JP4527501B2 - Temperature-sensitive color-change color memory composition and temperature-sensitive color-change color memory microcapsule pigment containing the same - Google Patents

Description

  The present invention relates to a thermochromic color memory composition and a thermochromic color memory microcapsule pigment containing the same. More specifically, it exhibits a large hysteresis characteristic due to a temperature change and exhibits a reversible color change of color development and decoloration. Even after the application of heat or cold heat required for the color change is removed, either the colored state or the decolored state The present invention relates to a temperature-sensitive color-changing color memory composition that holds the above in a reversible and reversible manner, and a temperature-sensitive color-changing color memory microcapsule pigment containing the same.

The present applicant has previously proposed this type of temperature-sensitive color-changing color memory material (see, for example, Patent Document 1).
The temperature-sensitive color-change color memory material changes color before and after the color change temperature as in the case of the conventional reversible thermo-color change material, and only one specific state exists in the normal temperature range of both the states before and after the color change. However, the other state is maintained while the heat or cold heat necessary for the state to be developed is applied, and when the heat or cold heat is no longer applied, the color changes compared with the type that returns to the state exhibited at room temperature. Either the color on the low temperature side or the color on the high temperature side can be selectively held in the normal temperature range, and can be held interchangeably by applying heat or cold as needed, and temperature sensitive recording. It is applied to various fields such as materials, toys, decoration, and printing.
Japanese Patent Publication No. 4-17154

This type of color memory effect, as disclosed in the Japanese Patent Publication No. 4-17154, is a system in which a specific compound is applied as a constituent component among compounds selected from esters that control the color reaction. Is only expressed.
The present invention further pursues a compound serving as a reaction medium that exhibits the color memory effect, increasing the degree of freedom of selection of the reaction medium, and further increasing the utilization of this type of temperature-sensitive color-changing color memory material. It is about to try.

〔式中、Ｒ₁ は水素原子又はメチル基を示し、ｍは０〜２の整数を示し、Ｘ₁ 、Ｘ₂ のいずれか一方は−（ＣＨ₂ ）_n ＯＣＯＲ₂ 又は−（ＣＨ₂ ）_n ＣＯＯＲ₂ 、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ₂ は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ₁ 及びＹ₂ は水素原子、炭素数１〜４のアルキル基、メトキシ基、又は、ハロゲンを示し、ｒ及びｐは１〜３の整数を示す。但し、（ハ）として下記式（２）で示される化合物を除く。

式中、Ｒ₃ は炭素数４以上のアルキル基又はアルケニル基を示す。〕
更には、前記感温変色性色彩記憶性組成物を内包してなる感温変色性色彩記憶性マイクロカプセル顔料を要件とする。
更には、前記感温変色性色彩記憶性マイクロカプセル顔料が色濃度−温度曲線に関して８℃乃至７０℃のヒステリシス幅を示して変色すること、完全消色温度（Ｔ₄ ）が４０℃以上であり、且つ、発色開始温度（Ｔ₂ ）が２０℃以下である、常温域で色彩記憶性を有すること等を要件とする。 The present inventor is a system in which a compound having a specific structure is applied as a reaction medium for a color reaction, exhibits a thermochromic characteristic with a large hysteresis width (ΔH), and exhibits an effective color memory effect. The headline and the present invention were completed.
The present invention provides (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium for controlling the color reaction of the above-mentioned (a) and (b). And a thermochromic color-memory composition comprising a homogeneous solution of the compound represented by

[Wherein, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and _one of X ₁ and X ₂ represents — (CH ₂ ) _n OCOR ₂ or — (CH ₂ ) _n COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom, 1 to 4 carbon atoms An alkyl group, a methoxy group, or halogen, and r and p each represent an integer of 1 to 3. However, the compound represented by the following formula (2) is excluded as (c).

In the formula, R ₃ represents an alkyl group or alkenyl group having 4 or more carbon atoms. ]
Furthermore, a temperature-sensitive color-changing color memory microcapsule pigment containing the temperature-sensitive color-changing color memory composition is required.
Furthermore, the temperature-sensitive color-changing color memory microcapsule pigment changes color with a hysteresis width of 8 ° C. to 70 ° C. with respect to the color density-temperature curve, and the complete color erasing temperature (T ₄ ) is 40 ° C. or higher. In addition, the color development start temperature (T ₂ ) is 20 ° C. or lower, and has color memory property in a normal temperature range.

  The present invention exhibits a wide hysteresis width (ΔH) with respect to the color density-temperature curve and causes a reversible color change of color development / decoloration. Memory can be retained, and by applying heat or cold as necessary, any color can be reversibly reproduced and the characteristics that can be retained can be effectively expressed. A thermochromic color memory composition having applicability in various fields such as an element and a thermochromic color memory microcapsule pigment containing the same can be provided.

The hysteresis characteristic in the color density-temperature curve of the temperature-sensitive color-changing color memory composition of the present invention and the temperature-sensitive color-changing color memory microcapsule pigment using the same will be described with reference to the graph of FIG.
In FIG. 1, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature T ₄ reaching the complete color erasing state (hereinafter referred to as the complete color erasing temperature), and B is a temperature T ₃ (hereinafter referred to as the color erasing start temperature) at which the complete color development state can be maintained. C is a point indicating a density at a temperature T ₂ at which a completely decolored state can be maintained (hereinafter referred to as a color development start temperature), and D is a temperature T ₁ at which a complete color development state is reached. This is a point indicating the density at (hereinafter referred to as a complete color development temperature).
The discoloration temperature region is the temperature region between T ₁ and T ₄ , and both the colored state and the decolored state can coexist, and the temperature region between T ₂ and T _3, which is the region where the difference in color density is large, is substantial. Discoloration temperature range (two-phase holding temperature range).
The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). It is easy to maintain each state before and after the color change.
The ΔH value that can be maintained in each state before and after the color change is in the range of 8 ° C to 70 ° C. Here, Δt, which is the difference between T ₄ and T ₃ , or the difference between T ₂ and T ₁ , is a scale indicating the sensitivity of discoloration, and a range of 1 ° C. to 10 ° C. is practical.
Further, in order to allow only one of the states before and after the color change to exist at room temperature, the complete decoloring temperature (T ₄ ) is 40 ° C. or higher, preferably 45 ° C. or higher, more preferably 50 ° C. or higher. And the color development start temperature (T ₂ ) is 20 ° C. or lower, preferably 10 ° C. or lower, more preferably 0 ° C. or lower.

In the present invention, the proportions of the three components (A), (B), and (C) depend on the concentration, the color change temperature, the color change form, and the type of each component, but in general, components that provide desired characteristics. The ratio is in the range of (b) component 1 to (b) component 0.1 to 50, preferably 0.5 to 20, (c) component 1 to 800, preferably 5 to 200 (the ratio). Are all parts by weight).
Each component may be a mixture of two or more, and an antioxidant, an ultraviolet absorber, an infrared absorber, a dissolution aid, and the like can be added as long as the function is not hindered.
Moreover, the color change from colored [1] to colored [2] can also be provided by mix | blending a general pigment (non-thermochromic property).

Specific examples of the compounds (a), (b) and (c) are shown below.
As the component (a) of the present invention, that is, the electron donating color-forming organic compound, conventionally known diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl in Examples thereof include drill azaphthalides, fluorans, styrinoquinolines, diazarhodamine lactones, and the like.
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3,3 -Bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- [2-ethoxy-4- ( N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,6-diphenylaminofluorane, 3,6-dimethoxyfluorane, 3,6-di -N-butoxyfluorane, 2-methyl-6- (N-ethyl-Np-tolylamino) fluorane, 3-chloro-6-cyclohexylaminofluorane, 2-methyl -6-cyclohexylaminofluorane, 2- (2-chloroanilino) -6-di-n-butylaminofluorane, 2- (3-trifluoromethylanilino) -6-diethylaminofluorane, 2- (N- Methylanilino) -6- (N-ethyl-Np-tolylamino) fluorane, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-diethylaminofluorane, 2-anilino-3- Methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, 2-xylidino-3-methyl-6-diethylaminofluorane, 1,2-benz-6-diethylamino Fluorane, 1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane, 1,2-benz-6 N-ethyl-N-isoamylamino) fluorane, 2- (3-methoxy-4-dodecoxystyryl) quinoline, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 ′ (3 'H) isobenzofuran] -3'-one, 2- (diethylamino) -8- (diethylamino) -4-methyl-, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1' (3′H) isobenzofuran] -3′-one, 2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl-, spiro [5H- (1) benzopyrano ( 2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (diethylamino) -4-methyl-, spiro [ 5H- (1) benzopyrano (2, 3-d) Pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (N-ethyl-Ni-amylamino) -4 -Methyl-, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino)- 8- (Di-n-butylamino) -4-phenyl, 3- (2-methoxy-4-dimethylaminophenyl) -3- (1-butyl-2-methylindol-3-yl) -4,5 6,7-tetrachlorophthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide 3- (2-ethoxy-4-diethylaminophenyl) 3- (1-pentyl-2-methylindole-3-yl) -4,5,6,7 can be given tetrachloro phthalide like.
Furthermore, there can be mentioned pyridine-based, quinazoline-based, bisquinazoline-based compounds and the like that are effective in developing fluorescent yellow to red color development.

As the electron-accepting compound of component (b), a group of compounds having active protons, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as an acid in the composition and cause component (a) to develop color), electrons There is a group of compounds having pores.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Or what has an amide group, a halogen group, etc., phenol-aldehyde condensation resin etc., such as a bis type and a tris type phenol, are mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

（式中、Ｒ₄ は炭素数１乃至８のアルキル基を示す。）
前記少なくとも３以上のベンゼン環を有し、且つ、分子量が２５０以上のフェノール性水酸基を有する化合物としては、
４，４′，４″−メチリデントリスフェノール、
２，６−ビス〔（２−ヒドロキシ−５−メチルフェノール）メチル〕−４−メチルフェノール、
４，４′−〔１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン〕ビスフェノール、
４，４′，４″−エチリデントリス〔２−メチルフェノール〕、
４，４′−〔（２−ヒドロキシフェニル）メチレン〕ビス［２，３，６−トリフェニルフェノール］、
２，２−メチレンビス［６−［（２−ヒドロキシ−５−メチルフェニル）メチル］−４−メチルフェノール］、
２，４，６−トリス（４−ヒドロキシフェニルメチル）１，３−ベンゼンジオール、
４，４′，４″−エチリデントリスフェノール、
４，４′−［（４−ヒドロキシフェニル）メチレン］ビス［２−メチルフェノール］、
４，４′−［（４−ヒドロキシフェニル）メチレン］ビス［２，６−ジメチルフェノール］、
４，４′−［（４−ヒドロキシフェニル）メチレン］ビス［２−メチルフェノール］、
４，４′−［（４−ヒドロキシフェニル］メチレン］ビス［２，６−ジメチルフェノール］、
４，４′−［（４−ヒドロキシ−３−メトキシフェニル）メチレン］ビス［２，６−ジメチルフェノール］、
２，４−ビス［（５−メチル−２−ヒドロキシフェニル）メチル］−６−シクロヘキシルフェノール、
４，４′−［１−［４−［１−（４−ヒドロキシ−３−メチルフェノール）−１−メチルエチル］フェニル］エチリデン］ビス［２−メチルフェノール］、
４，４′−［（４−ヒドロキシフェニル）メチレン］ビス［２−シクロヘキシル−５−メチルフェノール］、
４，６−ビス［（４−ヒドロキシフェニル）メチル］１，３−ベンゼンジオール、
４，４′−［（３，４−ジ−ヒドロキシフェニル）メチレン］ビス［２，６−ジメチルフェノール］、
４，４′−（１−フェニルエチリデン）ビスフェノール、
５，５′−（１−メチルエチリデン）ビス［１−フェニル−２−オール］、
４，４′，４″−メチリデントリスフェノール、
４，４′−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノール、
４，４′−（フェニルメチレン）ビスフェノール、
４，４′−［１，４−フェニレンビス（１−メチルエチリデン）］ビス［２−メチルフェノール］、
５，５′−（１，１−シクロヘキシリデン）ビス−［１−ビフェニル−２−オール］等が挙げられる。
前記式（３）で示されるフェノール性水酸基を有する化合物としては、
ビス（３−メチル−４−ヒドロキシフェニル）スルフィド、ビス（３，５−ジメチル−４−ヒドロキシフェニル）、ビス（３−エチル−４−ヒドロキシフェニル）スルフィド、ビス（３，５−ジエチル−４−ヒドロキシフェニル）スルフィド、ビス（３−プロピル−４−ヒドロキシフェニル）スルフィド、ビス（３，５−ジプロピル−４−ヒドロキシフェニル）スルフィド、ビス（３−ｔ−ブチル−４−ヒドロキシフェニル）スルフィド、ビス（３，５−ｔ−ブチル−４−ヒドロキシフェニル）スルフィド、ビス（３−ペンチル−４−ヒドロキシフェニル）スルフィド、ビス（３−ヘキシル−４−ヒドロキシフェニル）スルフィド、ビス（３−ヘプチル−４−ヒドキシフェニル）スルフィド、ビス（５−オクチル−２−ヒドロキシフェニル）スルフィド等が挙げられる。
前記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の脂肪族カルボン酸、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から選ばれる化合物等であってもよい。 Specific examples are given below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -3-methylbu 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxyphenyl) n-heptane, , 1-bis (4-hydroxyphenyl) n-octane, 1,1-bis (4-hydroxyphenyl) n-nonane, 1,1-bis (4-hydroxyphenyl) n-decane, 1,1-bis ( 4-hydroxyphenyl) n-dodecane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ethylpropionate, 2,2-bis (4-hydroxyphenyl)- 4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) n-heptane, 2,2-bis It is 4-hydroxyphenyl) n- nonane.
As the compound having a phenolic hydroxyl group, a compound having a phenolic hydroxyl group having at least three benzene rings and having a molecular weight of 250 or more, preferably a molecular weight of 250 to 500, or the following formula (3) When the compound having a phenolic hydroxyl group represented by is used, it is possible to make the color change sensitivity when shifting from the decolored state to the colored state more sensitive. Specifically, as shown in FIG. 2, the discoloration behavior at the time of reaching the temperature (T ₁ ) indicating the complete color development temperature from the temperature (T ₄ ) indicating the completely decolored state through the temperature (T ₂ ) for starting the color development. in the temperature to start the color development (T ₂₎ showed no behavior that develops color gradually shifted to the high temperature side, the temperature indicating the complete coloring temperature and the temperature (T ₂₎ to start the color development as in FIG. 1 (T The temperature difference of ₁ ) is small, and it becomes easy to show a behavior that shifts sharply from the decolored state to the colored state.

(In the formula, R ₄ represents an alkyl group having 1 to 8 carbon atoms.)
As the compound having at least 3 or more benzene rings and having a phenolic hydroxyl group having a molecular weight of 250 or more,
4,4 ', 4 "-methylidenetrisphenol,
2,6-bis [(2-hydroxy-5-methylphenol) methyl] -4-methylphenol,
4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol,
4,4 ', 4 "-ethylidene tris [2-methylphenol],
4,4 '-[(2-hydroxyphenyl) methylene] bis [2,3,6-triphenylphenol],
2,2-methylenebis [6-[(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol],
2,4,6-tris (4-hydroxyphenylmethyl) 1,3-benzenediol,
4,4 ', 4 "-ethylidene trisphenol,
4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylphenol],
4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol],
4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylphenol],
4,4 '-[(4-hydroxyphenyl] methylene] bis [2,6-dimethylphenol],
4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol],
2,4-bis [(5-methyl-2-hydroxyphenyl) methyl] -6-cyclohexylphenol,
4,4 '-[1- [4- [1- (4-hydroxy-3-methylphenol) -1-methylethyl] phenyl] ethylidene] bis [2-methylphenol],
4,4 '-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol],
4,6-bis [(4-hydroxyphenyl) methyl] 1,3-benzenediol,
4,4 '-[(3,4-di-hydroxyphenyl) methylene] bis [2,6-dimethylphenol],
4,4 '-(1-phenylethylidene) bisphenol,
5,5 ′-(1-methylethylidene) bis [1-phenyl-2-ol],
4,4 ', 4 "-methylidenetrisphenol,
4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol,
4,4 '-(phenylmethylene) bisphenol,
4,4 '-[1,4-phenylenebis (1-methylethylidene)] bis [2-methylphenol],
5,5 '-(1,1-cyclohexylidene) bis- [1-biphenyl-2-ol] and the like.
As the compound having a phenolic hydroxyl group represented by the formula (3),
Bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl), bis (3-ethyl-4-hydroxyphenyl) sulfide, bis (3,5-diethyl-4-) Hydroxyphenyl) sulfide, bis (3-propyl-4-hydroxyphenyl) sulfide, bis (3,5-dipropyl-4-hydroxyphenyl) sulfide, bis (3-t-butyl-4-hydroxyphenyl) sulfide, bis ( 3,5-t-butyl-4-hydroxyphenyl) sulfide, bis (3-pentyl-4-hydroxyphenyl) sulfide, bis (3-hexyl-4-hydroxyphenyl) sulfide, bis (3-heptyl-4-hydride) Xylphenyl) sulfide, bis (5-octyl-2-hydroxyphenyl) Rufido, and the like.
The compound having a phenolic hydroxyl group can develop the most effective thermochromic property, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

Next, the component (c) represented by the formula (1) is specifically shown.

Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is preferable because a temperature-sensitive color-changing color memory composition having a wider hysteresis width can be obtained. Further, R ₁ is a hydrogen atom. It is more preferable that m is 0.
The above-mentioned compound has a hysteresis width as large as or larger than that of the ester used in the conventional temperature-sensitive color-changing color memory composition, specifically, the hysteresis width ( (DELTA) H) is 8-70 degreeC.
By having the hysteresis width described above, it is excellent in the function of selectively holding either the color on the lower temperature side or the color on the higher temperature side than the color change temperature, and is excellent in applicability to various uses.

  The component (c) of the present invention uses the above compound, and other esters, alcohols, carboxylic acids, ketones, amides and the like can be added as long as the hysteresis characteristics do not greatly change. In this case, the amount added is preferably 20 or less (parts by weight) with respect to the compound 100 of the present invention in order to effectively exhibit the desired color memory effect.

The three-component homogeneous compatible mixture can be encapsulated in a microcapsule to form a reversible thermochromic microcapsule pigment, and can be protected with a capsule membrane wall to protect acidic substances, basic substances, peroxides, etc. The contact with a chemically active substance or other solvent component does not deteriorate its function, and the heat resistance stability can be improved.
Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
The average particle diameter of the microcapsules is 0.5 to 50 μm, preferably 1 to 30 μm, and more preferably 1 to 20 μm.
When the average value of the maximum outer diameter exceeds 50 μm, the microcapsule lacks dispersion stability and processability when blended into ink, paint, or thermoplastic resin.
On the other hand, in a system having an average value of the maximum outer diameter of 0.5 μm or less, it is difficult to exhibit high density color developability.
In addition, by making the capsules into fine particles, the ΔH value can be further expanded compared with the ΔH of the homogeneous solution of the essential three-component composition.
For the microcapsules, the range of inclusions / wall film = 7/1 to 1/1 (weight ratio) is effective, and when the wall film ratio is larger than the above range, the color density and sharpness during color development deteriorate. The inclusion / wall membrane = 6/1 to 1/1 (weight ratio) is preferable.
The microencapsulation includes conventionally known isocyanate-based interfacial polymerization methods, in-situ polymerization methods such as melamine-formalin, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, melting There are a dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to use.
The microcapsule pigment can be mixed with a general dye (non-thermochromic) to exhibit a color change behavior from colored (1) to colored (2).

The temperature-sensitive color-changing color memory composition and the temperature-sensitive color-changing color memory microcapsule pigment containing the composition are dispersed in a vehicle containing various additives as necessary, and screen printing, offset printing, process printing, gravure Printing ink used for printing, coater, tampo printing, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc., ink for inkjet, marking pen, ballpoint pen It can be used as a temperature-sensitive color-changing color-memory liquid composition such as ink for writing tools or applicators for fountain pens, fountain pens, etc., inks for crayons, paints, cosmetics, and coloring liquids for fibers.
The material of the support is not specified and is all effective, and can be exemplified by paper, synthetic paper, fiber, fabric, synthetic leather, leather, plastic, glass, ceramic material, metal, wood, stone, etc. Not only the shape but also the uneven shape may be used.
In the case where a non-thermochromic colored layer (including an image) is previously formed on the support, the colored layer can be concealed by a temperature change, and the aspect of the change is further diversified. be able to.
Furthermore, the temperature-sensitive color-change color memory composition and the temperature-sensitive color-change color memory microcapsule pigment containing the same are melt-blended into a thermoplastic resin, a thermosetting resin, a wax, etc., pellets, powder, Alternatively, it can be used as a resin composition for temperature-sensitive color-change color-memory molding as a paste form.
Using the molding resin, any form of three-dimensional modeled object, film, sheet, plate, filament, rod, pipe, etc. by means of general-purpose injection molding, extrusion molding, blow molding, or cast molding A molded body is obtained.
Examples of the additive include a crosslinking agent, a curing agent, a drying agent, a plasticizer, a viscosity modifier, a dispersant, an ultraviolet absorber, an antioxidant, a light stabilizer, an antisettling agent, a smoothing agent, a gelling agent, and an antifoaming agent. Agents, matting agents, penetrating agents, pH adjusting agents, foaming agents, coupling agents, moisturizing agents, fungicides, antiseptics, rust inhibitors and the like.
In addition, a general dye / pigment (non-thermochromic property) may be blended in the liquid composition or the molding resin composition to exhibit a color change behavior from color (1) to color (2).
A layered product in which a reversible thermochromic layer is formed on a support with the liquid material, or a layer containing a light stabilizer and / or a transparent metallic luster pigment is laminated on the molded product to improve light resistance. Alternatively, a durability can be improved by providing a topcoat layer.
Examples of the transparent metallic luster pigment include natural mica, synthetic mica, glass pieces, alumina, and a pigment obtained by coating the surface of a transparent film piece with a metal oxide such as titanium oxide.

  Specific examples of the products using the thermochromic color memory composition and the thermochromic color memory microcapsule pigment encapsulating the thermochromic color memory toy, doll or animal figure toy hair, doll or animal figure toy hair, doll Doll accessories such as homes and furniture, clothing, hats, bags, shoes, accessories toys, plush toys, drawing toys, toy picture books, puzzle toys such as jigsaw puzzles, building toys, block toys, clay toys, fluid toys, tops , Kite, musical instrument toy, cooking toy, gun toy, capture toy, background toy, vehicle, animal, plant, building, food, toy, T-shirt, trainer, blouse, dress, swimsuit, raincoat, ski wear Clothing, footwear such as shoes and shoelaces, handicrafts such as handkerchiefs, towels, furoshiki, carpets, curtains, curtain strings, table racks, rugs, cushions, picture frames, construction Interior decorations such as bedding, pillows, mattresses, bedding, rings, bangles, tiaras, earrings, hair stoppers, false nails, ribbons, scarves, etc., writing instruments, stamps, erasers, underlays, rulers, adhesive tape, etc. Stationery, lipstick, eye shadow, nail polish, hair dye, artificial nails, cosmetics such as artificial nail paint, cups, dishes, chopsticks, spoons, forks, pots, frying pans and other kitchenware, calendars, labels, cards, Recording materials, various printed materials for preventing counterfeiting, books such as picture books, gloves, ties, hats, bags, packaging containers, embroidery thread, exercise equipment, fishing equipment, toothbrushes, coasters, watches, glasses, lighting equipment, air conditioning equipment, Examples include musical instruments, warmers, cool storage agents, photo stands, wallets such as wallets, umbrellas, furniture, vehicles, buildings, temperature detection indicators, and teaching tools.

Examples are shown below, but the present invention is not limited thereto.
Explains the method for producing the temperature-sensitive color-changing color memory composition and the microcapsule pigment containing it in each example, and the method for measuring the temperature-sensitive color-changing color memory composition and the hysteresis characteristics due to temperature changes of the microcapsule pigment. To do.
In addition, the part in an Example shows a weight part.

Example 1
Preparation method of thermosensitive color-change color memory composition (A) 3- (2-Ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) [(I) Component A] 1.0 part, (b) Component 1,1-bis (4-hydroxyphenyl) -2-methylpropane [(B) Component a] 3.0 part, (C) Decanoic acid 4- 50.0 parts of (4-methylbenzyl) oxyphenylethyl [(ha) component compound 4] were homogeneously mixed to obtain a thermosensitive color-changing color memory composition.
The temperature-sensitive color-changing color memory composition changed its color from blue to colorless.

Preparation of measurement sample Methyl ethyl ketone solution (20% by weight) of the temperature-sensitive color-changing color memory composition was applied to a filter paper [Toyo Filter Paper Co., Ltd. 2 filter paper] and methyl ethyl ketone was completely evaporated to obtain a measurement sample.

Method of measuring hysteresis characteristics The measurement sample is set in the measurement part of a color difference meter [TC-3600 type color difference meter, manufactured by Tokyo Denshoku Co., Ltd.], and is 10 ° C / The measurement sample was heated and cooled at a rate of minutes, and the color density at each temperature was measured.
The lightness value displayed on the color difference meter at each temperature is plotted on the graph, and the color density-temperature curve of FIG. 1 is created, and T ₁ (complete color development temperature), T ₂ (color development start temperature) of the measurement sample, T ₃ (decoloring start temperature), T ₄ (complete decoloring temperature), T _H [T ₁ and T ₂ midpoint temperature (T ₁ + T ₂ ) / 2], T _G [T ₃ and T ₄ Midpoint temperature (T ₃ + T ₄ ) / 2] and ΔH (hysteresis width T _G −T _H ) were determined.

Examples 2-7
The temperature-sensitive color-changing color memory composition of Examples 2 to 7 was the same as Example 1 except that the component (c) of the temperature-sensitive color-changing color memory composition was changed to the compounds described in the following table. The hysteresis characteristics were measured.
The following table shows the component (c) and the values of T ₁ , T ₂ , T ₃ , T ₄ , T _H , T _G , and ΔH of the temperature-sensitive color-changing color memory compositions of Examples 2 to 7.
The parts by weight of the components (A), (B), and (C) are the same as in Example 1, and the color changes from blue to colorless.

Example 8
Preparation method of thermosensitive color-change color memory microcapsule pigment (interfacial polymerization)
3- (2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide [(I) component B] 2 as component (A) 1.0 part, (ro) component 1,1-bis (4-hydroxyphenyl) -2-methylpropane [(ro) component a] 6.0 parts, (c) decanoic acid 4- (4-methyl) A temperature-sensitive color-changing color memory composition comprising 50.0 parts of (benzyl) oxyphenylethyl [(ha) component compound 4] is uniformly heated and dissolved, and an aromatic polyvalent isocyanate prepolymer 20.0 is used as a wall film material. Part of the solution and 50 parts of the co-solvent are emulsified and dispersed in microdroplets in a 6% aqueous polyvinyl alcohol solution, and stirring is continued at 70 ° C. for about 1 hour, followed by addition of 2.5 parts of a water-soluble aliphatic amine, Temperature-sensitive discoloration color by stirring for a while To obtain a suspension of memory microcapsule pigment.
The microcapsule pigment was isolated from the suspension of the microcapsule pigment by centrifugation to obtain a thermosensitive color-changing color memory microcapsule pigment that changes color from blue to colorless (average particle size: 3 μm).

Preparation of measurement sample To 60 parts of an aqueous screen printing ink vehicle containing an ethylene-vinyl acetate emulsion as a binder resin, 40 parts of the temperature-sensitive color-changing color-memory microcapsule pigment (solid content 24 parts) are added and dispersed uniformly. Using the temperature-sensitive color-changing color memory ink obtained above, screen printing was performed on high-quality paper to prepare a measurement sample.

Method for Measuring Hysteresis Characteristics The hysteresis characteristics of the temperature-sensitive color-changing color-memory microcapsule pigment were measured in the same manner as in Example 1.

Examples 9-18
A temperature-sensitive color-changing color memory composition comprising the components (A), (B), and (C) shown in the following table is encapsulated in a microcapsule in the same manner as in Example 8, and the temperature-sensitive color-changing color is obtained. A memory microcapsule pigment was prepared, and the hysteresis characteristics were measured in the same manner as in Example 8.
Components (a), (b), (c) of the temperature-sensitive color-changing color memory composition encapsulated in the microcapsule pigments of Examples 8 to 18, the blending amount thereof, and the average particle diameter of the capsules are as follows: Shown in the table.

The color change and T ₁ , T ₂ , T ₃ , T ₄ , T _H , T _G , ΔH of the microcapsule pigments obtained in Examples 8 to 18 are shown in the following table.

Example 19
Preparation method of thermosensitive color-changing color memory microcapsule pigment (in situ polymerization method)
3- (2-Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide [(I) component B] 2 as component (A) 1.0 part, (ro) component 1,1-bis (4-hydroxyphenyl) -2-methylpropane [(ro) component a] 6.0 parts, (ha) component 2-phenylethyloxyphenyl hexadecanoate A solution in which a temperature-sensitive color-changing color memory composition comprising 50.0 parts of methyl [(C) component compound 141] was uniformly heated and dissolved was dissolved in a methyl vinyl ether-maleic anhydride copolymer resin (10%) / hydroxylation. After emulsifying and dispersing in microdroplets in an aqueous solution of sodium (2%) and adding a solution in which 8 parts of melamine and 20 parts of 37% formaldehyde aqueous solution are heated and uniformly dissolved as a wall membrane material, stirring is continued at 80 ° C. for about 3 hours. To obtain a primary suspension of thermochromic color-memory microcapsule pigment Te.
The microcapsule pigment isolated from the primary suspension of the microcapsule pigment by centrifugation is redispersed in an aqueous solution of methyl vinyl ether-maleic anhydride copolymer resin (10%) and sodium hydroxide (2%), and melamine After adding 8 parts and 20 parts of a 37% formaldehyde aqueous solution by heating and uniform dissolution, stirring was continued at 80 ° C. for about 3 hours to obtain a temperature-sensitive color-change color memory microcapsule pigment suspension. The microcapsule pigment was isolated from the suspension of the capsule pigment by centrifugation to obtain a temperature-sensitive color-changing color memory microcapsule pigment that changes color from blue to colorless (average particle size 3 μm).
A measurement sample of the temperature-sensitive color-change color memory microcapsule pigment was prepared in the same manner as in Example 8, and the hysteresis characteristics were measured.

Examples 20-28
A thermosensitive color-changing color memory composition comprising the components (a), (b), and (c) shown in the following table was encapsulated in microcapsules in the same manner as in Example 19, and Examples 20 to 28 were carried out. The thermosensitive color-changing color memory microcapsule pigment was prepared, and the hysteresis characteristics were measured in the same manner as in Example 8.
The components (a), (b) and (c) of the temperature-sensitive color-changing color memory composition encapsulated in the microcapsule pigments of Examples 19 to 28, their blending amounts, and the average particle diameter of the capsules are as follows: Shown in the table.

The color change and T ₁ , T ₂ , T ₃ , T ₄ , T _H , T _G and ΔH of the microcapsule pigments obtained in Examples 19 to 28 are shown in the following table.

In addition, (I) component C in a table | surface is the following compounds.
C: 2- (Dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine-5,1 ′ (3 ′, H) -isobenzofuran ] (3-) Components b and c in the table are the following compounds.
b: 1,1-bis (4-hydroxyphenyl) hexafluoropropane c: 1,1-bis (4-hydroxyphenyl) -1-phenylethane

Application example 1
40 parts (24 parts solid content) of thermosensitive color-change color memory microcapsule pigment prepared in Example 10 was added to 60 parts of an aqueous screen printing ink vehicle containing an ethylene-vinyl acetate emulsion as a binder resin, and dispersed uniformly. A temperature-sensitive color-changing color memory ink was prepared. Using the temperature-sensitive color-changing color-memory ink, screen printing is performed on a white polyester film (thickness 25 μm) to provide a reversible thermochromic layer, and further laminated with a transparent polyester film (thickness 16 μm). A discolorable color memory display was obtained.
The display is cooled to −7 ° C. or lower to completely develop the reversible thermochromic layer in a blue state, and then printed using a thermal transfer printer [Product No .: S4870, Showa Information Equipment Co., Ltd.] Formed letters.
As long as the said display body is hold | maintained in the temperature range of 5 degreeC-43 degreeC, the said white extraction letter is visually recognized.
Further, when the display body is cooled again to −7 ° C. or less and the reversible thermochromic layer is completely colored in blue, the white letters are not visually recognized, and white letters are formed using the thermal transfer printer. The operation could be repeated.

Application example 2
40 parts (24 parts solids) of thermosensitive color-change color memory microcapsule pigment prepared in Example 18 were added to 60 parts of an aqueous screen printing ink vehicle containing an ethylene-vinyl acetate emulsion as a binder resin, and dispersed uniformly. A temperature-sensitive color-changing color memory ink was prepared. Using the temperature-sensitive color-changing color-memory ink, screen printing is performed on a white polyester film (thickness 25 μm) to provide a reversible thermochromic layer, and further laminated with a transparent polyester film (thickness 16 μm). A discolorable color memory display was obtained.
The display body is cooled to -18 ° C. or lower to completely develop the reversible thermochromic layer in a blue state, and then printed using a thermal transfer printer [Part No .: S4870, Showa Information Equipment Co., Ltd.] Formed letters.
The white blank character is visible as long as the display body is held in a temperature range of −10 ° C. to 42 ° C., and can maintain a state where the character is visually recognized in a normal use state. It can be used as an indicator that can irreversibly detect the history when the temperature reaches a high temperature range.

Application example 3
Temperature-sensitive color-changing color memory microcapsule pigment prepared in Example 14 27.0 parts (solid content 16.2 parts), xanthan gum (shear thinning agent) 0.33 parts, urea 10 parts, glycerin 10 parts, Nonionic penetrant imparting agent [trade name: Nopco SW-WET-366, manufactured by San Nopco Co., Ltd.] 0.6 parts, modified silicone-based antifoaming agent [trade name: Nopco 8034, manufactured by San Nopco Co., Ltd.] 0.1 parts, prevention A temperature-sensitive color-changing color memory ink comprising 0.2 parts of glaze [trade name: Proxel XL-2, manufactured by Zeneca Co., Ltd.] and 51.77 parts of water was prepared.

Preparation of writing instrument The temperature-sensitive color-changing color memory ink (previously cooled to 2 ° C. or lower to develop a microcapsule pigment and then allowed to stand at room temperature) was placed in a polypropylene pipe having an inner diameter of 4.4 mm with 0.97 g. The sample was sucked and filled, and connected to a ballpoint pen tip holding a 0.7 mm stainless steel ball at the tip through a resin holder.
Next, from the rear end of the polyprene pipe, an ink backflow prevention body (liquid stopper) having viscoelasticity mainly composed of polybutene is filled, and a tail plug is fitted to the rear part of the pipe. After assembling the shaft cylinder and fitting the cap, the deaeration process was performed by centrifugation to obtain a temperature-sensitive color-changing color memory ballpoint pen.
The cap is formed by attaching SEBS rubber as a friction body at the top.

Blue letters (handwriting) were formed by writing on the paper using the ballpoint pen.
The handwriting has a blue color at room temperature (25 ° C.). When the character is scraped with a friction body, the character is decolored and colorless, and this state can be maintained unless cooled to 10 ° C. or lower. did it.
When the paper surface was placed in a freezer and cooled to 2 ° C. or lower, the color changed to blue again, and the color change behavior could be reproduced repeatedly.

Application example 4
22 parts of thermosensitive color-changing color memory microcapsule pigment prepared in Example 24 (solid content: 13.2 parts) were mixed with 5 parts of glycerin and an antifungal agent (trade name: Proxel XL-2, manufactured by Zeneca Corp.). 0 parts, silicone-based antifoaming agent (trade name: SN deformer 381, manufactured by San Nopco Co., Ltd.) 0.1 parts, water uniformly dispersed in an aqueous medium consisting of 63.9 parts, hydroxyethyl cellulose [water-soluble polymer agglomeration Agent, trade name: Cello size WP-09L, manufactured by Union Carbide Japan Ltd.] While stirring, 8 parts of a 5% aqueous solution is added to the liquid in the dispersion state, and the microcapsule pigment is suspended in a gently aggregated state. A temperature-sensitive color-changing color memory ink was prepared.

Preparation of writing instrument A fiber-focused ink sucker (porosity of about 80%) coated with a polyester resin sliver with a synthetic resin film, and the color-changing color memory ink (preliminarily cooled to 7 ° C or below) to develop a microcapsule pigment. After being allowed to stand at room temperature), it is impregnated and accommodated in the shaft tube, and assembled in contact with a polyester fiber resin processing pen body (porosity of about 50%) attached to the shaft tube tip, A cap was fitted to obtain a temperature-sensitive color-changing color memory marking pen.
The cap is provided with silicone rubber as a friction body at the top.

The character could be modified to pink by drawing a line on the character printed on the paper surface using the marking pen.
The modified portion of the character is pink at room temperature (25 ° C.), and when it is rubbed with a friction body, the modified portion is discolored and becomes colorless, and this state is maintained unless cooled to 13 ° C. or lower. I was able to.
In addition, when the paper surface was put in a freezer and cooled to 7 ° C. or lower, the modification portion showed a color change behavior that turned pink again, and the color change behavior could be reproduced repeatedly.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the temperature-sensitive color-changing color memory composition of the present invention. It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the temperature-sensitive color-changing color memory composition of the present invention.

Explanation of symbols

T ₁ complete color development temperature T ₂ color development start temperature T ₃ color erase start temperature T ₄ complete color erase temperature ΔH Hysteresis width

Claims (4)

(A) An electron-donating color-forming organic compound, (b) an electron-accepting compound, (c) a reaction medium for controlling the color reaction of (a) and (b) is represented by the following formula (1). A thermochromic color memory composition comprising a homogeneous solution of a compound.

[Wherein, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and _one of X ₁ and X ₂ represents — (CH ₂ ) _n OCOR ₂ or — (CH ₂ ) _n COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom, 1 to 4 carbon atoms An alkyl group, a methoxy group, or halogen, and r and p each represent an integer of 1 to 3. However, the compound represented by the following formula (2) is excluded as (c).

In the formula, R ₃ represents an alkyl group or alkenyl group having 4 or more carbon atoms. ]   A thermochromic color-memory microcapsule pigment comprising the temperature-sensitive color-changing color memory composition of claim 1.   The thermosensitive color-changing color memory microcapsule pigment according to claim 2, wherein the color density-temperature curve changes color with a hysteresis width of 8 ° C to 70 ° C. The color density-temperature curve has a color erasability in a normal temperature range in which a complete decoloring temperature (T ₄ ) is 40 ° C or higher and a color development start temperature (T ₂ ) is 20 ° C or lower. 3. A thermosensitive color-changing color memory microcapsule pigment according to 3.

Images