JPH1121479A - Liquid composition reversibly changing its color with heat - Google Patents

Liquid composition reversibly changing its color with heat

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Publication number
JPH1121479A
JPH1121479A JP20701397A JP20701397A JPH1121479A JP H1121479 A JPH1121479 A JP H1121479A JP 20701397 A JP20701397 A JP 20701397A JP 20701397 A JP20701397 A JP 20701397A JP H1121479 A JPH1121479 A JP H1121479A
Authority
JP
Japan
Prior art keywords
reversible thermochromic
weight
liquid composition
coating
ink
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
Application number
JP20701397A
Other languages
Japanese (ja)
Inventor
Katsuyuki Fujita
勝幸 藤田
Yoshiaki Ono
義明 小野
Yutaka Shibahashi
裕 柴橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pilot Ink Co Ltd
Original Assignee
Pilot Ink Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Pilot Ink Co Ltd filed Critical Pilot Ink Co Ltd
Priority to JP20701397A priority Critical patent/JPH1121479A/en
Publication of JPH1121479A publication Critical patent/JPH1121479A/en
Pending legal-status Critical Current

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  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Pyrrole Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a liquid composition for coating that can reversibly change its color with heat as the resistance to light is improved on the color development. SOLUTION: This composition comprises (a) an electron donor, (b) an electron acceptor, (c) an agent controlling the color-changing temperature and (d) a light resistance-imparting agent that is represented by the formula n=5-17 (straight and branched chain) X=1-4C (straight and branched chain), halogen, Y=1-4C (straight or branched chain), halogen, p=0-3, m=0-3}, has the electron acceptance properties at an amount of 0.3-70 pts.wt. per 1.0 of the electron donor (a), and (e) a liquid vehicle.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は特別の電子受容性を
有する耐光性付与剤を存在させることにより発色時の耐
光性を向上させた可逆的熱変色性被覆用液状組成物に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid composition for reversible thermochromic coating, which has improved light fastness at the time of color development by the presence of a light fastness imparting agent having a special electron accepting property.

【０００２】[0002]

【従来の技術】電子供与性化合物と電子受容性化合物を
組み合わせた熱変色性組成物は例えば米国特許第３，５
６０，２２９号明細書に示されるように公知である。こ
の組成物は組み合わせた両化合物の種類により変色温度
が定まるため、所望の温度で変色する組成物を得ること
が非常に困難であった。本発明者はこの問題を特定のア
ルコールやエステル、ケトンを変色温度調整剤として使
用し変色温度を所望の温度に調整する発明を提供した
（特公昭５１−４４７０６号、特公昭５１−４４７０８
号、特公昭５２−７７６４号、特公平６−５９７４６
号）。2. Description of the Related Art Thermochromic compositions combining an electron-donating compound and an electron-accepting compound are disclosed, for example, in US Pat.
No. 60,229. Since the discoloration temperature of this composition is determined by the type of the two compounds combined, it has been very difficult to obtain a composition that discolors at a desired temperature. The inventor of the present invention has provided inventions which solve this problem by using a specific alcohol, ester or ketone as a discoloration temperature adjusting agent to adjust the discoloration temperature to a desired temperature (JP-B-51-44706, JP-B-51-44708).
No., JP-B No. 52-7774, JP-B-6-59746
issue).

【０００３】[0003]

【発明が解決しようとする課題】本発明者が前に提供し
た発明は同一の電子供与性化合物と電子受容性化合物の
組み合わせであっても変色温度を所望の温度に調節する
ことができる等の点で画期的な発明である。しかしなが
らこれ等の電子供与性化合物と電子受容性化合物を組み
合わせた発明は電子供与性化合物の耐光性が大きくない
ためこれを用いた熱変色性組成物も耐光性が大きくない
欠点がある。そのため変色した色が光により薄くなった
り甚だしいときは完全に脱色する場合もある。従来化合
物に耐光性を付与するために紫外線吸収剤を配合するこ
とが行われているが、電子供与性化合物と電子受容性化
合物からなる熱変色性組成物に紫外線吸収剤を配合する
と消色状態では耐光性が向上するが発色状態ではほとん
ど効果がなく、特に間接光に対しては全く効果がない。
また金属光沢顔料と紫外線吸収剤を併用して可視光線の
一部も遮断すると消色状態の耐光性は飛躍的に改良され
るが発色状態では効果は小さく、特に間接光に対しては
効果がない。この他ヒンダードアミン系、ヒンダードフ
ェノール系、イオウ系、ニッケル錯塩系等の光安定剤は
消色状態でも発色状態でもほとんど効果はない。本発明
者はこのような問題を解決するため、特別な耐光性付与
剤を用いて発色時の耐光性を向上する方法の発明を出願
した。（特願平７−３５４７１１） 本発明は発色時の耐光性を向上した可逆的熱変色性を有
する塗料、印刷インキ、筆記用インキ、化粧料、繊維処
理剤、絵具等の被覆用液状組成物を提供するものであ
る。長期間の可逆的熱変色性の被膜を要求される被覆用
液状組成物には耐光性は非常に重要な性能である。SUMMARY OF THE INVENTION The invention provided by the present inventor before can control the discoloration temperature to a desired temperature even with a combination of the same electron donating compound and electron accepting compound. This is a groundbreaking invention. However, the invention in which the electron donating compound and the electron accepting compound are combined does not have high light fastness of the electron donating compound, and therefore, the thermochromic composition using the compound has a disadvantage that the light fastness is not high. Therefore, when the discolored color becomes thin or severe due to light, it may be completely bleached. Conventionally, an ultraviolet absorber is blended to impart light resistance to the compound. However, when the ultraviolet absorber is blended in a thermochromic composition comprising an electron donating compound and an electron accepting compound, the decolored state is obtained. In this case, the light resistance is improved, but there is almost no effect in the color-developed state, and there is no effect particularly on indirect light.
In addition, when a part of visible light is blocked by using a metallic luster pigment and an ultraviolet absorber together, the light resistance in the decolored state is dramatically improved, but the effect is small in the colored state, and it is particularly effective for indirect light. Absent. In addition, hindered amine-based, hindered phenol-based, sulfur-based, nickel complex salt-based light stabilizers have almost no effect in a decolored state or a colored state. In order to solve such a problem, the present inventor has applied for an invention of a method for improving light fastness at the time of coloring by using a special light fastness imparting agent. (Japanese Patent Application No. 7-354711) The present invention relates to a liquid composition for coating paints, printing inks, writing inks, cosmetics, fiber treatment agents, paints, etc. having reversible thermochromic properties with improved light fastness during color formation. Is provided. Lightfastness is a very important property for a coating liquid composition that requires a long-term reversible thermochromic coating.

【０００４】[0004]

【課題を解決した手段】本発明は、「１． ａ．電子供
与化合物と、 ｂ．電子受容化合物と、 ｃ．変色温度調整剤と、ｄ．つぎの一般式Ｉで示され、
ａ．の電子供与化合物１．０重量部に対し０．３〜７０
重量部の使用割合の電子受容性を有する耐光性付与剤と
一般式ＩAccording to the present invention, there is provided a compound represented by the following general formula I: 1. a. An electron donating compound, b. An electron accepting compound, c.
a. 0.3 to 70 parts by weight of 1.0 part by weight of the electron donating compound
A light-fastness imparting agent having an electron-accepting property and a general formula I

【０００５】[0005]

【化２】 Embedded image

【０００６】｛式中、ｎ＝５〜１７（直鎖及び分岐）、
Ｘ＝Ｃ１〜Ｃ４（直鎖及び分岐）、ハロゲン、Ｙ＝Ｃ１
〜Ｃ４（直鎖及び分岐）、ハロゲン、ｐ＝０〜３、ｍ＝
０〜３である。｝ ｅ．液状の展色料と、からなる、発色時の耐光性を向上
した可逆的熱変色性を有する被覆用液状組成物。２．
ｄ．の電子受容性を有する耐光性付与剤を、ｂ．の電子
受容体に兼用した、１項に記載された発色時の耐光性を
向上した可逆的熱変色性を有する被覆用液状組成物。 ３． ａ．〜ｄ．成分をマイクロカプセルに内蔵した、
１項または２項に記載された発色時の耐光性を向上した
可逆的熱変色性を有する被覆用液状組成物。 ４． ｅ．成分が合成樹脂ビヒクルである、１項ないし
３項のいずれか１項に記載された発色時の耐光性を向上
した可逆的熱変色性を有する被覆用液状組成物。 ５． １項ないし４項のいずれか１項に記載された被覆
用液状組成物のｅ．成分が塗料用展色料である、発色時
の耐光性を向上した可逆的熱変色性塗料。 ６． １項ないし４項のいずれか１項に記載された被覆
用液状組成物のｅ．成分が印刷インキ用展色料である、
発色時の耐光性を向上した可逆的熱変色性印刷インキ。 ７． １項ないし４項のいずれか１項に記載された被覆
用液状組成物のｅ．成分が筆記具用インキ用展色料であ
る、発色時の耐光性を向上した可逆的熱変色性筆記具用
インキ。 ８． １項ないし４項のいずれか１項に記載された被覆
用液状組成物のｅ．成分が化粧料用ラッカーである、発
色時の耐光性を向上した可逆的熱変色性化粧料。 ９． １項ないし４なのいずれか１項に記載された被覆
用液状組成物のｅ．成分が繊維処理剤用バインダであ
る、発色時の耐光性を向上した可逆的熱変色性繊維処理
剤。 １０． １項ないし４項のいずれか１項に記載された被
覆用液状組成物のｅ．成分が絵具用展色料である、発色
時の耐光性を向上した可逆的熱変色性絵具。」に関す
る。Wherein n = 5 to 17 (linear and branched);
X = C 1 ~C 4 (linear and branched), halogen, Y = C 1
-C 4 (linear and branched), halogen, p = 0 to 3, m =
0 to 3. ｝ E. A liquid composition for coating comprising a liquid vehicle and having reversible thermochromic properties with improved light fastness during color development. 2.
d. A lightfastness imparting agent having an electron accepting property of b. 4. The coating liquid composition having reversible thermochromic property and improved light fastness at the time of coloration according to item 1, which is also used as the electron acceptor. 3. a. ~ D. Ingredients built in microcapsules,
4. A coating liquid composition having reversible thermochromic properties as described in item 1 or 2, which has improved light fastness during coloring. 4. e. 4. The liquid composition for coating according to any one of items 1 to 3, wherein the component is a synthetic resin vehicle and has reversible thermochromic properties with improved light fastness during color development. 5. Item e. Of the liquid composition for coating described in any one of items 1 to 4. A reversible thermochromic paint with improved light fastness at the time of color development, which is a coloring agent for paint. 6. Item e. Of the liquid composition for coating described in any one of items 1 to 4. The component is a vehicle for printing ink,
A reversible thermochromic printing ink with improved lightfastness during color development. 7. Item e. Of the liquid composition for coating described in any one of items 1 to 4. A reversible thermochromic ink for writing implements whose component is a coloring agent for ink for writing implements and has improved light fastness during color development. 8. Item e. Of the liquid composition for coating described in any one of items 1 to 4. A reversible thermochromic cosmetic having an improved light fastness at the time of color development, which is a cosmetic lacquer. 9. E. Of the coating liquid composition described in any one of items 1 to 4; A reversible thermochromic fiber treating agent having an improved light resistance at the time of color development, wherein the component is a binder for a fiber treating agent. 10. Item e. Of the liquid composition for coating described in any one of items 1 to 4. A reversible thermochromic paint with improved light fastness during color development, which is a coloring agent for paint. About.

【０００７】本発明は、電子供与性化合物と電子受容性
化合物と変色温度調整剤と液状展色料とからなる可逆的
熱変色性組成物において、前述の一般式Ｉで示される、
耐光性付与剤を電子供与性化合物１．０重量部に対して
０．３〜７０重量部組成物中に存在させることにより発
色時の耐光性を向上させた被覆用液状組成物である。耐
光性付与剤の使用量は電子供与性化合物１．０重量部に
対し２．０〜７，０重量部が特に好ましい。電子供与性
化合物の代表としてロイコ染料があるが、電子供与性化
合物は電子を供与した状態つまりロイコ染料で説明する
と発色状態になるとイオン化されイオン状態となる。こ
のようにイオン化された状態になると耐光性が低下し、
光により電子供与性能が低下し可逆的熱変色性が劣化す
ることがわかった。この発色状態における耐光性の低下
は意外にも可視光線により発生するところが大きい。特
に間接光によって耐光性の低下は発生する。消色状態は
イオン化されてなく、無色の分子状態であるため、可視
光線の影響はほとんどない。The present invention provides a reversible thermochromic composition comprising an electron-donating compound, an electron-accepting compound, a color-changing temperature regulator and a liquid vehicle, represented by the general formula I described above.
It is a coating liquid composition in which the light resistance imparting agent is present in the composition in an amount of 0.3 to 70 parts by weight with respect to 1.0 part by weight of the electron donating compound, so that the light resistance at the time of color development is improved. The use amount of the light fastness-imparting agent is particularly preferably 2.0 to 7.0 parts by weight based on 1.0 part by weight of the electron donating compound. A leuco dye is a representative example of the electron donating compound, and the electron donating compound is ionized and becomes an ionic state when it is in a state of donating electrons, that is, when it is described as a leuco dye, in a colored state. When it is in such an ionized state, light resistance decreases,
It was found that the electron donating performance was reduced by light and the reversible thermochromic property was deteriorated. Surprisingly, the decrease in light resistance in the color-developed state is largely caused by visible light. In particular, the light resistance is reduced by indirect light. Since the decolored state is a non-ionized and colorless molecular state, there is almost no influence of visible light.

【０００８】耐光性を向上するために使用されている、
紫外線吸収剤、金属光沢顔料、酸化防止剤、老化防止剤
等はロイコ染料の消色状態の耐光性向上には効果がある
が、発色状態では効果が非常に小さい。従来使用されて
いるこのような耐光性配合剤は、分子状態にある物質の
耐光性を向上する作用はある。通常光を受ける可能性の
ある所で使用されている物質は分子状態にあるものがほ
とんどであって、イオン状態で使用されるものは稀であ
り、紫外線吸収剤等で充分効果があった。[0008] used to improve light fastness,
Ultraviolet absorbers, metallic luster pigments, antioxidants, antioxidants, etc. are effective in improving the light fastness of the decolorized state of the leuco dye, but are very small in the colored state. Such a light-fast compounding agent conventionally used has an effect of improving the light fastness of a substance in a molecular state. Most of the substances which are usually used in a place where there is a possibility of receiving light are in a molecular state, and those which are used in an ionic state are rare, and an ultraviolet absorber or the like is sufficiently effective.

【０００９】ところが、本発明の可逆的熱変色性を有す
る被覆用液状組成物は特殊な技術に属し、電子を供与し
た物質はイオン状態となりこの状態で組成物は発色す
る。そして消色状態では分子状態となっており、分子状
態では無色で可視光線を吸収しないため、紫外線のカッ
トだけで、十分な耐光性向上効果がある。一方、イオン
状態では、着色しているため、紫外線のカットだけでは
不十分であり、更に可視光線のカットも必要である。However, the coating liquid composition having reversible thermochromic properties of the present invention belongs to a special technique, and the electron donating substance becomes an ionic state, and the composition develops a color in this state. In the decolored state, it is in the molecular state, and in the molecular state, it is colorless and does not absorb visible light. Therefore, merely cutting off ultraviolet rays has a sufficient effect of improving light resistance. On the other hand, in the ionic state, since it is colored, it is not sufficient to cut only ultraviolet rays, and further, it is necessary to cut visible rays.

【００１０】本発明の可逆的熱変色性を有する被覆用液
状組成物の発色状態と消色状態について説明する。本発
明での可逆的熱変色性を有する被覆用液状組成物のａ．
成分、ｂ．成分、ｃ．成分は実際に取扱う状態ではイオ
ン化合物ではなく、全て分子状化合物である。これ等の
成分が均一に混合された可逆的熱変色性を有する被覆用
液状組成物において、変色温度以下になるとａ．成分と
ｂ．成分がイオン化して結合し発色状態となる。逆に変
色温度以上になるとａ．成分とｂ．成分のイオン的結合
が消滅して、ａ．成分とｂ．成分は互いに独立して分子
状化合物になり消色する。ｂ．成分のフェノール性水酸
基はｃ．成分の変色温度調整剤に溶解することにより溶
媒和してｃ．成分との親和力が強くなる。また変色過度
期においてはａ．成分とｂ．成分はイオン化状態と分子
状態の中間状態となり、ある程度イオン化された状態で
弱いイオン的結合をしていると考えられる。少しでもイ
オン化された状態となれば発色が生ずるので発色状態の
耐光性の問題が発生する。したがって、耐光性に関して
は遷移状態は発色状態とみなされる。したがって、通常
使用される紫外線吸収剤等の耐光性配合剤は消色状態の
組成物の耐光性の向上には有効であるが、発色状態にあ
る組成物の耐光性の向上にはあまり効果がない。この状
態のものは可視光線や間接光に対する耐光性は弱い。The color forming state and the color erasing state of the liquid composition for coating having reversible thermochromic property of the present invention will be described. A. Liquid reversible thermochromic coating composition according to the present invention:
A component, b. A component, c. The components are not ionic compounds but actually molecular compounds when actually handled. In a coating liquid composition having a reversible thermochromic property in which these components are uniformly mixed, when the color changing temperature is equal to or lower than a. Ingredients and b. The components are ionized and combined to form a colored state. Conversely, if the temperature exceeds the discoloration temperature, a. Ingredients and b. The ionic bonds of the components disappear, and a. Ingredients and b. The components become molecular compounds independently of each other and decolorize. b. The phenolic hydroxyl group of the component is c. Solvate by dissolving in the discoloring temperature controlling agent of the component; c. The affinity with the component is increased. In the discoloration transition period, a. Ingredients and b. It is considered that the component is in an intermediate state between the ionized state and the molecular state, and has a weak ionic bond in a state of being ionized to some extent. If a little ionized state occurs, a color is generated, so that a problem of light fastness in the colored state occurs. Therefore, regarding the light fastness, the transition state is regarded as a colored state. Therefore, a commonly used light-resistant compound such as an ultraviolet absorber is effective in improving the light resistance of a composition in a decolored state, but is not so effective in improving the light resistance of a composition in a colored state. Absent. In this state, light resistance to visible light and indirect light is weak.

【００１１】ところが本発明で使用する、一般式Ｉで示
される耐光性付与剤を発色時に存在させると耐光性か著
しく向上し、可視光や間接光でも老化しないことがわか
った。何故本発明の可逆的熱変色性を有する被覆用液状
組成物が、発色状態にあると、可視光線や、間接光で老
化しないのか、消色状態にあるとこれ等の光で老化しな
いのか、その学問的解明は未だ充分ではないが、本発明
者は一般式Ｉで示されるｄ．耐光性付与剤は、電子受容
性を有するため、ｃ．の変色温度調整剤中で、ａ．電子
供与性呈色性有機化合物と共存した場合、変色温度以下
では、ａ．電子供与性呈色性有機化合物とイオン的に強
く相互作用を行い、発色状態を形成することができる。
勿論、ａ．電子供与性呈色性有機化合物は、通常のｂ．
電子受容性化合物と、イオン的に強く相互作用し、発色
状態を形成するが、発色状態となった時の、イオン的な
相互作用に基づくイオン構造が、ａ．とｂ．の場合と、
ａ．とｄ．の場合で、光に対する安定性が大きく異なっ
ていると考えられる。However, it has been found that when the lightfastness-imparting agent represented by the general formula I used in the present invention is present at the time of coloring, the lightfastness is remarkably improved, and it does not age even with visible light or indirect light. Why the coating liquid composition having reversible thermochromic properties of the present invention, when in a color-developed state, does not age with visible light or indirect light, or does not age with such light when in a decolorized state, Although the scholarly elucidation is not yet sufficient, the present inventor has proposed that d. Since the light resistance imparting agent has an electron accepting property, c. In the discoloration temperature regulator of a. When coexisting with an electron-donating color-forming organic compound, a. It interacts strongly with the electron-donating color-forming organic compound in an ionic manner to form a colored state.
Of course, a. The electron-donating color-forming organic compound may be any of ordinary b.
It interacts strongly with the electron-accepting compound to form a colored state. When the colored state is reached, the ionic structure based on the ionic interaction is a. And b. And
a. And d. In this case, it is considered that the stability to light is greatly different.

【００１２】ｄ．耐光性付与剤は、長鎖アルキル基を有
しており、脂肪族雰囲気の強いｃ．変色温度調整剤への
溶解性が大きい。そのため、被覆用に使用され形成され
た被膜中において変色温度以下のｃ．変色温度調整剤が
結晶化した固体中においても、ａ．電子供与性呈色性有
機化合物と強く相互作用してイオン状態を形成したｄ．
耐光性付与剤は、ｃ．変色温度調整剤と弱く相互作用し
た状態で、長鎖アルキル基の部分がｃ．変色温度調整剤
が結晶化した固体中で、安定化しており、その結果、イ
オン状態の構造全体が光に対し安定化した状態になるの
ではないかと思われる。従って、イオン状態にあるａ．
電子供与性呈色性有機化合物が、可視光線を吸収して光
励起しても、光分解あるいは光酸化されずに、そのエネ
ルギーを放出して基底状態に戻る安定したサイクルにな
る状態を、全体として形成しているのではないかと推察
する。さらに、長鎖アルキル基を有する構造は各種存在
するが、その中でも、一般式Ｉで示される構造が優れた
耐光性向上効果を示すのは、中心炭素の片方に水素、も
う一方に長鎖アルキル基となった分岐していない構造で
あるため、ｃ．変色温度調整剤が結晶化した固体中にお
ける馴染み易さ、すなわち安定性が特に優れているから
ではないかと思われる。D. The light resistance imparting agent has a long-chain alkyl group and has a strong aliphatic atmosphere. High solubility in discoloration temperature regulator. Therefore, in the formed film used for coating, c. Even in a solid in which the discoloration temperature regulator has crystallized, a. Strongly interacts with an electron-donating color-forming organic compound to form an ionic state d.
The lightfastness-imparting agent is c. When weakly interacting with the color change temperature regulator, the long-chain alkyl moiety is c. It is considered that the discoloration temperature regulator is stabilized in the crystallized solid, and as a result, the entire structure in an ionic state is stabilized against light. Therefore, a.
Even if the electron-donating color-forming organic compound absorbs visible light and is photoexcited, it does not undergo photolysis or photo-oxidation, but releases its energy and returns to the ground state in a stable cycle. I guess it is forming. Further, there are various types of structures having a long-chain alkyl group. Among them, the structure represented by the general formula I shows an excellent effect of improving light resistance because one of the central carbon atoms has hydrogen and the other has a long-chain alkyl group. Because of the base unbranched structure, c. This is probably because the discoloration temperature regulator is particularly easy to blend into the crystallized solid, that is, has excellent stability.

【００１３】一方、通常のｂ．電子受容性化合物の場合
には、アルキル基が短く、変色温度以下のｃ．変色温度
調整剤が結晶化した固体中における馴染み易さが少な
く、安定性の悪い状態で、ａ．とｂ．のイオン状態の構
造が存在していると考えられる。従って、イオン状態に
あるａ．電子供与性呈色性有機化合物が、可視光線を吸
収して光励起すると、光分解あるいは光酸化する反応が
優先し、劣化がすすむのではないかと思われる。本発明
で使用するｄ．耐光性付与剤はそれ自体も電子受容性を
有しており電子供与性化合物１．０重量部に対し０．３
重量部以上発色状態で存在する必要がある。可逆的熱変
色性被覆用液状組成物が発色した状態で耐光性付与剤が
電子供与性化合物１．０重量部に対し０．３重量部以下
の量が存在したのでは形成された被膜は充分な耐光性が
得られない。On the other hand, the usual b. In the case of an electron-accepting compound, the alkyl group is short and has a color change temperature of c. In a state where the discoloration temperature adjusting agent is less easily compatible with the crystallized solid and has poor stability, a. And b. It is considered that the structure in the ionic state exists. Therefore, a. When the electron-donating color-forming organic compound absorbs visible light and is photo-excited, the reaction of photo-decomposition or photo-oxidation takes precedence, and it is thought that the deterioration proceeds. D. Used in the present invention; The light fastness imparting agent itself has an electron accepting property, and 0.3 part by weight of the electron donating compound is 1.0 part by weight.
It must be present in a color development state by weight part or more. If the lightfastness-imparting agent is present in an amount of 0.3 parts by weight or less based on 1.0 part by weight of the electron-donating compound in a state in which the liquid composition for reversible thermochromic coating has developed color, the formed film is insufficient. Light resistance cannot be obtained.

【００１４】本発明で使用する一般式Ｉで示されるｄ．
耐光性付与剤は、一般式ＩThe d. Compound represented by the general formula I used in the present invention.
The lightfastness-imparting agent has the general formula I

【００１５】[0015]

【化３】 Embedded image

【００１６】｛式中、ｎ＝５〜１７（直鎖及び分岐）、
Ｘ＝Ｃ１〜Ｃ４（直鎖及び分岐）、ハロゲン、Ｙ＝Ｃ１
〜Ｃ４（直鎖及び分岐）、ハロゲン、ｐ＝０〜３、ｍ＝
０〜３である。｝で示されるアルキル基に水酸基を有す
るフェニル環が２つついたビスフェノール化合物或いは
ビス（ヒドロキシフェニル）化合物であるが、その特徴
はアルキル基が炭素数５〜１７であることであって、炭
素数が５未満であると、アルキル基が短いので脂肪族雰
囲気が強いｃ．変色温度調整剤への溶解性が不足し、変
色温度以下の固体雰囲気下で、十分な安定化構造が得ら
れない。また炭素数１７を越えると、アルキル基が長過
ぎるので脂肪族雰囲気が強いｃ．変色温度調整剤への溶
解性があり過ぎ、実用面を考えた場合、呈色力が弱くな
るとともに、変色感度が悪化するため、実用的ではな
い。アルキル基が直鎖アルキル基であることが最も好ま
しく、分岐を有する場合は分岐の短いものが好ましい。
フェニル環には直鎖または分岐アルキル基やハロゲンの
置換基がつく場合があるがフェニル環が付いているアル
キル基が前記のものであれば耐光性はほぼ同様に奏され
る。本発明で使用する耐光性付与剤はそれ自体も電子受
容性があるのでこれを用いることにより電子受容性化合
物の使用量を調整したり、場合によっては置き換えるこ
ともできる。Wherein n = 5 to 17 (linear and branched);
X = C 1 ~C 4 (linear and branched), halogen, Y = C 1
-C 4 (linear and branched), halogen, p = 0 to 3, m =
0 to 3. A bisphenol compound or a bis (hydroxyphenyl) compound in which two phenyl rings having a hydroxyl group are present in the alkyl group represented by つ つ is characterized in that the alkyl group has 5 to 17 carbon atoms and the number of carbon atoms is If it is less than 5, the aliphatic atmosphere is strong because the alkyl group is short. C. The solubility in the discoloration temperature regulator is insufficient, and a sufficient stabilized structure cannot be obtained in a solid atmosphere at or below the discoloration temperature. If the number of carbon atoms exceeds 17, the alkyl group is too long and the aliphatic atmosphere is strong. C. It has too much solubility in the discoloring temperature adjusting agent, and when considered from a practical point of view, it is not practical because the coloring power is weakened and the discoloring sensitivity is deteriorated. Most preferably, the alkyl group is a straight-chain alkyl group.
The phenyl ring may have a straight-chain or branched alkyl group or a halogen substituent, but if the alkyl group having the phenyl ring is as described above, the light resistance is almost the same. Since the light fastness imparting agent used in the present invention itself has an electron accepting property, the use thereof can be used to adjust the amount of the electron accepting compound to be used or to replace it in some cases.

【００１７】一般式Ｉで示されるｄ．耐光性付与剤を
ｂ．成分の電子受容性化合物に置き換える場合はこの化
合物が長鎖アルキル基を有しており、フェノール性水酸
基の当量が小さくなっているので、ａ．成分の電子供与
性化合物１．０重量部に対し０．３〜７．０重量部使用
する必要があり、特に２．０〜７．０重量部が好まし
い。成分ｂ．の電子受容性化合物としては、活性プロト
ンを有する化合物、偽酸性化合物群〔酸ではないが、組
成物中で酸として作用して成分ａ．を発色させる化合物
群〕、電子空孔を有する化合物群などがある。フェノー
ル性水酸基を有する化合物が最も有効な熱変色特性を発
現させることができるが、芳香族カルボン酸及び炭素数
２〜５の脂肪酸カルボン酸、カルボン酸金属塩、酸性リ
ン酸エステル及びそれらの金属塩、１、２、３−トリア
ゾール及びその誘導体、チオ尿素及びその誘導体、尿素
及びその誘導体、グアニジン及びその誘導体、芳香族及
び脂肪酸カルボン酸無水物、ホウ酸エステル類、ハロゲ
ン化アルコール類、オキサゾール類、チアゾール類、イ
ミダゾール類、ピラゾール類、ピロール類、芳香族スル
ホンアミド類、芳香族スルホンイミド類から選ばれる化
合物であってもよい。D. Represented by the general formula I B. A lightfastness-imparting agent; When the component is replaced with an electron-accepting compound, since this compound has a long-chain alkyl group and the equivalent weight of the phenolic hydroxyl group is small, a. It is necessary to use 0.3 to 7.0 parts by weight, preferably 2.0 to 7.0 parts by weight, based on 1.0 part by weight of the component electron donating compound. Component b. Examples of the electron-accepting compound include compounds having an active proton and a group of pseudo-acidic compounds [not an acid, but act as an acid in the composition to form a component a. And a group of compounds having electron vacancies. A compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties. However, aromatic carboxylic acids and fatty acid carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acid phosphates, and metal salts thereof 1,2,3-triazole and its derivatives, thiourea and its derivatives, urea and its derivatives, guanidine and its derivatives, aromatic and fatty acid carboxylic anhydrides, boric esters, halogenated alcohols, oxazoles, It may be a compound selected from thiazoles, imidazoles, pyrazoles, pyrroles, aromatic sulfonamides, and aromatic sulfonimides.

【００１８】本発明で使用する一般式Ｉで示される耐光
性付与剤はそれ自身が電子受容性を有する化合物であ
り、ｂ．成分の電子受容性化合物の量を調整することが
好ましい。またｂ．成分に代えて耐光性付与剤で兼用す
ることもできる。The light-fastness-imparting agent represented by the general formula I used in the present invention is a compound which itself has an electron-accepting property, and b. It is preferable to adjust the amount of the component electron accepting compound. B. Instead of the components, a lightfastness-imparting agent can also be used.

【００１９】本発明で使用されるａ．成分の電子供与性
呈色性化合物を表１と表２に例示する。A. Used in the present invention. Tables 1 and 2 show examples of the component electron-donating color-forming compounds.

【００２０】[0020]

【表１】 [Table 1]

【００２１】[0021]

【表２】 [Table 2]

【００２２】本発明で使用されるｂ．成分の電子受容性
化合物を表３ないし表５に例示する。B. Used in the present invention. Tables 3 to 5 show examples of the component electron accepting compounds.

【００２３】[0023]

【表３】 [Table 3]

【００２４】[0024]

【表４】 [Table 4]

【００２５】[0025]

【表５】 [Table 5]

【００２６】本発明で使用するｃ．成分の変色温度調整
剤を表６ないし表１２に示す。The c. Used in the present invention. Tables 6 to 12 show the discoloring temperature regulators of the components.

【００２７】[0027]

【表６】 [Table 6]

【００２８】[0028]

【表７】 [Table 7]

【００２９】[0029]

【表８】 [Table 8]

【００３０】[0030]

【表９】 [Table 9]

【００３１】[0031]

【表１０】 [Table 10]

【００３２】[0032]

【表１１】 [Table 11]

【００３３】[0033]

【表１２】 [Table 12]

【００３４】本発明で使用するｄ．成分の耐光性付与剤
を表１３と表１４に示す。D. Used in the present invention. Tables 13 and 14 show the components of the light resistance imparting agent.

【００３５】[0035]

【表１３】 [Table 13]

【００３６】[0036]

【表１４】 [Table 14]

【００３７】本発明で使用するｅ．成分の液状展色料は
樹脂、溶剤、各種添加剤等の成分から構成される。液状
展色料に使用できる樹脂を表１５に示す。E. Used in the present invention. The liquid vehicle as a component is composed of components such as a resin, a solvent, and various additives. Table 15 shows resins that can be used in the liquid vehicle.

【００３８】[0038]

【表１５】 [Table 15]

【００３９】これらの樹脂は樹脂エマルジョン、一部の
中分子量ポリマー、及びエポキシ樹脂等の一部の反応型
樹脂を除き、室温では固体状態であるため、水、脂肪族
炭化水素類、芳香族炭化水素類、アルコール類、グリコ
ール類、グリコール誘導体類、エステル類、ケトン類等
の有機溶剤に溶解又は分散することにより、液状となす
ことができる。これらの樹脂により、被覆膜を形成する
ことができる。樹脂として合成樹脂又は合成中分子量ポ
リマーを使用した液状展色料を合成樹脂ビヒクルとい
う。Since these resins are in a solid state at room temperature except for resin emulsions, some medium-molecular-weight polymers, and some reactive resins such as epoxy resins, water, aliphatic hydrocarbons, and aromatic hydrocarbons are used. It can be made liquid by dissolving or dispersing it in an organic solvent such as hydrogens, alcohols, glycols, glycol derivatives, esters, and ketones. With these resins, a coating film can be formed. A liquid vehicle using a synthetic resin or a high molecular weight polymer during synthesis as a resin is called a synthetic resin vehicle.

【００４０】[0040]

【発明の実施の形態】本発明の可逆的熱変色性を有する
被覆用液状組成物は、ａ．成分〜ｅ．成分からなる液状
組成物で基材等に塗布して使用される。本発明の可逆的
熱変色性を有する被覆用液状組成物としては塗料、印刷
インキ、筆記用インキ、化粧料、繊維処理剤、絵具等が
ある。ａ．成分〜ｄ．成分はマイクロカプセルに内蔵し
て使用することが好ましい。このようなマイクロカプセ
ルに内蔵することによりａ．成分〜ｄ．成分は必ず全成
分が存在する状態でとなるのでこれを配合した被覆用液
状組成物は均一な組成物となり確実な効果を奏すること
ができる。DETAILED DESCRIPTION OF THE INVENTION The coating liquid composition having reversible thermochromic properties of the present invention comprises: a. Component-e. It is used by applying it to a substrate or the like with a liquid composition comprising the components. The coating liquid composition having reversible thermochromic properties of the present invention includes paints, printing inks, writing inks, cosmetics, fiber treatment agents, paints, and the like. a. Component-d. It is preferable that the components are used by being incorporated in microcapsules. By incorporating in such a microcapsule, a. Component-d. Since the components are always in a state where all the components are present, the coating liquid composition containing the components becomes a uniform composition and can exert a certain effect.

【００４１】ｅ．成分の展色料として塗料形成展色料を
用いれば可逆的熱変色性塗料となる。塗装方法には、刷
毛塗り、スプレー塗装、静電気塗装、浸漬塗装、流し塗
り、ローラー塗装、光重合塗装等があり、これらの塗装
方法、塗装対象素材に応じて蒸発乾燥型、浸透乾燥型、
エマルジョン型、酸化重合型、熱硬化樹脂型、光硬化樹
脂型塗料等が調製される。またｅ．成分として印刷イン
キ基材を用いれば可逆的熱変色性印刷インキが得られ
る。印刷方法には、凹版、凸版、平版、孔版、コーター
等による印刷方法があり、これらの印刷方法、印刷対象
素材に応じて蒸発乾燥型、浸透乾燥型、エマルジョン
型、酸化重合型、熱硬化樹脂型、光硬化樹脂型等の印刷
インキが調製される。ｅ．成分として筆記用インキ基材
の展色料を用いれば筆記用インキが得られる。筆記具用
インキには筆記機構に応じて、粘度、剪断減粘性等の流
動適性が調整され、筆記対象に応じて、蒸発乾燥型、エ
マルジョン型等各種の筆記具用インキが調製される。
ｅ．成分として化粧料用ラッカーを用いればマニキュア
用化粧料が得られる。化粧料には、マニキュア用化粧
料、メイクアップ用化粧料、毛髪用化粧料等があり、化
粧対象に応じて、各種の組成の化粧料が調製される。
ｅ．成分として繊維処理用のバインダーを用いれば繊維
処理剤が得られる。繊維処理方法としては、浸漬、スプ
レー塗装等があり、処理方法、対象素材に応じて、各種
の組成の繊維処理剤が調製される。ｅ．成分として絵具
用展色料を用いれば可逆的熱変色性絵具が得られる。こ
れらの各種の被覆方法に応じて、非熱変色性着色剤、架
橋剤、硬化剤、乾燥剤、可塑剤、粘度調整剤、分散剤、
紫外線吸収剤、酸化防止剤、光安定剤、沈降防止剤、平
滑剤、ゲル化剤、消泡剤、つや消し剤、浸透剤、ｐＨ調
整剤、発泡剤、カップリング剤、保湿剤、防かび剤、防
腐剤、防錆剤等の各種添加剤を適宜に加えることによ
り、被覆用液状組成物となす。E. When a paint forming vehicle is used as a vehicle for the components, a reversible thermochromic paint is obtained. Coating methods include brush coating, spray coating, electrostatic coating, dip coating, flow coating, roller coating, photopolymerization coating, etc., depending on these coating methods and the material to be coated, evaporative drying type, penetration drying type,
An emulsion type, an oxidative polymerization type, a thermosetting resin type, a photocurable resin type paint and the like are prepared. E. When a printing ink base is used as a component, a reversible thermochromic printing ink can be obtained. Printing methods include intaglio, letterpress, lithographic, stencil, and coater printing methods.Evaporation drying type, penetration drying type, emulsion type, oxidation polymerization type, thermosetting resin A printing ink such as a mold and a photocurable resin mold is prepared. e. If a coloring material of a writing ink base material is used as a component, a writing ink is obtained. Fluidity such as viscosity and shear thinning property is adjusted for the writing implement ink according to the writing mechanism, and various writing implement inks such as evaporative drying type and emulsion type are prepared according to the writing object.
e. If a lacquer for cosmetics is used as a component, a cosmetic for nail polish can be obtained. Cosmetics include manicure cosmetics, makeup cosmetics, hair cosmetics, and the like. Cosmetics having various compositions are prepared according to the makeup subject.
e. If a binder for fiber treatment is used as a component, a fiber treatment agent can be obtained. Fiber treatment methods include immersion and spray coating, and fiber treatment agents having various compositions are prepared according to the treatment method and the target material. e. Use of a paint colorant as a component provides a reversible thermochromic paint. Depending on these various coating methods, non-thermochromic colorants, crosslinking agents, curing agents, drying agents, plasticizers, viscosity modifiers, dispersants,
UV absorbers, antioxidants, light stabilizers, antisettling agents, leveling agents, gelling agents, defoamers, matting agents, penetrants, pH adjusters, foaming agents, coupling agents, humectants, fungicides A liquid composition for coating is formed by appropriately adding various additives such as a preservative and a rust preventive.

【００４２】[0042]

【実施例】次に実施例を上げて具体的に説明する。まず
熱変色性組成物の製造例を示す。 熱変色性組成物の製造例１ ３−（Ｎ−イソブチル−Ｎ−エチルアミノ）−７，８−
ベンゾフルオラン１．０重量部、セチルアルコール２
５．０重量部、カプリン酸ステアリル２５重量部、１，
１−ビス（４−ヒドロキシフェニル）−ｎ−デカン８．
０重量部からなる４成分を１２０℃にて加温溶解して均
質相溶体となし、エポン８２８（油化シェルエポキシ株
式会社製、エポキシ樹脂）１０重量部の混合溶液に混合
した後、これを１０％ゼラチン水溶液１００重量部中に
滴下し、微小滴になるように撹拌する。別に用意した
５．０重量部の硬化剤エピキュアＵ（油化シェルエポキ
シ株式会社製、エポキシ樹脂のアミン付加物）を４５．
０重量部の水に溶解させた溶液を前記撹拌中の溶液中に
徐々に添加し、液温を８０℃に保って約５時間撹拌を続
け、マイクロカプセル原液を得た。前記原液を遠心分離
処理することにより、ピンクから無色に変化するマイク
ロカプセルに内包した可逆熱変色性組成物１を得た。Next, the present invention will be described in detail with reference to examples. First, a production example of the thermochromic composition will be described. Production Example 1 of Thermochromic Composition 3- (N-isobutyl-N-ethylamino) -7,8-
Benzofluorane 1.0 part by weight, cetyl alcohol 2
5.0 parts by weight, stearyl caprate 25 parts by weight,
7. 1-bis (4-hydroxyphenyl) -n-decane
The four components consisting of 0 parts by weight were heated and dissolved at 120 ° C. to form a homogeneous solution, mixed with a mixed solution of 10 parts by weight of Epon 828 (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy resin), and mixed The solution is added dropwise to 100 parts by weight of a 10% gelatin aqueous solution, and the mixture is stirred so as to be fine droplets. Separately, 5.0 parts by weight of a curing agent EpiCure U (manufactured by Yuka Shell Epoxy Co., Ltd., amine adduct of epoxy resin) was used.
A solution dissolved in 0 parts by weight of water was gradually added to the stirring solution, and stirring was continued for about 5 hours while maintaining the solution temperature at 80 ° C. to obtain a stock solution of microcapsules. By centrifuging the stock solution, a reversible thermochromic composition 1 encapsulated in microcapsules that changed from pink to colorless was obtained.

【００４３】（１） 熱変色性組成物の製造例２〜１６ ａ．成分、ｂ．成分、ｃ成分、ｄ．成分の組み合わせを
変えて他は製造例１と同様にして熱変色性組成物２〜１
６を得た。これ等の熱変色性組成物の組成と色の変化を
表１６と表１７に示す。(1) Production Examples 2 to 16 of Thermochromic Composition a. A component, b. Component, c component, d. Thermochromic compositions 2 to 1 were the same as in Production Example 1 except for changing the combination of components.
6 was obtained. Tables 16 and 17 show the composition and color change of these thermochromic compositions.

【００４４】[0044]

【表１６】 [Table 16]

【００４５】[0045]

【表１７】 [Table 17]

【００４６】実施例１ 《水性スプレー塗料》 熱変色性組成物−１のマイクロカプセル顔料３０．０重
量部を、アクリル酸エステル樹脂エマルジョン４５．０
重量部、消泡剤１．０重量部、希釈水２４．０重量部か
らなるビヒクル中に均一分散し、１８０メッシュステン
レススクリーンで瀘過をして、可逆的熱変色性水性スプ
レー塗料を得た。次ぎに、透過率５０％の布帛に口径
０．６ｍｍのスプレーガンを用いて、ピンク色、黄色、
オレンジ色の非変色性スプレー塗装を塗装してカラフル
な花柄の図柄を形成した。前記、非変色性スプレー塗装
を用いて花柄を形成した布帛上の全面に前記スプレーガ
ンを用いて前記可逆的熱変色性スプレー塗装を塗装した
後乾燥させて可逆的熱変色性布帛を得た。また前記布帛
を縫製して可逆的熱変色性人形用ドレスを作製した。前
記人形用ドレスは３０℃以下の環境ではピンク色を呈
し、３０℃以上に加温すると鮮やかな花柄が現出する。Example 1 << Aqueous Spray Coating >> 30.0 parts by weight of the microcapsule pigment of the thermochromic composition-1 was added to an acrylic resin emulsion 45.0.
Parts by weight, a defoamer of 1.0 part by weight, and 24.0 parts by weight of diluting water were uniformly dispersed in a vehicle and filtered through a 180-mesh stainless screen to obtain a reversible thermochromic aqueous spray paint. . Next, using a spray gun with a caliber of 0.6 mm on a cloth having a transmittance of 50%, pink, yellow,
The orange non-discoloring spray paint was applied to form a colorful floral design. The reversible thermochromic spray coating was applied using the spray gun on the entire surface of the fabric on which the floral pattern was formed using the non-color-changing spray coating, followed by drying to obtain a reversible thermochromic fabric. . The cloth was sewn to produce a reversible thermochromic doll dress. The doll dress exhibits a pink color in an environment of 30 ° C. or lower, and a bright floral pattern appears when heated to 30 ° C. or higher.

【００４７】実施例２ 《油性スプレー塗料》 可逆的熱変色性組成物−４のマイクロカプセル顔料を１
５．０重量部及び蛍光顔料（蛍光ピンク）３．０重量
部、５０％アクリル樹脂／キシレン溶液４０．０重量
部、キシレン２０．０重量部、及びメチルイソブチルケ
トン２０．０重量部、ポリイソシアネート系硬化剤６．
０重量部からなるビヒクル中に撹拌混合して可逆的熱変
色性油性スプレー塗装を得た。前記可逆的熱変色性油性
スプレー塗装を、ＡＢＳ樹脂を射出成形した車型のミニ
チュアカーのボディーの全体に、口径０．６ｍｍのスプ
レーガンを用いてスプレー塗装を施して乾燥し、可逆的
熱変色性層を施したミニチュアカーを得た。前記の如く
塗装された可逆的熱変色性ミニチュアカーを３３℃以上
に加温するとピンク色を呈し、１４℃以下で紫色を呈す
る。その間の温度域では任意にピンク色と紫色を選択保
持できる。Example 2 << Oil-based spray paint >> The microcapsule pigment of the reversible thermochromic composition-4 was added to 1
5.0 parts by weight and fluorescent pigment (fluorescent pink) 3.0 parts by weight, 50% acrylic resin / xylene solution 40.0 parts by weight, xylene 20.0 parts by weight, methyl isobutyl ketone 20.0 parts by weight, polyisocyanate 5. System curing agent
The mixture was stirred and mixed in a vehicle consisting of 0 parts by weight to obtain a reversible thermochromic oil-based spray coating. The reversible thermochromic oil-based spray coating is applied to the entire body of a car-shaped miniature car injection molded with ABS resin using a spray gun having a diameter of 0.6 mm and dried, and then dried. A layered miniature car was obtained. When the reversible thermochromic miniature car painted as described above is heated to 33 ° C. or higher, it exhibits a pink color, and at 14 ° C. or lower, a purple color. In the temperature range between them, pink and purple can be arbitrarily selected and held.

【００４８】実施例３ 《油性刷毛塗り塗料》 可逆的熱変色性−６のマイクロカプセル顔料３４．２重
量部を、低粘度型エポキシ樹脂１８．５重量部、揺変性
付与剤２．０重量部、消泡剤０．３重量部、軟質エポキ
シ樹脂４５．０重量部からなるビヒクル中に均一分散練
合させて得られた可逆的熱変色性エポキシインキ中に常
温硬化型の脂肪族ポリアミン４０．０重量部を添加し、
均一に撹拌混合して可逆的熱変色性軟質エポキシインキ
を得た。前記、可逆的熱変色性軟質エポキシインキを、
ポリブタジエン樹脂で成形したエビフライ型成形物の全
体に刷毛を用いて塗装し、７０℃で１時間加温硬化させ
て、可逆的熱変色性エビフライ型塗装物が得られた。前
記の如く塗装された可逆的熱変色性エビフライ型塗装物
は３４℃以上に加温すると無色となり、３４℃以下で橙
色を呈する。Example 3 << Oil-based brush coating composition >> 34.2 parts by weight of a reversible thermochromic -6 microcapsule pigment, 18.5 parts by weight of a low-viscosity epoxy resin, and 2.0 parts by weight of a thixotropic agent Cold-curable aliphatic polyamine in a reversible thermochromic epoxy ink obtained by uniformly dispersing and kneading in a vehicle consisting of 0.3 parts by weight of a defoamer and 45.0 parts by weight of a soft epoxy resin; 0 parts by weight,
The mixture was uniformly stirred and mixed to obtain a reversible thermochromic soft epoxy ink. The reversible thermochromic soft epoxy ink,
The entire shrimp fry mold formed of the polybutadiene resin was applied using a brush, and was heated and cured at 70 ° C. for 1 hour to obtain a reversible thermochromic shrimp fry paint. The reversible thermochromic shrimp fry type painted product as described above becomes colorless when heated to 34 ° C. or higher, and exhibits an orange color at 34 ° C. or lower.

【００４９】実施例４ 《ディッピング塗料》 可逆的熱変色性−８のマイクロカプセル顔料４０．０重
量部及び粉末蛍光顔料（蛍光イエロー）５．０重量部、
アクリル酸エステル樹脂エマルジョン５８．３重量部、
消泡剤０．３重量部、揺変性付与剤１．３重量部、防腐
剤０．１重量部からなるビヒクル中に均一撹拌混合して
可逆的熱変色性水性ディッピングインキを得た。前記、
可逆的熱変色性水性ディッピングインキを用いて、ＡＢ
Ｓ樹脂の射出成形によって得られたボール型の成形物全
面にディッピング塗工し、乾燥させて可逆的熱変色層を
形成した。前記の如く塗工されたボール型の可逆的熱変
色性ディッピング塗工物は４０℃以上の温水を注ぐこと
により、黄色を呈し、また４０℃以下では緑色を呈し
た。Example 4 << Dipping Paint >> 40.0 parts by weight of microcapsule pigment having reversible thermochromic -8 and 5.0 parts by weight of a powdery fluorescent pigment (fluorescent yellow)
58.3 parts by weight of an acrylate resin emulsion,
A reversible thermochromic water-based dipping ink was obtained by uniformly stirring and mixing in a vehicle comprising 0.3 parts by weight of an antifoaming agent, 1.3 parts by weight of a thixotropic agent, and 0.1 part by weight of a preservative. Said,
AB using reversible thermochromic aqueous dipping ink
The entire surface of the ball-shaped molded product obtained by injection molding of S resin was dipped and dried to form a reversible thermochromic layer. The ball-type reversible thermochromic dipping coating material coated as described above exhibited yellow by pouring warm water at 40 ° C. or higher, and green at 40 ° C. or lower.

【００５０】実施例５ 《水性スクリーンインキ》 可逆的熱変色性組成物−３のマイクロカプセル顔料３
８．０重量部及び蛍光顔料（蛍光ピンク）２．０重量
部、エチレン−酢酸ビニル共重合樹脂エマルジョン４
０．０重量部、消泡剤３．０重量部、増粘剤（水溶性ポ
リアルギン酸ナトリウム樹脂）１．０重量部、レベリン
グ剤３．０重量部、防腐剤１．０重量部からなるビヒク
ル中に均一に混合して可逆的熱変色性スクリーンインキ
を得た。前記可逆的熱変色性スクリーンインキを、８０
μｍ厚の白色合成紙に接着剤をコーティングして１ｍｍ
厚のポリエチレンフォームを貼り合わせた支持体上に、
ポリエステル製の１５０メッシュシートのスクリーン版
を用いて印刷して可逆的熱変色層を形成した。前記の如
く形成した可逆的熱変色性シートは３０℃以上に加温す
ると全面がピンク色を呈し、３０℃以下で紫色を呈す
る。Example 5 << Aqueous Screen Ink >> Microcapsule Pigment 3 of Reversible Thermochromic Composition-3
8.0 parts by weight and 2.0 parts by weight of a fluorescent pigment (fluorescent pink), ethylene-vinyl acetate copolymer resin emulsion 4
A vehicle comprising 0.0 parts by weight, 3.0 parts by weight of an antifoaming agent, 1.0 part by weight of a thickener (water-soluble sodium polyalginate resin), 3.0 parts by weight of a leveling agent, and 1.0 part by weight of a preservative. The mixture was mixed uniformly to obtain a reversible thermochromic screen ink. 80 g of said reversible thermochromic screen ink
μm white synthetic paper coated with adhesive and 1mm
On a support with a thick polyethylene foam attached,
Printing was performed using a screen plate of a 150 mesh sheet made of polyester to form a reversible thermochromic layer. When the reversible thermochromic sheet formed as described above is heated to 30 ° C. or higher, the entire surface exhibits a pink color, and exhibits a purple color at 30 ° C. or lower.

【００５１】実施例６ 《水性スクリーンインキ》 可逆的熱変色性組成物−１のマイクロカプセル顔料４
０．０重量部をエチレン酢酸ビニル共重合樹脂エマルジ
ョン５２．０重量部、消泡剤３．０重量部、増粘剤（ポ
リアルギン酸ナトリウム樹脂）１．０重量部、レベリン
グ剤３．０重量部、防腐剤１．０重量部からなるビヒク
ル中に均一に混合して可逆的熱変色性スクリーンインキ
を得た。白色顔料をブレンドした軟質塩化ビニル樹脂か
らなる不透明支持体に淡橙色の一般色印刷インキにより
絵柄像を印刷形成した後、前記絵柄像上に可逆的熱変色
性スクリーンインキを用いて１８０メッシュシートのス
クリーン版にて可逆的熱変色層を設けた。得られた印刷
物を所定寸法及び形状の花びら状に裁断し造花を作製し
た。前記の如く構成された造花の花びらは３０℃以上に
加温すると可逆的熱変色層が消色し、淡橙色の一般色絵
柄像が視認される。また、室温下では可逆的熱変色層が
ピンク色を呈するため一般色像は潜像として視認されな
い。Example 6 << Aqueous Screen Ink >> Microcapsule Pigment 4 of Reversible Thermochromic Composition-1
0.0 parts by weight of 52.0 parts by weight of an ethylene-vinyl acetate copolymer resin emulsion, 3.0 parts by weight of a defoamer, 1.0 part by weight of a thickener (sodium polyalginate resin), and 3.0 parts by weight of a leveling agent The mixture was uniformly mixed in a vehicle consisting of 1.0 part by weight of a preservative to obtain a reversible thermochromic screen ink. After forming a pattern image by printing a pale orange general color printing ink on an opaque support made of a soft vinyl chloride resin blended with a white pigment, a 180-mesh sheet is formed on the pattern image by using a reversible thermochromic screen ink. The screen plate was provided with a reversible thermochromic layer. The obtained printed matter was cut into a petal having a predetermined size and shape to produce an artificial flower. When the artificial flower petals configured as described above are heated to 30 ° C. or higher, the reversible thermochromic layer is decolorized, and a pale orange general color picture image is visually recognized. At room temperature, the general color image is not visually recognized as a latent image because the reversible thermochromic layer exhibits a pink color.

【００５２】実施例７ 《水性グラビアインキ》 可逆的熱変色性−３のマイクロカプセル顔料５０．０重
量部をアクリルスチレン共重合樹脂４３．０重量部、消
泡剤６．０重量部、防腐剤１．０重量部からなるビヒク
ル中に均一に撹拌混合して可逆的熱変色性グラビアイン
キを得た。前記可逆的熱変色性グラビアインキを、４０
μｍのＯＰＰフイルムシート上に、従来公知のグラビア
印刷方法に準じて印刷し可逆的熱変色層を形成した。前
記の如く形成された熱変色ＯＰＰフイルムシートは室温
下では青色を呈し、３０℃以上では無色となる。Example 7 << Aqueous Gravure Ink >> 50.0 parts by weight of a microcapsule pigment having reversible thermochromic -3 was 43.0 parts by weight of an acrylic styrene copolymer resin, 6.0 parts by weight of a defoamer, and a preservative. A reversible thermochromic gravure ink was obtained by uniformly stirring and mixing in a vehicle consisting of 1.0 part by weight. 40 g of the reversible thermochromic gravure ink
A reversible thermochromic layer was formed on a μm OPP film sheet by printing according to a conventionally known gravure printing method. The thermochromic OPP film sheet formed as described above exhibits a blue color at room temperature and becomes colorless above 30 ° C.

【００５３】実施例８ 《水性布用スクリーンインキ》 可逆的熱変色性−７のマイクロカプセル顔料３０．０重
量部及び、蛍光顔料（蛍光イエロー）５．０重量部、ア
クリル酸エステル共重合樹脂エマルジョン４５．０重量
部、消泡剤３．０重量部を均一に分散し、アルカリ増粘
剤（アクリル酸エステル樹脂エマルジョン）１３．０重
量部、防腐剤０．５重量部、アンモニア水（３５％）
３．５重量部を添加して均一に撹拌混合して可逆的熱変
色性スクリーン水性インキを得た。前記、可逆的熱変色
性スクリーン水性インキを白色のＴ−シャツ生地上に１
２０メッシュポリエステル製のスクリーン版を用いて印
刷して熱変色層を形成した。前記の如く形成された可逆
的熱変色性Ｔ−シャツは３３℃以上に加温すると黄色を
呈し、１４℃以下では緑色を呈する。その間の温度域で
は任意に緑色と黄色を選択保持できる。Example 8 << Screen Ink for Aqueous Cloth >> 30.0 parts by weight of microcapsule pigment having reversible thermochromic -7, 5.0 parts by weight of fluorescent pigment (fluorescent yellow), acrylate copolymer resin emulsion 45.0 parts by weight and 3.0 parts by weight of an antifoaming agent are uniformly dispersed, and 13.0 parts by weight of an alkali thickener (acrylate resin emulsion), 0.5 part by weight of a preservative, and ammonia water (35%) )
3.5 parts by weight were added and uniformly stirred and mixed to obtain a reversible thermochromic screen aqueous ink. Apply the reversible thermochromic screen water-based ink to a white T-shirt cloth
Printing was performed using a 20-mesh polyester screen plate to form a thermochromic layer. The reversible thermochromic T-shirt formed as described above exhibits a yellow color when heated to 33 ° C or higher, and a green color when 14 ° C or lower. Green and yellow can be arbitrarily selected and held in the temperature range between them.

【００５４】実施例９ 《油性コーティングインキ》 可逆的熱変色性組成物−６のマイクロカプセル顔料５．
０重量部を塩化ビニル−酢酸ビニル共重合樹脂１５．０
重量部、キシレン３５．０重量部、酢酸エチル３９．０
重量部、消泡剤１．０重量部からなるビヒクル中に分
散、混合して可逆的熱変色性油性コーティングインキを
得た。前記、可逆的熱変色性油性コーティングインキを
ドクターコーターにより、透明虹彩性多層フイルム（Ｉ
ＲＩＤＥＥＳＣＥＮＴ ＦＩＬＭ ＩＦ−８１８１Ｒ／
Ｇ）〔ＭＥＡＲＬ社製〕上に塗布して、可逆的熱変色層
を設けた。さらに可逆的熱変色層上にアクリル系樹脂ト
ルエン・酢酸エチル溶液（固形分４０％）を塗布して溶
剤を蒸発させた後、厚み１６μｍの透明ポリエチレンテ
レフタレートフイルムをロールで厚着し虹彩可逆熱変色
性積層体を得た。前記、虹彩可逆熱変色性積層体は３４
℃以下では虹彩光沢を有するオレンジ色を呈し、３４℃
以下では無色半透明を呈する。Example 9 << Oil-based coating ink >> Microcapsule pigment of reversible thermochromic composition-6
0 parts by weight of vinyl chloride-vinyl acetate copolymer resin 15.0
Parts by weight, xylene 35.0 parts by weight, ethyl acetate 39.0
The mixture was dispersed and mixed in a vehicle consisting of 1.0 part by weight of a defoaming agent to obtain a reversible thermochromic oil-based coating ink. The reversible thermochromic oil-based coating ink was coated with a transparent iris multilayer film (I) by a doctor coater.
RIDEESCENT FILM IF-8181R /
G) A reversible thermochromic layer was formed by coating on [MEARL]. Acrylic resin toluene / ethyl acetate solution (40% solid content) is applied on the reversible thermochromic layer, and the solvent is evaporated. After that, a 16 μm-thick transparent polyethylene terephthalate film is thickly coated with a roll, and the iris reversible thermochromic property is applied. A laminate was obtained. The iris reversible thermochromic laminate is 34
Below ℃, it shows an orange color with iris gloss, 34 ℃
In the following, it is colorless and translucent.

【００５５】実施例１０ 《油性エポキシインキ》 可逆的熱変色性組成物−５のマイクロカプセル顔料４
３．３重量部、硬質タイプの液状エポキシ樹脂５６．４
重量部、消泡剤０．３重量部を均一に混練させて得られ
た可逆的熱変色性エポキシインキ中に常温硬化型の脂肪
族ポリアミン３５．０重量部を添加し、均一に撹拌混合
して可逆的熱変色性エポキシインキを得た。前記、エポ
キシインキを陶器マグカップ表面にステンレス製１００
メッシュスクリーン版を用いて曲面スクリーン印刷を施
し７０℃〜６０分間熱硬化して可逆的熱変色層を設け
た。前記の如く形成された可逆熱変色マグカップは室温
環境温度では青色を呈し、湯水を注いで表面温度が４８
℃以上になると無色となる。Example 10 << Oil-based epoxy ink >> Microcapsule pigment 4 of reversible thermochromic composition-5
3.3 parts by weight, hard type liquid epoxy resin 56.4
Parts by weight and 0.3 parts by weight of an antifoaming agent are uniformly kneaded, and 35.0 parts by weight of a room temperature-curable aliphatic polyamine is added to a reversible thermochromic epoxy ink obtained and uniformly stirred and mixed. Thus, a reversible thermochromic epoxy ink was obtained. The epoxy ink is applied to the surface of a ceramic mug
Curved screen printing was performed using a mesh screen plate, and heat cured at 70 ° C. for 60 minutes to form a reversible thermochromic layer. The reversible thermochromic mug formed as described above has a blue color at room temperature and the surface temperature is 48 ° C.
It becomes colorless above ℃.

【００５６】実施例１１ 《マーキングペン用インキ》 可逆的熱変色性組成物−２のマイクロカプセル顔料２
７．０重量部及び水分散型蛍光顔料（蛍光ブルー）３．
０重量部、カルボキ変性ポリオレフィン系自己乳化エマ
ルジョン（固形分２４〜２５％）３０重量部、ポリグリ
セリルアクリレート系湿潤剤４重量部、トリエタノール
アミン１重量部、メチルセルロース０．５重量部、防徴
剤０．２重量部及び消泡剤０．４重量部、水３４重量部
からなるビヒクル中に均質に混合して可逆的熱変色性マ
ーキングペンインキを得た。なお、前記インキの比重は
１．０１粘度３５ｃｐｓである。前記可逆的熱変色性マ
ーキングペンインキを毛細管路を有するインキ吸蔵体に
含浸させて軸筒に内蔵し、筆記先端部にプラスチックポ
ーラス体よりなるペン体を設けて可逆的熱変色性マーキ
ングペンインキを得た。前記、可逆的熱変色性マーキン
グペンインキにより筆記して得られる筆跡は、１４℃以
下に冷却すると紫色を示し、３３℃以上で青色となる。
１４℃ないし３３℃の温度域では、任意に紫色と青色を
選択保持できる。Example 11 << Ink for Marking Pen >> Microcapsule pigment 2 of reversible thermochromic composition-2
2. 7.0 parts by weight and a water-dispersed fluorescent pigment (fluorescent blue)
0 parts by weight, 30 parts by weight of a carboxy-modified polyolefin-based self-emulsifying emulsion (solid content: 24 to 25%), 4 parts by weight of a polyglyceryl acrylate-based humectant, 1 part by weight of triethanolamine, 0.5 part by weight of methylcellulose, 0 In a vehicle consisting of 0.2 parts by weight, 0.4 parts by weight of an antifoaming agent and 34 parts by weight of water, they were homogeneously mixed to obtain a reversible thermochromic marking pen ink. The specific gravity of the ink is 1.01 and the viscosity is 35 cps. The reversible thermochromic marking pen ink is impregnated in an ink occlusion body having a capillary tube, built in a barrel, and provided with a pen body made of a plastic porous body at the writing tip to provide a reversible thermochromic marking pen ink. Obtained. The handwriting obtained by writing with the reversible thermochromic marking pen ink exhibits a purple color when cooled to 14 ° C or lower, and turns blue at 33 ° C or higher.
In the temperature range of 14 ° C. to 33 ° C., purple and blue can be optionally selected and held.

【００５７】実施例１２ 《ボールペンインキ》 可逆的熱変色性組成物−３のマイクロカプセル顔料４
４．０重量部（固形分２７．３％）を、剪断減粘性付与
剤を含む水性ビヒクル５６．０重量部中に均一分散混合
して、可逆的熱変色性水性ボールペン用インキを調製し
た。前記、可逆的熱変色性水性ボールペン用インキを充
填したボールペンを用いてレポート用紙に筆記したとこ
ろ書き出しが良好な青色の筆跡が得られた。なお、筆跡
の熱変色性を試験した結果、３０℃以上で無色となり、
３０℃以下で青色を呈する。Example 12 << Ballpoint pen ink >> Microcapsule pigment 4 of reversible thermochromic composition-3
4.0 parts by weight (solid content 27.3%) was uniformly dispersed and mixed in 56.0 parts by weight of an aqueous vehicle containing a shear-thinning agent to prepare a reversible thermochromic aqueous ballpoint pen ink. Writing on report paper using the ballpoint pen filled with the reversible thermochromic water-based ballpoint pen ink yielded blue handwriting with a good writing start. In addition, as a result of testing the thermal discoloration of the handwriting, it becomes colorless at 30 ° C. or higher,
It exhibits a blue color below 30 ° C.

【００５８】実施例１３ 《絵具》 可逆的熱変色性組成物７のマイクロカプセル顔料４０．
０重量部及び炭酸カルシウム５．０重量部をアラビアガ
ム１４．０重量部、グリセリン１０．０重量部、粘性調
整剤５．０重量部、防腐剤１．０重量部、水２５．０重
量部殻なるビヒクル中に均一分散混合して、可逆的熱変
色性水性絵具を得た。前記絵具を水で２倍に希釈し、筆
穂に含ませて画用紙に絵を描いた。前記描いた絵の熱変
色性を試験した結果、１４℃以下に冷却すると青緑色を
呈し、３３℃以上で無色となる。その間の温度域では任
意に青緑色と無色が選択保持できる。Example 13 << Paint >> Microcapsule pigment of reversible thermochromic composition 7
0 parts by weight and 5.0 parts by weight of calcium carbonate are 14.0 parts by weight of gum arabic, 10.0 parts by weight of glycerin, 5.0 parts by weight of a viscosity modifier, 1.0 part by weight of a preservative, and 25.0 parts by weight of water. The mixture was uniformly dispersed and mixed in a shell vehicle to obtain a reversible thermochromic aqueous paint. The paint was diluted two-fold with water and included in a brush to draw a picture on a drawing paper. As a result of examining the thermochromic property of the drawn picture, it turns blue-green when cooled to 14 ° C or lower, and becomes colorless at 33 ° C or higher. In the temperature range between them, blue-green and colorless can be arbitrarily selected and held.

【００５９】実施例１４ 《付け爪用スプレー化粧料》 可逆的熱変色性組成物−４のマイクロカプセル顔料１
５．０重量部及び蛍光顔料（蛍光ピンク）３，０重量
部、５０％アクリル樹脂／キシレン溶液４０．０重量
部、キシレン２０．０重量部、及びメチルイソブチルケ
トン２０．０重量部、ポリイソシアネート系硬化剤６．
０重量部からなるビヒクル中に撹拌混合して可逆的熱変
色性付け爪用油性スプレー化粧料を得た。前記可逆的熱
変色性付け爪用油性スプレー化粧料を、アセチルセルロ
ース樹脂製の付け爪の表面に、口径０．６ｍｍのスプレ
ーガンを用いてスプレー塗装を施した後、乾燥して可逆
的熱変色層を設けた。さらに、その上面に真珠光沢顔料
（イリオジン２１９・メルクジャパン製）３．０重量
部、５０％アクリル樹脂／キシレン溶液４０．０重量
部、キシレン２０．０重量部、及びメチルイソブチルケ
トン２０．０重量部、ポリイソシアネート系硬化剤６．
０重量部からなる真珠光沢顔料含有スプレーガンを用い
てスプレ−塗装を施し、さらにその上面に、５０％アク
リル樹脂／キシレン溶液４０．０重量部、キシレン２
０．０重量部、及びメチルイソブチルケトン２０．０重
量部、ポリイソシアネート系硬化剤６．０重量部、光安
定剤適量部からなる光沢性トップコート剤塗装して真珠
光沢調可逆的熱変色性付け爪を得た。前記真珠光沢調可
逆的熱変色性付け爪は３３℃以上に加温するとパール調
ピンク色を呈し、１４℃以下ではパール調のバイレット
を呈する。その間の温度域では任意にパール調のピンク
色とパール調のバイレット色が選択保持できる。Example 14 << Spray cosmetic for false nails >> Microcapsule pigment 1 of reversible thermochromic composition-4
5.0 parts by weight and fluorescent pigment (fluorescent pink) 3.0 parts by weight, 50% acrylic resin / xylene solution 40.0 parts by weight, xylene 20.0 parts by weight, methyl isobutyl ketone 20.0 parts by weight, polyisocyanate 5. System curing agent
The mixture was stirred and mixed in a vehicle consisting of 0 parts by weight to obtain a reversible thermochromic oily spray for nails. The reversible thermochromic oily spray cosmetic is applied to the surface of an acetylcellulose resin artificial nail using a spray gun having a diameter of 0.6 mm, and then dried to perform reversible thermochromic discoloration. Layers were provided. Further, on the upper surface, 3.0 parts by weight of a pearlescent pigment (Iriodin 219, manufactured by Merck Japan), 40.0 parts by weight of a 50% acrylic resin / xylene solution, 20.0 parts by weight of xylene, and 20.0 parts by weight of methyl isobutyl ketone Part, polyisocyanate-based curing agent
Spray coating was performed using a pearlescent pigment-containing spray gun consisting of 0 parts by weight, and 40.0 parts by weight of a 50% acrylic resin / xylene solution, xylene 2
A glossy top coat agent consisting of 0.0 parts by weight, 20.0 parts by weight of methyl isobutyl ketone, 6.0 parts by weight of a polyisocyanate-based curing agent, and an appropriate amount of a light stabilizer is applied to form a pearlescent glossy reversible thermochromic. I got false nails. The pearl luster reversible thermochromic artificial nail exhibits a pearly pink color when heated to 33 ° C. or higher, and exhibits a pearly billet at 14 ° C. or lower. In the temperature range between them, pearly pink and pearly billet colors can be selectively retained.

【００６０】実施例１５ 《付け爪用刷毛塗り化粧料》 可逆的熱変色性組成物−１のマイクロカプセル顔料１
５．０重量部を５０％アクリル樹脂／キシレン溶液４
０．０重量部、キシレン５．０重量部、及びメチルイソ
ブチルケトン５．０重量部、ポリイソシアネート系硬化
剤６．０重量部からなるビヒクル中に撹拌混合して可逆
的熱変色性刷毛塗り溶液を得た。前記刷毛塗り溶液をア
セチルセルロース樹脂製の付け爪の表面に刷毛塗りを施
して可逆的熱変色性付け爪を得た。前記可逆的熱変色性
付け爪は室温環境下ではピンク色を呈し、３０℃以上で
は無色となる。Example 15 << Brush Cosmetics for False Nails >> Microcapsule Pigment 1 of Reversible Thermochromic Composition-1
5.0 parts by weight of 50% acrylic resin / xylene solution 4
A reversible thermochromic brush coating solution by stirring and mixing in a vehicle consisting of 0.0 parts by weight, 5.0 parts by weight of xylene, 5.0 parts by weight of methyl isobutyl ketone, and 6.0 parts by weight of a polyisocyanate-based curing agent. I got The above-mentioned brush coating solution was brush-coated on the surface of an artificial nail made of acetylcellulose resin to obtain a reversible thermochromic artificial nail. The reversible thermochromic artificial nail exhibits a pink color in a room temperature environment and becomes colorless at 30 ° C. or more.

【００６１】実施例１６ 《熱変色性繊維処理剤》 可逆的熱変色性組成物−３のマイクロカプセル顔料２
５．０重量部をビヒクルとしてアクリル酸エステル樹脂
エマルジョン８０．０重量部に均一分散した可逆的熱変
色性水性コーティング液中に、７０ｍｍの長さにカット
した７デニールのポリアクリロニトリル原綿１００．０
重量部を浸漬させ、その後遠心分離により余分なコーテ
ィング液を排除後９０℃１０分間乾燥させて可逆的熱変
色性ポリアクリルニトリル原綿を得た。前記可逆的熱変
色性ポリアクリルニトリル原綿をカードにかけスライバ
ーにした後ハイパイル編機で製編しシャーリング加工し
て得られたパイル長２０ｍｍの可逆的熱変色性ハイパイ
ル生地を得た。前記可逆的熱変色性ハイパイル生地を縫
製しクマの可逆的熱変色性ぬいぐるみを得た。前記可逆
的熱変色性ぬいぐるみは室温下では青色を呈し、３４℃
以上では無色となる。Example 16 << Thermochromic fiber treating agent >> Microcapsule pigment 2 of reversible thermochromic composition-3
In a reversible thermochromic aqueous coating solution uniformly dispersed in 80.0 parts by weight of an acrylate resin emulsion using 5.0 parts by weight of a vehicle as a vehicle, 7 denier polyacrylonitrile raw cotton cut to a length of 70 mm was used.
By weight, the excess coating solution was removed by centrifugation and dried at 90 ° C. for 10 minutes to obtain a reversible thermochromic polyacrylonitrile raw cotton. The reversible thermochromic polyacrylonitrile raw cotton was slivered on a card, knitted with a high pile knitting machine, and sheared to obtain a reversible thermochromic high pile fabric having a pile length of 20 mm. The reversible thermochromic high pile fabric was sewn to obtain a reversible thermochromic stuffed bear. The reversible thermochromic stuffed animal exhibits a blue color at room temperature,
Above is colorless.

【００６２】実施例１７ 《熱変色性の繊維処理剤》 可逆的熱変色性組成物−１のマイクロカプセル顔料５
０．０重量部をビヒクルとしてアクリル酸エステル樹脂
エマルジョン５０．０重量部に均一分散した可逆的熱変
色性水性コーティング液中に、７デニールのポリアクリ
ロニトリル素繊維を８０．０重量部を浸漬させ、その後
遠心分離により余分なコーティング液を排除後１００℃
５分間乾燥させ可逆的熱変色性ポリアクリルニトリル素
繊維を得た。前記繊維を捲縮加工し８０ｍｍ〜１３０ｍ
ｍの長さにバイアスカットして可逆的熱変色性原綿を得
た。前記原綿をカードにかけ、撚り加工を施して可逆的
熱変色性糸を３本束ねて可逆的熱変色性毛糸を得た。前
記可逆的熱変色性毛糸を頭髪植毛ミシンを用いて人形の
頭部にて植毛して、可逆的熱変色性毛髪を有する人形を
得た。前記可逆的熱変色性毛髪を有する人形の毛髪は室
温下ではピンク色を呈し、３０℃以上では無色となる。Example 17 << Thermochromic fiber treating agent >> Microcapsule pigment 5 of reversible thermochromic composition-1
80.0 parts by weight of 7 denier polyacrylonitrile base fiber is immersed in a reversible thermochromic aqueous coating liquid uniformly dispersed in 50.0 parts by weight of an acrylate resin emulsion using 0.0 parts by weight as a vehicle, Then remove excess coating solution by centrifugation and then 100 ℃
After drying for 5 minutes, a reversible thermochromic polyacrylonitrile fiber was obtained. The fiber is crimped to 80 mm to 130 m
The length of m was bias cut to obtain reversible thermochromic raw cotton. The raw cotton was put on a card, twisted, and three reversible thermochromic yarns were bundled to obtain a reversible thermochromic yarn. The reversible thermochromic wool was implanted at the head of the doll using a hair-implanted sewing machine to obtain a doll having reversible thermochromic hair. The hair of the doll having the reversible thermochromic hair exhibits a pink color at room temperature and becomes colorless at 30 ° C. or higher.

【００６３】比較例１ 《水性スプレー塗料》 可逆的熱変色性組成物−９のマイクロカプセル顔料を用
いて実施例１と同様に可逆的熱変色性布帛を得た。また
前記布帛を縫製して可逆的熱変色性人形用ドレスを作製
した。Comparative Example 1 << Aqueous Spray Paint >> A reversible thermochromic fabric was obtained in the same manner as in Example 1 using the microcapsule pigment of the reversible thermochromic composition-9. The cloth was sewn to produce a reversible thermochromic doll dress.

【００６４】比較例２ 《油性スプレー塗料》 可逆的熱変色性組成物−１２のマイクロカプセル顔料を
用いて実施例２と同様に可逆的熱変色性油性スプレー塗
装を得た。さらに前記可逆的熱変色性油性スプレー塗装
を用いて可逆的熱変色性層を施したミニチュアカーを得
た。Comparative Example 2 << Oilous Spray Paint >> A reversible thermochromic oil-based spray coating was obtained in the same manner as in Example 2 using the microcapsule pigment of the reversible thermochromic composition-12. Further, a miniature car having a reversible thermochromic layer was obtained using the reversible thermochromic oil-based spray coating.

【００６５】比較例３ 《油性刷毛塗り塗料》 可逆的熱変色性組成物−１４のマイクロカプセル顔料を
用いて実施例３と同様に可逆的熱変色性軟質エポキシイ
ンキを得た。さらに、ポリブタジエン製のエビフライ型
成形物全体に刷毛を用いて前記可逆的熱変色性軟質エポ
キシインキで塗装し加温硬化させて、可逆的熱変色性エ
ビフライ型塗装物を得た。Comparative Example 3 << Oil-Based Brush Coating Paint >> A reversible thermochromic soft epoxy ink was obtained in the same manner as in Example 3 using the microcapsule pigment of the reversible thermochromic composition-14. Further, the entire shrimp fly molded product made of polybutadiene was coated with the reversible thermochromic soft epoxy ink using a brush and heated and cured to obtain a reversible thermochromic shrimp fly paint.

【００６６】比較例４ 《ディッピング塗料》 可逆的熱変色性組成物−１６のマイクロカプセル顔料を
用いて、実施例４と同様に可逆的熱変色性水性ディッピ
ングインキを得た。さらに、前記可逆的熱変色性水性デ
ィッピングインキを用いてＡＢＳ樹脂製のボール型成形
物の全面にディッピング塗工し、乾燥させてボール型の
可逆的熱変色性ディッピング塗工物を得た。Comparative Example 4 << Dipping Paint >> A reversible thermochromic water-based dipping ink was obtained in the same manner as in Example 4 using the microcapsule pigment of the reversible thermochromic composition-16. Further, the entire surface of a ball-shaped molded article made of an ABS resin was dipped using the reversible thermochromic water-based dipping ink, and dried to obtain a ball-shaped reversible thermochromic dipping coated article.

【００６７】比較例５ 《水性スクリーンインキ》 可逆的熱変色性組成物−１１のマイクロカプセル顔料を
用いて、実施例５と同様に可逆的熱変色性スクリーンイ
ンキを得た。前記可逆的熱変色性スクリーンインキを用
いて白色合成紙にポリエチレンフォームを貼り合わせた
支持体上にスクリーン印刷して可逆的熱変色性シートを
得た。Comparative Example 5 << Aqueous Screen Ink >> A reversible thermochromic screen ink was obtained in the same manner as in Example 5 using the microcapsule pigment of the reversible thermochromic composition-11. Using the reversible thermochromic screen ink, screen printing was performed on a support in which polyethylene foam was bonded to white synthetic paper to obtain a reversible thermochromic sheet.

【００６８】比較例６ 《水性スクリーンインキ》 可逆的熱変色性組成物−９のマイクロカプセル顔料を用
いて、実施例６と同様に可逆的熱変色性スクリーンイン
キを得た。前記可逆的熱変色性スクリーンインキを用い
て、絵柄像を形成した塩化ビニルシートの絵柄上全面に
スクリーン印刷を施して可逆的熱変色層を設けた印刷物
を得た。さらに、前記印刷物を花びら状に裁断し造花を
作製した。Comparative Example 6 << Aqueous Screen Ink >> A reversible thermochromic screen ink was obtained in the same manner as in Example 6 using the microcapsule pigment of the reversible thermochromic composition-9. Using the reversible thermochromic screen ink, screen printing was performed on the entire surface of the pattern of the vinyl chloride sheet on which the pattern image was formed to obtain a printed material having a reversible thermochromic layer. Further, the printed matter was cut into petals to produce artificial flowers.

【００６９】比較例７ 《水性グラビアインキ》 可逆的熱変色性組成物−１１のマイクロカプセル顔料を
用いて、実施例７と同様に可逆的熱変色性グラビアイン
キを得た。前記可逆的熱変色性グラビアインキを用いて
ＯＰＰフイルムシート上にグラビア印刷を施し可逆的熱
変色性ＯＰＰフイルムシートを得た。Comparative Example 7 << Aqueous Gravure Ink >> A reversible thermochromic gravure ink was obtained in the same manner as in Example 7, using the microcapsule pigment of the reversible thermochromic composition-11. Gravure printing was performed on the OPP film sheet using the reversible thermochromic gravure ink to obtain a reversible thermochromic OPP film sheet.

【００７０】比較例８ 《水性布用スクリーンインキ》 可逆的熱変色性組成物−１５のマイクロカプセル顔料を
用いて、実施例８と同様に可逆的熱変色性スクリーン水
性インキを得た。前記可逆的熱変色性スクリーン水性イ
ンキを用いてＴ−シャツ生地上にスクリーン印刷を施し
て可逆的熱変色性Ｔ−シャツを得た。Comparative Example 8 << Aqueous Screen Ink for Aqueous Cloth >> A reversible thermochromic screen aqueous ink was obtained in the same manner as in Example 8 using the microcapsule pigment of the reversible thermochromic composition-15. Screen printing was performed on a T-shirt fabric using the reversible thermochromic screen aqueous ink to obtain a reversible thermochromic T-shirt.

【００７１】比較例９ 《油性コーティングインキ》可
逆的熱変色性組成物−１４のマイクロカプセル顔料を用
いて、実施例９と同様に可逆的熱変色性油性コーティン
グインキを得た。前記可逆的熱変色性油性コーティング
インキを用いて透明虹彩性多層フイルム上にドクターコ
ーターにより塗布して、可逆的熱変色層を設けた。さら
に可逆的熱変色層上にポリエチレンテレフタレートフイ
ルムをロールで厚着し虹彩可逆熱変色性積層体を得た。Comparative Example 9 << Oil-Based Coating Ink >> A reversible thermochromic oil-based coating ink was obtained in the same manner as in Example 9 using the microcapsule pigment of the reversible thermochromic composition-14. The reversible thermochromic oil-based coating ink was used to coat a transparent iris multilayer film with a doctor coater to form a reversible thermochromic layer. Further, a polyethylene terephthalate film was thickly deposited on the reversible thermochromic layer with a roll to obtain an iris reversible thermochromic laminate.

【００７２】比較例１０ 《油性エポキシインキ》 可逆的熱変色性組成物−１３のマイクロカプセル顔料を
用いて、実施例１０と同様に可逆的熱変色性エポキシイ
ンキを得た。前記可逆的熱変色性エポキシインキを用い
て陶器マグカップに曲面印刷を施し加熱硬化して可逆熱
変色マグカップを得た。Comparative Example 10 << Oil-Based Epoxy Ink >> A reversible thermochromic epoxy ink was obtained in the same manner as in Example 10 using the microcapsule pigment of the reversible thermochromic composition-13. Using the reversible thermochromic epoxy ink, a ceramic mug was subjected to surface printing and cured by heating to obtain a reversible thermochromic mug.

【００７３】比較例１１ 《マーキングペン用インキ》 可逆的熱変色性組成物−１０のマイクロカプセル顔料を
用いて、実施例１１と同様に可逆的熱変色性マーキング
ペン用インキを得た。前記可逆的熱変色性マーキングペ
ン用インキを充填し可逆的熱変色性マーキングペンイン
キを得た。Comparative Example 11 << Ink for Marking Pen >> An ink for a reversible thermochromic marking pen was obtained in the same manner as in Example 11 using the microcapsule pigment of the reversible thermochromic composition-10. The reversible thermochromic marking pen ink was filled to obtain a reversible thermochromic marking pen ink.

【００７４】比較例１２ 《ボールペンインキ》 可逆的熱変色性組成物−１１のマイクロカプセル顔料を
用いて、実施例１２と同様に可逆的熱変色性水性ボール
ペン用インキを得た。前記可逆的熱変色性水性ボールペ
ン用インキを充填した可逆的熱変色性ボールペンを得
た。Comparative Example 12 << Ballpoint Pen Ink >> A reversible thermochromic water-based ballpoint pen ink was obtained in the same manner as in Example 12, using the microcapsule pigment of the reversible thermochromic composition-11. A reversible thermochromic ballpoint pen filled with the reversible thermochromic aqueous ballpoint pen ink was obtained.

【００７５】比較例１３ 《絵具》 可逆的熱変色性組成物１５のマイクロカプセル顔料を用
いて、実施例１３と同様に可逆的熱変色性水性絵具を得
た。前記絵具を水で２倍に希釈し、筆穂に含ませて画用
紙に絵を描いた。Comparative Example 13 << Paint >> Using the microcapsule pigment of the reversible thermochromic composition 15, a reversible thermochromic aqueous paint was obtained in the same manner as in Example 13. The paint was diluted two-fold with water and included in a brush to draw a picture on a drawing paper.

【００７６】比較例１４ 《付け爪用スプレー化粧料》 可逆的熱変色性組成物−１２のマイクロカプセル顔料を
用いて、実施例１４と同様に可逆的熱変色性付け爪用油
性スプレー化粧料を得た。前記可逆的熱変色性付け爪用
油性スプレー化粧料を用いてアセチルセルロース樹脂製
の付け爪にスプレー塗装を施し可逆的熱変色層を設け
た。さらにその上面に真珠光沢顔料含有スプレーガンを
用いてスプレー塗装を施しさらにその上面に光沢性トッ
プコート剤を塗装して真珠光沢調可逆的熱変色性付け爪
を得た。Comparative Example 14 << Spray Cosmetic for False Nails >> Using the microcapsule pigment of the reversible thermochromic composition-12, an oil-based spray cosmetic for reversible thermochromic nails was prepared in the same manner as in Example 14. Obtained. The reversible thermochromic oily spray cosmetic was applied to an acetylcellulose resin false nail to provide a reversible thermochromic layer. Further, the upper surface was spray-painted using a pearlescent pigment-containing spray gun, and the upper surface was further coated with a glossy top coat agent to obtain a pearlescent tone reversible thermochromic nail.

【００７７】比較例１５ 《付け爪用刷毛塗り化粧料》 可逆的熱変色性組成物−９のマイクロカプセル顔料を用
いて、実施例１５と同様に可逆的熱変色性刷毛塗り溶液
を得た。前記刷毛塗り溶液をアセチルセルロース樹脂製
の付け爪の表面に刷毛塗りを施して可逆的熱変色性付け
爪を得た。Comparative Example 15 << Brush Cosmetic for False Nails >> A reversible thermochromic brush coating solution was obtained in the same manner as in Example 15 using the microcapsule pigment of the reversible thermochromic composition-9. The above-mentioned brush coating solution was brush-coated on the surface of an artificial nail made of acetylcellulose resin to obtain a reversible thermochromic artificial nail.

【００７８】比較例１６ 《熱変色性繊維処理剤》 可逆的熱変色性組成物−１１のマイクロカプセル顔料を
用いて、実施例１６と同様に可逆的熱変色性ハイパイル
生地を得た。前記可逆的熱変色性ハイパイル生地を用い
て可逆的熱変色性ぬいぐるみを得た。Comparative Example 16 << Thermochromic fiber treating agent >> A reversible thermochromic high pile fabric was obtained in the same manner as in Example 16 using the microcapsule pigment of the reversible thermochromic composition-11. A reversible thermochromic plush was obtained using the reversible thermochromic high pile fabric.

【００７９】比較例１７ 《熱変色性繊維処理剤》 可逆的熱変色性組成物−９のマイクロカプセル顔料を用
いて、実施例１７と同様に可逆的熱変色性毛糸を得た。
前記可逆的熱変色性毛糸を頭髪植毛ミシンを用いて人形
の頭部にて植毛して、可逆的熱変色性毛髪を有する人形
を得た。Comparative Example 17 << Thermochromic fiber treating agent >> A reversible thermochromic yarn was obtained in the same manner as in Example 17 using the microcapsule pigment of the reversible thermochromic composition-9.
The reversible thermochromic wool was implanted at the head of the doll using a hair-implanted sewing machine to obtain a doll having reversible thermochromic hair.

【００８０】耐光性試験方法次ぎにこれらの可逆的熱変
色性を有する被覆用液状組成物の耐光堅牢度を示す。 （１） 耐光堅牢度試験試料の調製 実施例１の可逆的熱変色性布帛を耐光性試験試料とす
る。実施例２の可逆的熱変色性油性スプレー塗装を用い
て白色塩化ビニルシートにスプレーガンにてスプレー塗
装を施し、厚み４０μｍの可逆的熱変色層を設け、これ
を試験試料とする。実施例３の可逆的熱変色性軟質エポ
キシインキを用いて合成紙に塗工し加熱硬化させた塗工
物を試験試料とする。実施例４の可逆的熱変色性水性デ
ィッピングインキを用いてスプレー状のスチロール樹脂
全体をディッピング塗工し、それを試験試料とする。実
施例５の可逆的熱変色性シートを試験試料とする。実施
例６の可逆的熱変色性シートを試験試料とする。実施例
７の可逆的熱変色性ＯＰＰフイルムシートを試験試料と
する。実施例８の可逆的熱変色性Ｔ−シャツ生地を試験
試料とする。実施例９の虹彩可逆的熱変色性積層体を試
験試料とする。実施例１０の可逆的熱変色性エポキシイ
ンキを用いて合成紙に１００メッシュのスクリーン版に
て印刷し加熱硬化させた印刷物を試験試料とする。実施
例１１の可逆的熱変色性マーキングペンを用いてレポー
ト用紙に筆記した筆跡を試験試料とする。実施例１２の
可逆的熱変色性水性ボールペンを用いてレポート用紙に
筆記した筆跡を試験試料とする。実施例１３の可逆的熱
変色性水性絵具を用いて画用紙に描いた絵を試験試料と
する。実施例１４の真珠光沢調可逆的熱変色性付け爪を
試験試料とする。実施例１５の可逆的熱変色性付け爪を
試験試料とする。実施例１６の可逆的熱変色性ハイパイ
ル生地を試験試料とする。実施例１７の可逆的熱変色性
毛糸を試験試料とする。実施例と同様に比較例も耐光性
試験試料を調製した。比較例１の可逆的熱変色性布帛を
耐光性試験試料とする。比較例２の可逆的熱変色性油性
スプレー塗装を用いて白色塩化ビニルシートにスプレー
ガンにてスプレー塗装を施し、厚み４０μｍの可逆的熱
変色層を設け、これを試験試料とする。比較例３の可逆
的熱変色性軟質エポキシインキを用いて合成紙に塗工し
加熱硬化させた塗工物を試験試料とする。比較例４の可
逆的熱変色性水性ディッピングインキを用いてスプレー
状のスチロール樹脂全体をディッピング塗工し、それを
試験試料とする。比較例５の可逆的熱変色性塩化ビニル
を試験試料とする。比較例６の可逆的熱変色性塩化ビニ
ルを試験試料とする。比較例７の可逆的熱変色性ＯＰＰ
フイルムシートを試験試料とする。比較例８の可逆的熱
変色性Ｔ−シャツ生地を試験試料とする。比較例９の虹
彩可逆的熱変色性積層体を試験試料とする。比較例１０
の可逆的熱変色性エポキシインキを用いて合成紙に１０
０メッシュのスクリーン版にて印刷し加熱硬化させた印
刷物を試験試料とする。比較例１１の可逆的熱変色性マ
ーキングペンを用いてレポート用紙に筆記した筆跡を試
験試料とする。比較例１２の可逆的熱変色性水性ボール
ペンを用いてレポート用紙に筆記した筆跡を試験試料と
する。比較例１３の可逆的熱変色性水性絵具を用いて画
用紙に描いた絵を試験試料とする。比較例１４の真珠光
沢調可逆的熱変色性付け爪を試験試料とする。比較例１
５の可逆的熱変色性付け爪を試験試料とする。比較例１
６の可逆的熱変色性ハイパイル生地を試験試料とする。
比較例１７の可逆的熱変色性毛糸を試験試料とする。Light fastness test method Next, the light fastness of these coating liquid compositions having reversible thermochromic properties is shown. (1) Preparation of light fastness test sample The reversible thermochromic fabric of Example 1 is used as a light fastness test sample. Using the reversible thermochromic oil-based spray coating of Example 2, a white vinyl chloride sheet is spray-coated with a spray gun to provide a reversible thermochromic layer having a thickness of 40 μm, which is used as a test sample. A test sample was a coated product which was coated on synthetic paper using the reversible thermochromic soft epoxy ink of Example 3 and cured by heating. Using the reversible thermochromic water-based dipping ink of Example 4, the entire sprayed styrene resin is dipped and used as a test sample. The reversible thermochromic sheet of Example 5 is used as a test sample. The reversible thermochromic sheet of Example 6 is used as a test sample. The reversible thermochromic OPP film sheet of Example 7 is used as a test sample. The reversible thermochromic T-shirt fabric of Example 8 is used as a test sample. The iris reversible thermochromic laminate of Example 9 is used as a test sample. Using a reversible thermochromic epoxy ink of Example 10 on synthetic paper with a 100-mesh screen plate and heat-curing, a printed material is used as a test sample. The handwriting written on the report paper using the reversible thermochromic marking pen of Example 11 is used as a test sample. The handwriting written on the report paper using the reversible thermochromic water-based ballpoint pen of Example 12 is used as a test sample. A picture drawn on a drawing paper using the reversible thermochromic water-based paint of Example 13 is used as a test sample. The pearlescent reversible thermochromic artificial nail of Example 14 is used as a test sample. The reversible thermochromic artificial nail of Example 15 is used as a test sample. The reversible thermochromic high pile fabric of Example 16 is used as a test sample. The reversible thermochromic wool of Example 17 is used as a test sample. Light resistance test samples were prepared in the comparative examples as in the examples. The reversible thermochromic fabric of Comparative Example 1 is used as a light fastness test sample. The white vinyl chloride sheet was spray-coated with a spray gun using the reversible thermochromic oil-based spray coating of Comparative Example 2 to provide a reversible thermochromic layer having a thickness of 40 μm, and this was used as a test sample. The test sample is a coated product which is coated on synthetic paper using the reversible thermochromic soft epoxy ink of Comparative Example 3 and cured by heating. Using the reversible thermochromic water-based dipping ink of Comparative Example 4, the entire sprayed styrene resin is dipped and applied as a test sample. The reversible thermochromic vinyl chloride of Comparative Example 5 is used as a test sample. The reversible thermochromic vinyl chloride of Comparative Example 6 is used as a test sample. Reversible thermochromic OPP of Comparative Example 7
The film sheet is used as the test sample. The reversible thermochromic T-shirt fabric of Comparative Example 8 is used as a test sample. The iris reversible thermochromic laminate of Comparative Example 9 was used as a test sample. Comparative Example 10
10 on synthetic paper using reversible thermochromic epoxy ink
A printed material printed on a 0 mesh screen plate and cured by heating is used as a test sample. The handwriting written on the report paper using the reversible thermochromic marking pen of Comparative Example 11 is used as a test sample. The handwriting written on report paper using the reversible thermochromic aqueous ballpoint pen of Comparative Example 12 is used as a test sample. The picture drawn on the drawing paper using the reversible thermochromic water-based paint of Comparative Example 13 is used as a test sample. The pearlescent tone reversible thermochromic artificial nail of Comparative Example 14 is used as a test sample. Comparative Example 1
5 is used as a test sample. Comparative Example 1
The reversible thermochromic high pile fabric of No. 6 is used as a test sample.
The reversible thermochromic wool of Comparative Example 17 is used as a test sample.

【００８１】（２） 耐光堅牢度の試験方法 実施例１〜１７及び比較例１〜１７の試料をキセノンア
ーク灯光試験機（ヘラウス社製）を使用して耐光堅牢度
試験を行い耐光堅牢度を比較した。キセノンアーク灯耐
光堅牢度試験は、ＪＩＳ Ｌ−０８４３（キセノンアー
ク灯光に対する染色堅牢度試験）の規格に準じて行っ
た。キセノンアーク灯の照射時間は１０時間、２０時
間、３０時間照射の３ポイントにおいて測定した。(2) Test method for light fastness The samples of Examples 1 to 17 and Comparative Examples 1 to 17 were subjected to a light fastness test using a xenon arc lamp light tester (manufactured by Heraus) to determine the light fastness. Compared. The light fastness test of a xenon arc lamp was performed in accordance with the standard of JIS L-0843 (dyeing fastness test for xenon arc lamp light). The irradiation time of the xenon arc lamp was measured at three points of irradiation for 10 hours, 20 hours, and 30 hours.

【００８２】（３） 耐光堅牢度試験結果について 表１８〜表２１に、前記の耐光堅牢度試験による結果を
示す。前記耐光堅牢度試験結果の着色濃度保持率につい
て説明する。一定時間照射した各試料片と未照射状態の
試料片を、色差計（東京電色製）を用いて、試験の着色
状態での濃度刺激値（Ｘ値）を測定する。着色濃度保持
率は次の計算式から算出した。 着色濃度保持率（％）＝１００−照射後の刺激値（Ｘ）
／１００−照射前の刺激値（Ｘ）×１００(3) Results of light fastness test Tables 18 to 21 show the results of the light fastness test. The color density retention rate of the light fastness test result will be described. Using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd.), each of the sample pieces irradiated for a certain time and the sample pieces in the non-irradiated state are measured for the density stimulus value (X value) in the colored state of the test. The coloring density retention was calculated from the following formula. Color density retention rate (%) = 100−stimulus value (X) after irradiation
/ 100-stimulus value before irradiation (X) x 100

【００８３】[0083]

【表１８】 [Table 18]

【００８４】[0084]

【表１９】 [Table 19]

【００８５】[0085]

【表２０】 [Table 20]

【００８６】[0086]

【表２１】 [Table 21]

【００８７】[0087]

【発明の効果】本発明による被覆用液状組成物は発色時
の耐光性が著しく向上し、使用命数が大きく延長する優
れた効果を奏する。The liquid composition for coating according to the present invention has an excellent effect of remarkably improving the light fastness at the time of color development and extending the life expectancy.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｄ０６Ｍ 23/12 Ｄ０６Ｍ 23/12 // Ｃ０７Ｄ 207/323 Ｃ０７Ｄ 207/323 213/38 213/38 213/69 213/69 233/56 233/56 235/08 235/08 239/88 239/88 263/58 263/58 277/64 277/64 277/72 277/72 493/10 493/10 Ｅ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI D06M 23/12 D06M 23/12 // C07D 207/323 C07D 207/323 213/38 213/38 213/69 213/69 233 / 56 233/56 235/08 235/08 239/88 239/88 263/58 263/58 277/64 277/64 277/72 277/72 493/10 493/10 E

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 ａ．電子供与化合物と、 ｂ．電子受容化合物と、 ｃ．変色温度調整剤と、 ｄ．つぎの一般式Ｉで示され、ａ．の電子供与化合物
１．０重量部に対し０．３〜７０重量部の使用割合の電
子受容性を有する耐光性付与剤と一般式Ｉ 【化１】 ｛式中、ｎ＝５〜１７（直鎖及び分岐）、Ｘ＝Ｃ１〜Ｃ
４（直鎖及び分岐）、ハロゲン、Ｙ＝Ｃ１〜Ｃ４（直鎖
及び分岐）、ハロゲン、ｐ＝０〜３、ｍ＝０〜３であ
る。｝ ｅ．液状の展色料と、からなる、発色時の耐光性を向上
した可逆的熱変色性を有する被覆用液状組成物。1. A method comprising: a. An electron donating compound; b. An electron accepting compound; c. A discoloration temperature adjuster; d. Represented by the following general formula I, a. A light-fastness-imparting agent having an electron-accepting property in an amount of 0.3 to 70 parts by weight based on 1.0 part by weight of the electron-donating compound of formula (I) and a general formula I 中 wherein n = 5-17 (straight and branched), X = C 1 -C
4 (linear and branched), halogen, Y = C 1 -C 4 (linear and branched), halogen, p = 0 to 3, is m = 0 to 3. ｝ E. A liquid composition for coating comprising a liquid vehicle and having reversible thermochromic properties with improved light fastness during color development. 【請求項２】 ｄ．の電子受容性を有する耐光性付与剤
を、ｂ．の電子受容体に兼用した、請求項１に記載され
た発色時の耐光性を向上した可逆的熱変色性を有する被
覆用液状組成物。2. d. A lightfastness imparting agent having an electron accepting property of b. The liquid composition for coating having reversible thermochromic property and improved light fastness at the time of color development according to claim 1, which is also used as an electron acceptor. 【請求項３】 ａ．〜ｄ．成分をマイクロカプセルに内
蔵した、請求項１または２に記載された発色時の耐光性
を向上した可逆的熱変色性を有する被覆用液状組成物。3. A method according to claim 1, wherein: a. ~ D. The coating liquid composition according to claim 1 or 2, wherein the component is incorporated in a microcapsule and has a reversible thermochromic property with improved light fastness during color development. 【請求項４】 ｅ．成分が合成樹脂ビヒクルである、請
求項１ないし３のいずれか１項に記載された発色時の耐
光性を向上した可逆的熱変色性を有する被覆用液状組成
物。E. The liquid composition for coating according to any one of claims 1 to 3, wherein the component is a synthetic resin vehicle and has a reversible thermochromic property with improved light fastness during color development. 【請求項５】 請求項１ないし４のいずれか１項に記載
された被覆用液状組成物のｅ．成分が塗料用展色料であ
る、発色時の耐光性を向上した可逆的熱変色性塗料。5. The coating liquid composition according to any one of claims 1 to 4, wherein e. A reversible thermochromic paint with improved light fastness at the time of color development, which is a coloring agent for paint. 【請求項６】 請求項１ないし４のいずれか１項に記載
された被覆用液状組成物のｅ．成分が印刷インキ用展色
料である、発色時の耐光性を向上した可逆的熱変色性印
刷インキ。6. The coating liquid composition according to any one of claims 1 to 4, wherein e. A reversible thermochromic printing ink whose component is a coloring agent for printing inks and has improved light fastness during color development. 【請求項７】 請求項１ないし４のいずれか１項に記載
された被覆用液状組成物のｅ．成分が筆記具用インキ用
展色料である、発色時の耐光性を向上した可逆的熱変色
性筆記具用インキ。7. The coating liquid composition according to any one of claims 1 to 4, wherein e. A reversible thermochromic ink for writing implements whose component is a coloring agent for ink for writing implements and has improved light fastness during color development. 【請求項８】 請求項１ないし４のいずれか１項に記載
された被覆用液状組成物のｅ．成分が化粧料用ラッカー
である、発色時の耐光性を向上した可逆的熱変色性化粧
料。8. The liquid composition for coating according to any one of claims 1 to 4, wherein e. A reversible thermochromic cosmetic having an improved light fastness at the time of color development, which is a cosmetic lacquer. 【請求項９】 請求項１ないし４のいずれか１項に記載
された被覆用液状組成物のｅ．成分が繊維処理剤用バイ
ンダである、発色時の耐光性を向上した可逆的熱変色性
繊維処理剤。9. The coating liquid composition according to any one of claims 1 to 4, wherein e. A reversible thermochromic fiber treating agent having an improved light resistance at the time of color development, wherein the component is a binder for a fiber treating agent. 【請求項１０】 請求項１ないし４のいずれか１項に記
載された被覆用液状組成物のｅ．成分が絵具用展色料で
ある、発色時の耐光性を向上した可逆的熱変色性絵具。10. The coating liquid composition according to any one of claims 1 to 4, wherein e. A reversible thermochromic paint with improved light fastness during color development, which is a coloring agent for paint.
JP20701397A 1997-06-27 1997-06-27 Liquid composition reversibly changing its color with heat Pending JPH1121479A (en)

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JP20701397A JPH1121479A (en) 1997-06-27 1997-06-27 Liquid composition reversibly changing its color with heat

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JPH1121479A true JPH1121479A (en) 1999-01-26

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2382560A (en) * 2001-11-29 2003-06-04 Rockware Glass Ltd Environmentally Sensitive Bottle
JP2012241175A (en) * 2011-05-24 2012-12-10 Mitsubishi Pencil Co Ltd Aqueous ink composition for writing utensil
CN104499298A (en) * 2015-01-04 2015-04-08 哈尔滨工业大学 Temperature-indicating fiber and preparation method thereof
JP2017115049A (en) * 2015-12-25 2017-06-29 株式会社パイロットコーポレーション Reversible thermochromic pigment composition, pigment and pigment set using the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2382560A (en) * 2001-11-29 2003-06-04 Rockware Glass Ltd Environmentally Sensitive Bottle
JP2012241175A (en) * 2011-05-24 2012-12-10 Mitsubishi Pencil Co Ltd Aqueous ink composition for writing utensil
CN104499298A (en) * 2015-01-04 2015-04-08 哈尔滨工业大学 Temperature-indicating fiber and preparation method thereof
JP2017115049A (en) * 2015-12-25 2017-06-29 株式会社パイロットコーポレーション Reversible thermochromic pigment composition, pigment and pigment set using the same

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