aqueous dispersion of a blue pigment are uniformly dispersed in 60 parts of a vehicle for a screen ink containing an ethylene-vinyl acetate copolymer resin emulsion as a main component, and heat is added. Discoloring ink A [black ← → blue, coloring temperature (low temperature side color changing point) 15 ° C., decoloring temperature (high temperature side color changing point) 30 ° C.] was prepared.
【００２２】同様にして、感温変色性色彩記憶性顔料と
非変色性顔料との組合せにより、熱変色性インキＢ〔黒
色←→赤紫色、着色温度（低温側変色点）１５℃、消色
温度（高温側変色点）３０℃〕、熱変色性インキＣ〔黒
色←→桃色、着色温度（低温側変色点）１５℃、消色温
度（高温側変色点）３０℃〕、熱変色性インキＤ〔黒色
←→橙色、着色温度（低温側変色点）１５℃、消色温度
（高温側変色点）３０℃〕、熱変色性インキＥ〔黒色←
→黄色、着色温度（低温側変色点）１５℃、消色温度
（高温側変色点）３０℃〕を調製した。Similarly, a thermochromic ink B [black ← → red-purple, coloring temperature (low-temperature side discoloring point) 15 ° C., decoloring was obtained by combining a thermochromic color memory pigment and a non-color-changing pigment. Temperature (high temperature side color changing point) 30 ° C], thermochromic ink C [black ← → pink color, coloring temperature (low temperature side color changing point) 15 ° C, erasing temperature (high temperature side color changing point) 30 ° C], thermocolorable ink D [black ← → orange, coloring temperature (low temperature side discoloring point) 15 ° C, decoloring temperature (high temperature side discoloring point) 30 ° C], thermochromic ink E [black ←
→ Yellow, coloring temperature (low temperature side color change point) 15 ° C., decoloring temperature (high temperature side color change point) 30 ° C.] were prepared.
【００２３】更に、黒色顔料の水性分散体からなる非熱
変色性顔料１．２部をエチレン−酢酸ビニル共重合体樹
脂エマルジョンを主成分とするスクリーンインキ用ビヒ
クル９５部および水３．８部に均一に混合し、黒色の非
変色性インキＧを調製した。Further, 1.2 parts of a non-thermochromic pigment consisting of an aqueous dispersion of a black pigment was added to 95 parts of a vehicle for a screen ink containing ethylene-vinyl acetate copolymer resin emulsion as a main component and 3.8 parts of water. By uniformly mixing, a black non-discoloring ink G was prepared.
【００２４】前記熱変色性インキＡ、Ｂ、Ｃ、Ｄ、Ｅ及
び非変色性インキＧにより、支持体２として裏面に粘着
層を有する白色合成紙〔商品名：ＳＳユポ（ＰＡＴ
Ｉ）、１１０μｍ厚、ＦＳＫ（株）製〕上に１０９メッ
シュのスクリーン版を用いて魚の絵柄を印刷して図柄層
３を形成した。The thermochromic inks A, B, C, D and E and the non-color-changing ink G are used as a support 2 and a white synthetic paper having a pressure-sensitive adhesive layer on the back surface [trade name: SS YUPO (PAT
I), 110 μm thick, manufactured by FSK Co., Ltd.] was used to print a fish pattern using a 109 mesh screen plate to form a pattern layer 3.
【００２５】前記図柄層３は、１５℃以下の温度で、前
記した各熱変色性インキにより形成した像が黒色を呈す
るが、各々の像は近似した黒色であるため、注視すると
黒色の魚の形状を視覚することができる。At the temperature of 15 ° C. or less, the pattern layer 3 shows black images of the above-mentioned thermochromic inks. However, since each image is similar to black, the shape of a black fish when observed carefully. Can be seen.
【００２６】次いで、感温変色性色彩記憶性顔料〔黒色
←→無色、着色温度（低温側変色点）１５℃、消色温度
（高温側変色点）３０℃〕３０部、をエチレン−酢酸ビ
ニル共重合体樹脂エマルジョンを主成分とするスクリー
ンインキ用ビヒクル６０部中に均一に分散して得た熱変
色性インキＦ〔黒色←→無色、着色温度（低温側変色
点）１５℃、消色温度（高温側変色点）３０℃〕を前記
図柄層３上面にスクリーン版でインキ塗布量８０ｇ／ｍ
2 で印刷して可逆熱変色性隠蔽層４を形成して熱変色性
積層体１を得た。Next, 30 parts of a thermosensitive color-changing color memory pigment (black ← → colorless, coloring temperature (color changing point on low temperature side) 15 ° C., decoloring temperature (color changing point on high temperature side) 30 ° C.) was added to ethylene-vinyl acetate. Thermochromic ink F obtained by uniformly dispersing in 60 parts of a vehicle for a screen ink containing a copolymer resin emulsion as a main component [black ← → colorless, coloring temperature (color changing point on low temperature side) 15 ° C, decoloring temperature (High-temperature side color change point) 30 ° C.] on the upper surface of the pattern layer 3 with a screen plate to apply ink of 80 g / m
By printing with 2 , a reversible thermochromic hiding layer 4 was formed to obtain a thermochromic laminate 1.
【００２７】前記熱変色性積層体１は、１５℃以下の温
度に冷却すると、可逆熱変色性隠蔽層４及び図柄層３が
黒色を呈するため、全面が黒色を呈し、３０℃未満の温
度でこの様相は保持された。又、前記黒色を呈する熱変
色性積層体１を３０℃以上に加温すると、前記可逆熱変
色性隠蔽層４が消色すると共に、図柄層２は黒色から多
彩な色調の魚の絵柄を示し、全体として鮮やかな魚の絵
柄の熱変色性積層体１が視覚される。尚、この様相は１
５℃を越える温度で保持され、再び１５℃以下に冷却す
ると全面が黒色を呈し、繰り返し行うことができた。When the thermochromic laminate 1 is cooled to a temperature of 15 ° C. or lower, the reversible thermochromic hiding layer 4 and the pattern layer 3 are black, so that the entire surface is black and the temperature is lower than 30 ° C. This aspect was retained. Further, when the thermochromic laminate 1 exhibiting the black color is heated to 30 ° C. or higher, the reversible thermochromic hiding layer 4 is decolored, and the pattern layer 2 shows a fish pattern of various colors from black, The thermochromic laminate 1 having a vivid fish pattern as a whole is visually recognized. In addition, this aspect is 1
When kept at a temperature over 5 ° C. and cooled again at 15 ° C. or lower, the entire surface became black and it could be repeated.
【００２８】前記熱変色性積層体１は、表１に示したよ
うに図柄層２を完全に隠蔽することができ、しかも可逆
熱変色性隠蔽層４が消色した状態における図柄層も鮮明
であった。前記図柄層の形成に用いた熱変色性インキ
Ａ、Ｂ、Ｃ、Ｄ、Ｅで印刷した可逆熱変色層の各発色時
（０℃）および消色時（５０℃）のＣＩＥ表色値及び熱
変色性インキＦの発色時（０℃）のＣＩＥ表色値を表２
に示し、非変色性インキＧで印刷した非変色層のＣＩＥ
表色値を表３に示す。尚、ＣＩＥ表色値は色差計ＴＣ−
３６００（東京電色株式会社製）により測定し、ｘ、ｙ
はＣＩＥ色度図における色度座標を示し、Ｙは視感反射
率を示す。As shown in Table 1, the thermochromic laminate 1 can completely hide the pattern layer 2, and the pattern layer in the state where the reversible thermochromic masking layer 4 is decolored is also clear. there were. CIE color value at each color development (0 ° C.) and decolorization (50 ° C.) of the reversible thermochromic ink layer printed with the thermochromic inks A, B, C, D and E used for forming the pattern layer, and Table 2 shows the CIE colorimetric values of the thermochromic ink F at the time of color development (0 ° C).
And the CIE of the non-color-changing layer printed with the non-color-changing ink G
The colorimetric values are shown in Table 3. In addition, the CIE colorimetric value is a color difference meter TC-
3600 (manufactured by Tokyo Denshoku Co., Ltd.), x, y
Indicates the chromaticity coordinates in the CIE chromaticity diagram, and Y indicates the luminous reflectance.
【００２９】比較例１ 実施例１における熱変色性インキＡ、Ｂ、Ｃ、Ｄ、Ｅの
感温変色性色彩記憶性顔料をエチレン−酢酸ビニル共重
合体樹脂エマルジョンを主成分とするスクリーンインキ
用ビヒクルに替えて非変色性インキＨ（青色）、非変色
性インキＩ（赤紫色）、非変色性インキＪ（桃色）、非
変色性インキＫ（橙色）、非変色性インキＬ（黄色）を
調製した。Comparative Example 1 For screen inks containing the thermochromic inks A, B, C, D and E of the thermochromic color-changing color memory pigments of Example 1 as the main component of an ethylene-vinyl acetate copolymer resin emulsion. Replace the vehicle with non-color-changing ink H (blue), non-color-changing ink I (magenta), non-color-changing ink J (pink), non-color-changing ink K (orange), non-color-changing ink L (yellow). Prepared.
【００３０】前記非変色性インキと実施例１で用いた非
変色性インキＧにより、実施例１と同様の白色合成紙上
に魚の絵柄を印刷して図柄層を形成した。Using the non-discoloring ink and the non-discoloring ink G used in Example 1, a fish pattern was printed on the same white synthetic paper as in Example 1 to form a pattern layer.
【００３１】次いで、熱変色性インキＦを前記図柄層上
面に各種メッシュのスクリーン版を用いてインキ塗布量
８０ｇ／ｍ2 、１００ｇ／ｍ2 、１５０ｇ／ｍ2 にて印
刷して、熱変色性積層体を得た。前記熱変色性積層体
は、表１に示したように、インキ塗布量を多くしても魚
の絵柄を完全に隠蔽することができず、又、可逆熱変色
性隠蔽層が消色した状態における図柄層も不鮮明であっ
た。前記図柄層の非変色性インキＧ、Ｈ、Ｉ、Ｊ、Ｋ、
Ｌで印刷した部分のＣＩＥ表色値を表３に示す。Then, the thermochromic ink F was printed on the upper surface of the pattern layer using a screen plate of various meshes at an ink coating amount of 80 g / m 2 , 100 g / m 2 , 150 g / m 2 to obtain the thermochromic property. A laminated body was obtained. As shown in Table 1, the thermochromic laminate was unable to completely hide the fish pattern even when the amount of ink applied was increased, and the reversible thermochromic masking layer was in a decolored state. The pattern layer was also unclear. Non-discoloring ink G, H, I, J, K of the design layer,
Table 3 shows the CIE colorimetric values of the portion printed with L.
【００３２】実施例２ 可逆熱変色性材料として熱変色性顔料（紫色←→無色、
着色温度３０℃、消色温度３３℃）４０部、黄色顔料
０．２部を含む水性分散体０．５部をアクリル酸エステ
ル樹脂エマルジョンを主成分とするスクリーン用インキ
ビヒクル１２０部中に均一に分散し、熱変色性インキＭ
（紫色←→黄色、着色温度３０℃、消色温度３３℃）を
調製した。Example 2 A thermochromic pigment (purple ← → colorless, as a reversible thermochromic material)
Coloring temperature 30 ° C, decolorization temperature 33 ° C) 40 parts, 0.5 parts of an aqueous dispersion containing 0.2 parts of a yellow pigment are uniformly dispersed in 120 parts of a screen ink vehicle containing an acrylic ester resin emulsion as a main component. Dispersed and thermochromic ink M
(Purple ← → yellow, coloring temperature 30 ° C., decolorization temperature 33 ° C.) were prepared.
【００３３】同様にして、感温変色性色彩記憶性顔料と
非変色性顔料との組合せにより、熱変色性インキＮ（紫
色←→桃色、着色温度３０℃、消色温度３３℃）、熱変
色性インキＯ（紫色←→青色、着色温度３０℃、消色温
度３３℃）を調製した。Similarly, a thermochromic ink N (purple ← → pink color, coloring temperature 30 ° C., decoloring temperature 33 ° C.), thermochromic color was obtained by combining a thermosensitive color-changing color memory pigment and a non-color-changing pigment. Ink O (purple ← → blue, coloring temperature 30 ° C., decoloring temperature 33 ° C.) was prepared.
【００３４】熱変色性顔料（紫色←→無色、着色温度３
０℃、消色温度３３℃）４０部をアクリル酸エステル樹
脂エマルジョンを主成分とするスクリーン用インキビヒ
クル１２０部中に均一に分散し、熱変色性インキＰ（紫
色←→無色、着色温度３０℃、消色温度３３℃）を調製
した。Thermochromic pigment (purple ← → colorless, coloring temperature 3
40 parts (0 ° C., decoloring temperature 33 ° C.) are uniformly dispersed in 120 parts of an ink vehicle for a screen containing an acrylic ester resin emulsion as a main component, and thermochromic ink P (purple ← → colorless, coloring temperature 30 ° C.) , Erasing temperature 33 ° C.) were prepared.
【００３５】更に、紫色顔料の水性分散体１５部をアク
リル酸エステル樹脂エマルジョンを主成分とするスクリ
ーン用インキビヒクル１２０部中に均一に分散し、紫色
の非変色性インキＱを調製した。Further, 15 parts of an aqueous dispersion of a purple pigment was uniformly dispersed in 120 parts of an ink vehicle for a screen containing an acrylic ester resin emulsion as a main component to prepare a purple non-discoloring ink Q.
【００３６】前記熱変色性インキＭ、Ｎ、Ｏを用いて白
色のキャンバス生地（綿製）に１０９メッシュのスクリ
ーン版を用いて花の絵柄を印刷し、非熱変色性インキＱ
を用いて背景を印刷して図柄層を形成した。A non-thermochromic ink Q is printed by using the thermochromic inks M, N and O to print a flower pattern on a white canvas fabric (cotton) using a 109 mesh screen plate.
Was used to print the background to form a pattern layer.
【００３７】前記した印刷物を３０℃以下の温度にする
と全面が紫色を呈するが、熱変色性インキによる花柄が
背景部分よりも暗紫色であり、且つ、各熱変色性インキ
により形成した像の色調が近似した色調であるため、注
視すると花柄の形状を視覚することができる。When the above-mentioned printed matter is heated to a temperature of 30 ° C. or less, the entire surface exhibits purple, but the flower pattern of the thermochromic ink is darker purple than the background portion, and the color tone of the image formed by each thermochromic ink. Since the color tone is close to, the shape of the flower pattern can be seen when gazing.
【００３８】前記図柄層の花の絵柄部分に熱変色性イン
キＰを１０９メッシュのスクリーン版で印刷して可逆熱
変色性隠蔽層を形成した結果、花の絵柄部分を前記より
視覚濃度の薄い紫色とすることができ、全体が均一な紫
色を呈する。又、手触等によって３３℃以上に加温する
と、紫色のベタ柄から黄色、桃色および青色からなる鮮
やかな花柄が現出した。尚、この様相は再び３０℃以下
に冷却すると全面が紫色を呈し、繰り返し行うことがで
きた。The thermochromic ink P was printed on a 109 mesh screen plate on the flower pattern portion of the pattern layer to form a reversible thermochromic concealing layer. And has a uniform purple color throughout. Further, when heated to 33 ° C. or higher by touch or the like, a vivid floral pattern consisting of a purple solid pattern, yellow, pink and blue appeared. Incidentally, when this aspect was cooled again to 30 ° C. or lower, the entire surface exhibited a purple color and could be repeated.
【００３９】前記図柄層の熱変色性インキＭ、Ｎ、Ｏで
印刷した可逆熱変色層の各発色時（０℃）および消色時
（５０℃）のＣＩＥ表色値及び熱変色性インキＰの発色
時（０℃）のＣＩＥ表色値を表２に示し、非変色性イン
キＱで印刷した非変色層のＣＩＥ表色値を表３に示す。CIE color value and thermochromic ink P at each color development (0 ° C.) and decolorization (50 ° C.) of the reversible thermochromic ink layer printed with the thermochromic ink M, N, O of the pattern layer. Table 2 shows the CIE colorimetric values when the color was developed (0 ° C), and Table 3 shows the CIE colorimetric values of the non-color-changing layer printed with the non-color-changing ink Q.
【表１】 尚、表１の記号は以下のとおり。 図柄隠蔽性（目視による図柄に対する隠蔽性） ○：下層の図柄は視覚されず、十分な隠蔽性を有する。 △：下層の図柄が隠蔽層をとおして視覚できる。 図柄鮮明性（目視による図柄の鮮明性） ○：図柄の色調や輪郭が鮮明に視覚される。 △：下層の図柄の色調や輪郭が隠蔽層によって不鮮明に
視覚される。[Table 1] The symbols in Table 1 are as follows. Design hiding property (visually hiding property): The lower layer pattern is not visually recognized and has sufficient hiding property. Δ: The pattern in the lower layer is visible through the concealing layer. Design sharpness (visual clarity) ○: The color tone and outline of the design are clearly visible. Δ: The color tone and outline of the lower pattern are visually obscured by the concealing layer.
【表２】 [Table 2]
【表３】 尚、表２、表３のｘ、ｙはＣＩＥ色度図における色度座
標を示し、Ｙは視感反射率を示す。[Table 3] In Tables 2 and 3, x and y represent chromaticity coordinates in the CIE chromaticity diagram, and Y represents luminous reflectance.
【００４０】実施例３ 黒色のプラスチック製ミニチュアカーのフロント部分に
白色の非熱変色性油性塗料をスプレーガンにてスプレー
塗装し、炎の形状の白色塗装部分を形成した。前記炎の
形状の白色塗装上面の外周部分に熱変色性油性塗料（茶
色←→黄色、着色温度１６℃、消色温度１８℃）をスプ
レー塗装し、白色塗装上面の中心部分に熱変色性油性塗
料（茶色←→赤色、着色温度１６℃、消色温度１８℃）
をスプレー塗装して図柄層を形成した。Example 3 A white non-thermochromic oil paint was spray-painted with a spray gun on the front part of a black plastic miniature car to form a flame-shaped white paint part. Thermochromic oil paint (brown ← → yellow, coloring temperature 16 ℃, decolorization temperature 18 ℃) is spray-painted on the outer periphery of the flame-shaped white paint, and thermochromic oiliness is applied to the center of the white paint. Paint (brown ← → red, coloring temperature 16 ℃, decolorization temperature 18 ℃)
Was spray-painted to form a pattern layer.
【００４１】前記ミニチュアカーは、１６℃以下の温度
に冷却したところ、前記した各熱変色性油性塗料により
彩色した図柄層が茶色を呈するが、各々の像が近似した
茶色であるため、注視すると黒地に茶色の炎の形状を視
覚することができる。When the miniature car is cooled to a temperature of 16 ° C. or lower, the pattern layers colored by the above-mentioned thermochromic oil-based paints show a brown color, but each image is a brown color similar to each other. You can see the shape of a brown flame on a black background.
【００４２】更に、炎の部分全体に熱変色性油性塗料
（黒色←→無色、着色温度１６℃、消色温度１８℃）を
スプレー塗装した。Further, a thermochromic oily paint (black ← → colorless, coloring temperature 16 ° C., decoloring temperature 18 ° C.) was spray-painted on the entire flame portion.
【００４３】前記の如くして得たミニチュアカーを１６
℃以下に冷却したところ、炎の部分が完全に隠蔽されて
黒色を呈し、１８℃以上に加温したところ黒色のミニチ
ュアカーのフロント部分から鮮やかな赤色、黄色の炎の
絵柄が現出した。尚、この様相は再び１６℃以下に冷却
すると全面が黒色を呈し、繰り返し行うことができた。16 miniature cars obtained as described above
When it was cooled to below ℃, the flame part was completely hidden and exhibited a black color, and when heated above 18 ℃, bright red and yellow flame patterns appeared from the front part of the black miniature car. Incidentally, when this aspect was cooled to 16 ° C. or lower again, the entire surface became black and could be repeated.
【００４４】[0044]
【発明の効果】本発明は、図柄層が多彩な色調を呈する
場合や濃い色調の場合であっても、図柄層を有色（１）
から有色（２）に可逆的に変色する可逆熱変色層により
形成し、前記図柄層を覆う可逆熱変色性隠蔽層による隠
蔽効果を効果的に発現させるため、図柄層の色調と隠蔽
層の色調の相関関係を適性に調整でき、可逆熱変色性隠
蔽層の膜厚を薄くすることができるため、鮮明で多彩な
図柄層を視覚することのできる機能性の高い熱変色性積
層体を提供することができる。According to the present invention, even when the design layer has various color tones or a dark color tone, the design layer is colored (1).
To a colored (2), the color tone of the pattern layer and the color tone of the hiding layer are formed by a reversible thermochromic layer that reversibly changes to a color (2), and the hiding effect of the reversible thermochromic hiding layer that covers the pattern layer is effectively exhibited. The thickness of the reversible thermochromic hiding layer can be adjusted appropriately, and a highly functional thermochromic laminate capable of visually recognizing a variety of clear pattern layers is provided. be able to.
【図１】本発明熱変色性積層体の一実施例の、縦断面図
である。FIG. 1 is a vertical sectional view of an embodiment of a thermochromic laminate of the present invention.
１ 熱変色性積層体 ２ 支持体 ３ 図柄層 ４ 可逆熱変色性隠蔽層 1 Thermochromic Laminate 2 Support 3 Design Layer 4 Reversible Thermochromic Hiding Layer
Claims (2)
を隠蔽する可逆熱変色性隠蔽層よりなる熱変色性積層体
であって、前記図柄層は少なくとも一部が温度変化によ
り有色（１）と有色（２）の可逆的互変性を有し、いず
れか一方が他方より視覚濃度が大である色調を呈する可
逆熱変色層であり、前記可逆熱変色性隠蔽層は、前記可
逆熱変色層の視覚濃度が大である色調に対して、発色時
の色調が同等以上の視覚濃度であるか又は同一乃至近似
色である熱変色性積層体。1. A thermochromic laminate comprising a pattern layer provided on a support and a reversible thermochromic masking layer for masking the pattern layer, wherein at least a part of the pattern layer is colored by a temperature change. (1) and the colored (2) reversible tautomerism, one of which is a reversible thermochromic layer exhibiting a color tone having a greater visual density than the other, and the reversible thermochromic hiding layer is the reversible thermochromic hiding layer. A thermochromic laminate in which the color tone at the time of color development is equal to or higher than the visual tone of the thermochromic layer having a high visual density, or is the same or an approximate color.
色濃度の変化をプロットした曲線の形状が、温度を変色
温度域より低温側から温度を上昇させていく場合と、逆
に変色温度より高温側から下降させていく場合とで大き
く異なる経路を辿って変色し、低温側変色点と高温側変
色点の間の温度域において、有色（１）と有色（２）間
の互変性を呈し、前記有色（１）と有色（２）の両相が
共存できる二相保持領域が常温域にあり、低温側変色点
以下又は高温側変色点以上の温度で変化させた状態を記
憶保持できる熱変色性材料により形成されてなる請求項
１の熱変色性積層体。2. The reversible thermochromic layer has a curve shape plotting a change in coloring density due to a temperature change, in which the temperature rises from a temperature lower than the color change temperature region to a temperature opposite to the color change temperature. Discoloration follows a path that is significantly different when descending from the high-temperature side, and exhibits mutual change between colored (1) and colored (2) in the temperature range between the low-temperature and high-temperature discoloration points. A heat capable of storing and retaining a state in which there is a two-phase holding region in which both the colored (1) and colored (2) phases can coexist in the normal temperature range and which is changed at a temperature lower than the low temperature side discoloration point or higher than the high temperature side discoloration point. The thermochromic laminate according to claim 1, which is formed of a color-changing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8151734A JPH09309174A (en) | 1996-05-22 | 1996-05-22 | Thermal discoloring laminated body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8151734A JPH09309174A (en) | 1996-05-22 | 1996-05-22 | Thermal discoloring laminated body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09309174A true JPH09309174A (en) | 1997-12-02 |
Family
ID=15525132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8151734A Pending JPH09309174A (en) | 1996-05-22 | 1996-05-22 | Thermal discoloring laminated body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09309174A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008063938A (en) * | 2006-08-18 | 2008-03-21 | Mondo Spa | Method for drawing graphic symbol on cover material such as flooring, and cover material relevant to the same |
| JP2016132482A (en) * | 2015-01-21 | 2016-07-25 | 凸版印刷株式会社 | Manufacturing method of thermochromic paper-made lid material and thermochromic paper-made lid material |
| CN110733283A (en) * | 2019-09-26 | 2020-01-31 | 纪可薇 | intelligent temperature-control color-changing ceramic hanging disc and preparation method and control method thereof |
| CN114562759A (en) * | 2022-02-18 | 2022-05-31 | 中熵科技(徐州)有限公司 | Thermochromic heating picture and manufacturing method thereof |
-
1996
- 1996-05-22 JP JP8151734A patent/JPH09309174A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008063938A (en) * | 2006-08-18 | 2008-03-21 | Mondo Spa | Method for drawing graphic symbol on cover material such as flooring, and cover material relevant to the same |
| JP2016132482A (en) * | 2015-01-21 | 2016-07-25 | 凸版印刷株式会社 | Manufacturing method of thermochromic paper-made lid material and thermochromic paper-made lid material |
| CN110733283A (en) * | 2019-09-26 | 2020-01-31 | 纪可薇 | intelligent temperature-control color-changing ceramic hanging disc and preparation method and control method thereof |
| CN114562759A (en) * | 2022-02-18 | 2022-05-31 | 中熵科技(徐州)有限公司 | Thermochromic heating picture and manufacturing method thereof |
| CN114562759B (en) * | 2022-02-18 | 2023-12-29 | 中熵科技(徐州)有限公司 | Thermochromic heating picture and manufacturing method thereof |
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