JP2006063238A - Thermally erasable writing utensil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermally erasable writing utensil that simply and thermally erases a holograph, which is formed by ink in a colored state of a temperature-sensitively color-changing color-memorizing composition, by scraping, having practicality of keeping the holograph in an erased state at a normal temperature. <P>SOLUTION: The thermally erasable writing utensil is packed with a temperature-sensitively color-changing color-memorizing ink composition that comprises at least microcapsule pigment having a temperature-sensitively color-changing color-memorizing composition consisting of a uniformly compatibilized body composed of (a) an electron-donating coloring organic compound, (b) an electron-accepting compound and (c) a reaction medium for controlling the color reaction of the components (a) and (b), a solvent and a resin in which the microcapsule pigment exhibits hysteresis width (▵H) of 40°C-70°C with respect to a color intensity-temperature curve, has 45-95°C complete decolorizing temperature (T<SB>4</SB>) and ≤0°C coloring start temperature (T<SB>2</SB>) and changes in color from a colored color to a colorless color. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat erasable writing instrument. More specifically, the present invention relates to a heat erasable writing instrument having a function of allowing handwriting formed on a writing surface to remain in a normal storage state and to erase by applying heat by a simple means when unnecessary.

Conventionally, as a type of writing instrument that can erase the handwriting formed on the writing surface, the writing instrument is composed of a writing instrument filled with an ink containing a dye that develops and decolors depending on PH and an erasing liquid, and the writing instrument formed by the writing instrument. A method of erasing by applying an erasing liquid thereon is disclosed (for example, see Patent Document 1).
However, since the writing instrument needs to carry an erasing liquid, it is difficult to carry and safe, and since the erasing liquid remains in the erased portion, write using the same type of writing instrument. However, the dye was decolored so that it was impossible to form handwriting.
Further, although a writing instrument is disclosed that is filled with ink containing a pigment and a film-forming resin and can erase the handwriting with an eraser (see, for example, Patent Document 2), the handwriting does not peel off by hand, and However, it was difficult to provide both the fixability enough to peel off by rubbing with an eraser, and the storability and erasability of handwriting were not sufficiently satisfied.
And (b) an electron-donating color-forming organic compound, (b) an electron-accepting compound, (c) a sensation comprising a compound that is a reaction medium that reversibly causes the electron-donating reaction of (a) and (b). A writing instrument filled with ink in which a thermochromic color memory composition is dispersed in a solvent is disclosed (see, for example, Patent Document 3), and only one state exists in the normal temperature range among both states before and after the color change. However, when the writing instrument is put to practical use, it does not necessarily satisfy the function of maintaining the color tone in the normal temperature range. The thermochromic color memory composition may be discolored, or the recorded material obtained by writing with the ink may be discolored to exhibit the desired function.
The erasing method includes body temperature such as touch, hair dryer, hot water, etc., but the temperature-sensitive color-changing color memory composition that changes color at body temperature cannot maintain a colored state in summer. Even if the temperature-sensitive color-changing color memory composition that changes color with a hair dryer or warm water can provide a function of changing color at a relatively high temperature, it cannot be said that it is a simple means and does not satisfy portability. .
Japanese Patent Publication No.55-18471 Japanese Patent Laid-Open No. 10-195366 JP-A-7-186588

  The present invention is capable of thermally erasing the handwriting formed from the thermochromic color memory composition in a colored state by a simple means of rubbing, maintaining the erased state of the handwriting in a normal temperature range, and erasing The present invention intends to provide a heat erasable writing instrument that can be repeatedly written at a location.

（式中、Ｒは炭素数４以上のアルキル基又はアルケニル基を示す。）
筆記先端部にボールペンチップを備えたこと、擦過部材を備えてなること、筆記先端部を覆うキャップを有してなり、前記キャップ先端部に擦過部材を固着してなること、軸筒先端部に擦過部材を固着してなること、擦過部材がＳＥＢＳ樹脂であること等を要件とする。 The present invention comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a homogeneous solution of a reaction medium that controls the color reaction of (a) and (b). It comprises at least a microcapsule pigment encapsulating a temperature-sensitive color-changing color memory composition, a solvent, and a resin. The microcapsule pigment has a hysteresis width (ΔH) of 40 ° C. to 70 ° C. with respect to a color density-temperature curve. Filled with a temperature-sensitive color-changing color memory ink composition that has a complete decolorization temperature (T ₄ ) of 45 to 95 ° C. and a color development start temperature (T ₂ ) of 0 ° C. or less, and changes from colored to colorless. A heat erasable writing instrument is required.
Furthermore, (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, (c) a sensitivity comprising a homogeneous solution of a reaction medium that controls the color reaction of (a) and (b) above. It comprises at least a microcapsule pigment encapsulating a thermochromic color memory composition, a solvent, and a resin, and the microcapsule pigment exhibits a hysteresis width (ΔH) of 40 ° C. to 70 ° C. with respect to a color density-temperature curve. A complete color erasing temperature (T ₄ ) of 45 to 95 ° C. and a color development start temperature (T ₂ ) of 0 ° C. or less, and a temperature-sensitive color-changing color memory ink composition that changes from colored to colorless is filled. A heat erasable writing instrument having rewritability capable of erasing the handwriting formed from the ink composition with a rubbing member and repeatedly forming the handwriting with the ink composition at the erasing portion is a requirement.
Furthermore, the hysteresis width (ΔH) is 50 to 70 ° C., the complete color erasing temperature (T ₄ ) is 50 to 90 ° C., and the color development start temperature (T ₂ ) is −3 ° C. or less. The complete color development temperature (T ₁ ) is −30 ° C. or higher, the (c) reaction medium is an ester compound represented by the following general formula (1),

(In the formula, R represents an alkyl group or alkenyl group having 4 or more carbon atoms.)
It is provided with a ballpoint pen tip at the writing tip, a rubbing member, a cap that covers the writing tip, and a rubbing member fixed to the cap tip, The requirement is that the rubbing member is fixed, and that the rubbing member is SEBS resin.

  The present invention exhibits a wide hysteresis width (ΔH) with respect to a color density-temperature curve, causes reversible discoloration, and allows temperature-sensitive discoloration that can clearly and alternately store and hold both a colored state and a decolored state in a normal temperature range. The handwriting formed with the ink in a state in which the color-coloring memory composition is colored can be easily erased by heat by rubbing, and the state where the handwriting is erased can be maintained at room temperature and can be repeatedly written on the erased portion. It is possible to provide a heat erasable writing instrument with excellent practicality.

The hysteresis characteristics in the color density-temperature curve of the temperature-sensitive color-changing color memory composition used in the present invention will be described below 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) capable of maintaining the complete color development state. 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 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.
Here, the difference between T ₄ and T ₃ , or the difference between T ₂ and T ₁ (Δt) is a scale indicating the sensitivity of discoloration.

In the present invention, the ΔH value that can be maintained in each of the colored state and the decolored state is in the range of 40 ° C. to 70 ° C., preferably 50 to 70 ° C., more preferably 60 to 70 ° C.
Furthermore, among the two states before and after the color change of the temperature-sensitive color-change color memory composition, only one specific state exists in the normal temperature range, and the handwriting by the temperature-change color-change color memory composition is easily erased by rubbing. In order to achieve this, the complete color erasing temperature (T ₄ ) is 45 to 90 ° C., and the color development start temperature (T ₂ ) is 0 ° C. or lower.
Here, both the coloring state and the decoloring state can coexist in the normal temperature range, and in order to facilitate the erasability by scratching the handwriting, the complete decoloring temperature (T ₄ ) is 45 to 95 ° C., and Explaining whether the color development start temperature (T ₂ ) is 0 ° C. or less, when heating is stopped in a state where the color development state does not reach the complete color erasure temperature (T ₄ ) through the color erasure start temperature (T ₃ ), The phenomenon of returning to the coloring state again occurs, and the state in which coloring occurs even if the cooling is stopped in a state where the color developing start temperature (T ₂ ) is not reached from the decolored state and the complete coloring temperature (T ₁ ) is not reached. Therefore, if the complete color erasing temperature (T ₄ ) is 45 ° C. or more exceeding the normal temperature range, the color development state is maintained in the normal use state, and the color development start temperature (T ₂ ) is normal temperature. If it is 0 ° C. or less below the range, the decolored state is maintained in normal use.
Furthermore, when the handwriting is erased by rubbing, if the complete color erasing temperature (T ₄ ) is 95 ° C. or less, the handwriting formed on the writing surface can be sufficiently erased by frictional heat due to several rubbing by the rubbing member. .
When the complete decoloring temperature (T ₄ ) exceeds 95 ° C., the frictional heat obtained by rubbing with the rubbing member becomes difficult to reach the complete decoloring temperature, making it difficult to erase easily and increasing the number of scratches. Alternatively, the writing surface may be damaged because the load tends to be excessively rubbed. Therefore, the temperature setting is an important requirement for a heat-erasable writing instrument that selectively displays the colored and decolored handwriting on the writing surface, and can satisfy convenience and practicality. .
In the temperature setting of the above-mentioned complete decoloring temperature (T ₄ ), it is preferable that the temperature is higher in order to maintain the color development state in the normal use state, and the frictional heat due to scratching is the complete decolorization temperature ( In order to exceed T ₄ ), a low temperature is preferred.
Therefore, the complete decoloring temperature (T ₄ ) is preferably 50 to 90 ° C, more preferably 50 to 85 ° C.
Furthermore, in the temperature setting of the color development start temperature (T ₂ ) described above, a lower temperature is preferable in order to maintain the decolored state in a normal use state, and −3 ° C. or lower is preferable. 5 degrees C or less is more suitable.
In the present invention, it is necessary to bring the temperature-sensitive color-changing color memory composition in a state filled in the writing instrument into a colored state. Therefore, it is necessary to cool the writing instrument, the ink composition, or the microcapsule pigment in advance to develop the temperature-sensitive color-changing color memory composition.
As a cooling means in the production process, it is preferable to cool in a general-purpose freezer, but considering the cooling capacity of the freezer, the limit is up to −30 ° C. Therefore, the complete coloring temperature (T ₁ ) is −30 ° C. or higher. It is preferable that

Specific examples of the compounds for the components (A), (B), and (C) of the temperature-sensitive color-changing color memory composition showing the above-mentioned color change behavior are shown below.
As the component (a), that is, the electron donating color-forming organic compound, conventionally known diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl aza Examples thereof include phthalides, 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, carboxyl groups and esters thereof as substituents thereof. 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、Ｒは炭素数１乃至８のアルキル基を示す。）
具体的には、図２に示すように完全消色状態を示す温度（Ｔ₄ ）から発色を開始する温度（Ｔ₂ ）を経て完全発色温度を示す温度（Ｔ₁ ）に達する際の変色挙動において、発色を開始する温度（Ｔ₂ ）が高温側にシフトして徐々に発色する挙動を示さず、図１のように発色を開始する温度（Ｔ₂ ）と完全発色温度を示す温度（Ｔ₁ ）の温度差が小さく、消色状態から発色状態に鋭敏に移行する挙動を示し易くなる。
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。
前記一般式（２）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-dihydroxydiphenyl sulfone, 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 Methylbutane, 1,1-bis (4'-hydroxyphenyl) -2-methylpropane, 1,1-bis (4'-hydroxyphenyl) n-hexane, 1,1-bis (4'-hydroxyphenyl) n- Heptane, 1,1-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) ethyl propionate, 2,2 -Bis (4'-hydroxyphenyl) -4-methylpentane, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 2,2-bis (4'-hydroxyphenyl) Sulfonyl) n- heptane, there is 2,2-bis (4'-hydroxyphenyl) n- nonane.
As the compound having a phenolic hydroxyl group, a compound having a phenolic hydroxyl group having at least 3 benzene rings and having a molecular weight of 250 or more, preferably a molecular weight of 250 to 500, or the general formula (2) 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.

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms.)
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.
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 general formula (2),
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 ester compound of component (c) will be specifically exemplified.
The ester compound suitably used in the present invention is an ester compound represented by the general formula (1) composed of an alcohol compound having two aromatic rings in the molecule and a saturated or unsaturated fatty acid having 4 or more carbon atoms. is there.
R in the formula represents an alkyl group or alkenyl group having 4 or more carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 8 to 18 carbon atoms.
Specific examples of the compound include butanoic acid-4-benzyloxyphenylethyl, pentanoic acid-4-benzyloxyphenylethyl, hexanoic acid-4-benzyloxyphenylethyl, heptanoic acid-4-benzyloxyphenylethyl, and octanoic acid. -4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, dodecanoic acid-4-benzyloxyphenylethyl, tridecanoic acid -4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid-4-benzylo Cyphenylethyl, octadecanoic acid-4-benzyloxyphenylethyl, nonadecanoic acid-4-benzyloxyphenylethyl, eicosanoic acid-4-benzyloxyphenylethyl, tricosanoic acid-4-benzyloxyphenylethyl, tetracosanoic acid-4-benzyl Oxyphenylethyl, pentacosanoic acid-4-benzyloxyphenylethyl, hexacosanoic acid-4-benzyloxyphenylethyl, heptacosanoic acid-4-benzyloxyphenylethyl, octacosanoic acid-4-benzyloxyphenylethyl, nonacosanoic acid-4-benzyl Examples thereof include oxyphenyl ethyl, triacontanoic acid-4-benzyloxyphenylethyl, and hentriacontanoic acid-4-benzyloxyphenylethyl.

  The ester compound has a wide hysteresis width equivalent to or greater than that of the ester compound used in the conventional temperature-sensitive color-changing color memory composition. Excellent in properties.

  As the component (c) of the present invention, the ester compound is used, 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 addition amount is preferably 20 or less (parts by weight) with respect to the ester compound 100 in order to effectively exhibit the desired color memory effect.

The proportions of the components (A), (B), and (C) depend on the concentration, the color change temperature, the color change form, and the type of each component. In general, the component ratio at which a desired characteristic is obtained is (B) Component 0.1 to 50, preferably 0.5 to 20, (c) Component 1 to 800, preferably 5 to 200 (all the parts are parts by weight) Is).
Each component may be a mixture of two or more, and an antioxidant, an ultraviolet absorber, an infrared absorber, a dissolution aid, etc. can be added as long as the function is not hindered.

The three-component homogeneous solution is used by being encapsulated in microcapsules. It does not deteriorate its function even when it comes in contact with chemically active substances such as acidic substances, basic substances, peroxides, or other solvent components. This is because the temperature-sensitive color-changing color memory composition can be maintained in the same composition and exhibit the same effects under various usage conditions.
The microcapsules satisfy the practicality in the range of an average particle size of 0.5 to 20 μm, preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm.
When the average value of the maximum outer diameter exceeds 20 μm, the microcapsule lacks dispersion stability for use in ink.
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, the range of inclusion / wall membrane = 7/1 to 1/1 (weight ratio) is effective for the microcapsule. When the ratio of inclusion is larger than the above range, the color density and sharpness at the time of color development. However, 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. 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.

In the present invention, the microcapsule pigment is dispersed in a solvent to obtain an ink composition.
As a solvent used for the ink, water and, if necessary, a water-soluble organic solvent are used.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2- Pyrrolidone, and the like.

Examples of resins include ketone resins, ketone-formaldehyde resins, amide resins, alkyd resins, rosin-modified resins, rosin-modified phenol resins, phenol resins, xylene resins, polyvinylpyrrolidone, α- and β-pinene / phenol polycondensation resins, and polyvinyl butyral. Resins, acrylic resins, styrene-maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, and the like can be mentioned. By being present in the ink, adhesion to the writing surface and viscosity can be imparted.
In the present invention, the handwriting adheres to the writing surface and has a fixing property that does not peel off by rubbing with a normal finger touch or the like. Addition of the resin is an important requirement because it needs to be fixed.

Further, if necessary, a shear thinning agent can be added.
By adding the shear thinning agent, it is possible to suppress bleeding of the handwriting, so that even if writing on a fiber material such as a highly penetrating cloth as well as paper, the handwriting does not bleed and a good handwriting is achieved. Can be formed.
Furthermore, when the writing instrument to be filled with the ink is in the form of a ballpoint pen, it prevents ink leakage from the gap between the ball and the tip when not in use, or the ink when the writing tip is left upward (upright state). Backflow can be prevented.
The viscosity of the ink composition to which the shear thinning agent is added is 20 to 300 mPa · s at a shear rate of 3.84 S ⁻¹ by an E-type rotational viscometer at 20 ° C., and It is preferable that the shear thinning index is 0.1 to 0.9.
The shear thinning index (n) is expressed by an empirical formula T = Kj ⁿ (K is a non-Newtonian viscosity coefficient) obtained from rheological measurement using a viscometer such as a shear stress value (T) and a shear rate value (j). It is a value calculated by fitting.

  Examples of the shear thinning agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 to 8 million) whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose, alka gum, guar gum, locust bean gum and A gel having the ability to be extracted from seaweeds such as glucomannan, agar, carrageenan, etc., polymers having a molecular weight of 100,000 to 150,000 mainly composed of derivatives thereof, hydroxyethyl cellulose, alginic acid alkyl esters, and alkyl esters of methacrylic acid. Viscous polysaccharides, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester Nonionics having an HLB value of 8 to 12, such as polyoxyethylene castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivatives, polyoxyethylene alkyl ether / polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid amide, etc. Examples of the surfactant include salts of dialkyl or dialkenylsulfosuccinic acid, a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.

  When the ink composition of the present invention is used by filling a ballpoint pen, a higher fatty acid such as oleic acid, a nonionic surfactant having a long chain alkyl group, a polyether-modified silicone oil, a thiophosphorous acid tri (alkoxycarbonylmethyl ester) ) And thiophosphite triester (alkoxycarbonylethyl ester), etc., polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether It is preferable to add a lubricant such as a phosphoric acid diester or a metal salt, an ammonium salt, an amine salt, an alkanolamine salt thereof to give the ball seat an antiwear effect.

  In addition, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium night as necessary Rust prevention agent such as light, saponin, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetra Preservatives or fungicides such as chloro-4- (methylsulfonyl) pyridine, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin , Sorbit, N'nitto, wetting agents such as pyrophosphate sodium, defoamers, may be used a dispersing agent, a fluorine based surfactant to improve ink permeability and nonionic surfactants.

The ink composition is put into practical use by filling a marking pen or ballpoint pen with a tip attached to the writing tip.
When filling the marking pen, the structure and shape of the marking pen itself are not particularly limited. For example, a fiber tip, felt tip, plastic tip is attached to the writing tip, and the fiber bundle contained in the shaft cylinder is used. The ink occlusion body is impregnated with ink, the ink is supplied to the tip of the writing, the ink is directly stored inside the shaft cylinder, and the ink flow rate adjustment member consisting of a comb groove-like ink flow rate adjustment member or fiber bundle is interposed The marking pen of structure is mentioned.
When filling the ball-point pen, the structure and shape of the ball-point pen itself are not particularly limited. For example, an ink occlusion body composed of a fiber bundle housed in the shaft tube is impregnated with ink and supplied to the writing tip. Structure, ink is stored directly inside the shaft cylinder, and there is an ink storage tube filled with the ink composition in the shaft cylinder, with a comb groove-shaped ink flow control member and an ink flow control member consisting of fiber bundles interposed The ink storage tube communicates with a chip having a ball attached to the tip, and a ballpoint pen having a structure in which a liquid stopper for backflow prevention is in intimate contact with the end surface of the ink.

The ballpoint pen tip will be described in more detail. A tip formed by holding a ball in a ball holding portion obtained by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, or a metal material is cut by a drill or the like A chip formed by holding the ball in the ball holding part formed by the above, a chip provided with a resin ball receiving seat inside a metal or plastic chip, or a ball held by the chip is moved forward by a spring body Energized items can be applied.
Moreover, the said ball | bowl can use the thing about 0.3-3 mm diameters, such as a cemented carbide alloy, stainless steel, a ruby, a ceramic, resin, rubber | gum.
In addition, the writing instrument filled with the ink of the present invention includes those provided with a rolling mechanism such as a roller at the tip of the writing for forming a handwriting by the same rolling operation as that of the ball.

For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon is used as the ink storage tube that stores the ink composition.
Furthermore, by using a transparent, colored transparent, or translucent molded body as the ink containing tube, the ink color, the remaining amount of ink, and the like can be confirmed.
In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member.
The ink storage tube may be a refill type in which the refill is accommodated in the shaft cylinder, or the shaft cylinder itself having a tip mounted on the tip is used as an ink container to directly fill the shaft cylinder with ink. May be.

The back end of the ink composition accommodated in the ink accommodating tube may be filled with an ink backflow prevention body.
The ink backflow prevention body composition is composed of a non-volatile liquid or a hardly volatile liquid.
Specifically, petroleum jelly, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil, and one or more can be used in combination.

It is preferable to add a gelling agent to the nonvolatile liquid and / or the hardly volatile liquid to increase the viscosity to a suitable viscosity. The surface of the silica is hydrophobized, the surface is methylated fine particle silica, and aluminum silicate. , Swellable mica, hydrophobic thickeners such as bentonite and montmorillonite, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, fatty acid amide, amide modified Examples include dextrin compounds such as polyethylene wax, hydrogenated castor oil, fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow prevention body composition and a solid ink backflow prevention body composition can be used in combination.

The rubbing member used for erasing the handwriting formed by the heat erasable writing instrument of the present invention is an elastomer and plastic foam which is rich in elasticity and can generate frictional heat by generating appropriate friction during rubbing. An elastic body such as, for example, is suitable, but may be a plastic molded body or a metal.
In addition, as with a writing instrument filled with a conventional eraser erasable ink, the eraser can be used to scratch the handwriting. However, since an erased residue is generated at the time of rubbing, the above-mentioned scraping member is preferably used. .
As the material of the rubbing member, silicone resin or SEBS resin (styrene ethylene butadiene styrene block copolymer) is preferably used. However, the silicone resin easily adheres to the portion erased by rubbing, and when repeatedly written. Since the handwriting tends to be repelled, SEBS resin is more preferably used.
The scraping member may be a member having an arbitrary shape that is separate from the writing instrument, but is excellent in portability by being fixed to the writing instrument.
Examples of the location where the rubbing member is fixed include a cap tip (top) or a shaft tube tip (portion where no writing tip is provided).
Furthermore, it is also possible to provide a small protrusion of any shape on a part of the cap or a part of the shaft tube to make a scraping member.

Examples of the present invention are shown below, but the present invention is not limited thereto.
Example 1
Preparation of temperature-sensitive color-changing color-memory microcapsule pigment (i) 4.5 parts by weight of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (1,) 1,1- Bis (4'-hydroxyphenyl) n-decane 4.5 parts by weight, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 7.5 parts by weight, (c) 4-benzyloxyphenyl caprate as component A temperature-sensitive color-changing color memory composition comprising 50.0 parts by weight of ethyl is uniformly heated and dissolved, and 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 40.0 parts by weight of a co-solvent are used as wall film materials. The mixed solution is emulsified and dispersed in 8% aqueous polyvinyl alcohol solution so as to form fine droplets. After stirring at 70 ° C. for about 1 hour, 2.5 parts by weight of a water-soluble aliphatic modified amine is added. Stirring was continued for 6 hours to obtain a temperature-sensitive color-change color-memory microcapsule pigment suspension.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has a hysteresis width (ΔH) of 63 ° C., a complete color development temperature (T ₁ ) of −20 ° C., a color development start temperature (T ₂ ) of −9 ° C., and a decolorization start temperature (T ₃ ) of 40 ° C. The complete decoloring temperature (T ₄ ) is 57 ° C., and the color changes from black to colorless with temperature change.

Preparation of temperature-sensitive color-changing color memory ink 25.7 parts by weight of the microcapsule pigment, 0.2 parts by weight of succinoglycan (shear thinning agent), 5.5 parts by weight of urea, 7.5 parts by weight of glycerin, Nonionic permeability imparting agent [manufactured by San Nopco Co., Ltd., trade name: Nopco SW-WET-366] 0.03 parts by weight, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.15 parts by weight, preservative [Zeneca Co., Ltd., trade name: Proxel XL-2] 0.1 parts, lubricant [Daiichi Kogyo Seiyaku Co., Ltd. Prisurf A212C] 0.5 parts by weight A temperature-sensitive color-changing color memory ink comprising 0.5 parts by weight of triethanolamine and 59.82 parts by weight of water was prepared.

Preparation of writing instrument 0.97 g of the ink (previously cooled to −20 ° C. or lower and allowed to stand at room temperature after coloring the microcapsule pigment in black) was sucked and filled in 0.97 g of a polypropylene pipe having an inner diameter of 4.4 mm, It connected with the ball-point pen tip through the resin holder.
Next, from the rear part of the polypropylene 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 the cylinder was assembled and the cap was fitted, a deaeration process was performed by a centrifugal process to obtain a ballpoint pen.
The ball-point pen tip has a stainless steel ball having a diameter of 1.0 mm held at the tip end of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. The cap is biased forward by the body, and the cap is formed by fixing SEBS resin as a friction member on the top.

Black characters (handwriting) were formed by writing on the paper using the ballpoint pen.
The handwriting was black at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−9 ° C.) and not higher than the complete color erasing temperature (57 ° C.).
When the character is abraded with a friction member fixed to the cap, the character disappears and becomes colorless, and this state is maintained at a temperature not lower than the color development start temperature (−9 ° C.) and not higher than the complete color erasing temperature (57 ° C.). Was holding.
In addition, the character could be formed again with the ball-point pen at the location where the handwriting was erased, and the handwriting could be formed at the location where the handwriting was repeatedly erased.

Example 2
Preparation of thermosensitive color-changing color memory microcapsule pigment (a) As component (3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4- 2.0 parts by weight of azaphthalide, 8.0 parts by weight of bis (3-methyl-4-hydroxyphenyl) sulfide as component (b), 5.0 parts by weight of 2,2-bis (4′-hydroxyphenyl) hexafluoropropane A temperature-sensitive color-changing color memory composition comprising 50.0 parts by weight of 4-benzyloxyphenylethyl caprate as the component (c) is uniformly heated and dissolved, and the aromatic polyvalent isocyanate prepolymer 30 is used as the wall film material. A solution prepared by mixing 0.0 part by weight and 40.0 parts by weight of a co-solvent is emulsified and dispersed in an 8% aqueous solution of polyvinyl alcohol so as to form fine droplets. After stirring for a while, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued for 6 hours to obtain a temperature-sensitive color-changing color memory microcapsule pigment suspension.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has a hysteresis width (ΔH) of 64 ° C., a complete color development temperature (T ₁ ) of −14 ° C., a color development start temperature (T ₂ ) of −6 ° C., and a decolorization start temperature (T ₃ ) of 48. ° C., complete decoloring temperature (T ₄ ) is 60 ° C., and the color changes from blue to colorless with temperature change.

Preparation of temperature-sensitive color-changing color memory ink 25.7 parts by weight of the microcapsule pigment, 0.2 parts by weight of succinoglycan (shear thinning agent), 5.5 parts by weight of urea, 7.5 parts by weight of glycerin, Nonionic permeability imparting agent [manufactured by San Nopco Co., Ltd., trade name: Nopco SW-WET-366] 0.03 parts by weight, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.15 parts by weight, preservative [Zeneca Co., Ltd., trade name: Proxel XL-2] 0.1 parts, lubricant [Daiichi Kogyo Seiyaku Co., Ltd. Prisurf A212C] 0.5 parts by weight A temperature-sensitive color-changing color memory ink comprising 0.5 parts by weight of triethanolamine and 59.82 parts by weight of water was prepared.

Preparation of writing instrument 0.97 g of the ink (previously cooled to −14 ° C. or less and allowed to color the microcapsule pigment in blue and then left at room temperature) was sucked and filled into a polypropylene pipe having an inner diameter of 4.4 mm, It connected with the ball-point pen tip through the resin holder.
Next, from the rear part of the polypropylene 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 the cylinder was assembled and the cap was fitted, a deaeration process was performed by a centrifugal process to obtain a ballpoint pen.
The ball-point pen tip has a stainless steel ball having a diameter of 0.7 mm held at the tip end of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. The cap is biased forward by the body, and the cap is formed by fixing SEBS resin as a friction member on the top.

Blue letters (handwriting) were formed by writing on the paper using the ballpoint pen.
The handwriting exhibited a blue color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−6 ° C.) and not higher than the complete decoloring temperature (60 ° C.).
When the character is rubbed with a scraping member fixed to the cap, the character is decolored to become colorless, and this state is maintained at a temperature not lower than the color development start temperature (−6 ° C.) and not higher than the complete color erasing temperature (60 ° C.). Was holding.
In addition, the character could be formed again with the ball-point pen at the location where the handwriting was erased, and the handwriting could be formed at the location where the handwriting was repeatedly erased.

Example 3
Preparation of thermosensitive color-changing color memory microcapsule pigment (a) 2- (butylamino) -8- (diphenylamino) -4-methylspiro [5H- [1] benzopyrano [2-3-g] pyrimidine- as component (a) 5,1 (3′H) -isobenzofuran] -3-one 2.0 parts by weight, (ro) component 1,1-bis (4′-hydroxyphenyl) n-decane 3.0 parts by weight, 2, A temperature-sensitive color-changing color memory composition comprising 5.0 parts by weight of 2-bis (4′-hydroxyphenyl) hexafluoropropane (c) and 50.0 parts by weight of 4-benzyloxyphenylethyl caprate is uniformly formed. A solution prepared by heating and dissolving and mixing 30.0 parts by weight of an aromatic polyisocyanate prepolymer and 40.0 parts by weight of a co-solvent as a wall membrane material is made into fine droplets in an 8% aqueous polyvinyl alcohol solution. The mixture was emulsified and dispersed at 70 ° C. for about 1 hour, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and the mixture was further stirred for 6 hours to change the temperature-sensitive color change color memory microcapsule pigment. A suspension was obtained.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The hysteresis width (ΔH) of the microcapsule pigment is 63 ° C., the complete color development temperature (T ₁ ) is −14 ° C., the color development start temperature (T ₂ ) is −6 ° C., and the color disappearance start temperature (T ₃ ) is 48. ° C., complete decoloring temperature (T ₄ ) is 58 ° C., and changes from pink to colorless with temperature change.

Preparation of temperature-sensitive color-changing color memory ink 25.7 parts by weight of the microcapsule pigment, 0.2 parts by weight of succinoglycan (shear thinning agent), 5.5 parts by weight of urea, 7.5 parts by weight of glycerin, Nonionic permeability imparting agent [manufactured by San Nopco Co., Ltd., trade name: Nopco SW-WET-366] 0.03 parts by weight, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.15 parts by weight, preservative [Zeneca Co., Ltd., trade name: Proxel XL-2] 0.1 parts, lubricant [Daiichi Kogyo Seiyaku Co., Ltd. Prisurf A212C] 0.5 parts by weight A temperature-sensitive color-changing color memory ink comprising 0.5 parts by weight of triethanolamine and 59.82 parts by weight of water was prepared.

Preparation of a writing instrument 0.97 g of the ink (cooled to -14 ° C. or less in advance and allowed to stand at room temperature after coloring the microcapsule pigment in pink) was sucked and filled into a polypropylene pipe having an inner diameter of 4.4 mm. The ballpoint pen tip was connected via a resin holder.
The ballpoint pen tip has a stainless steel ball having a diameter of 1.0 mm held in a ball holding portion formed by cutting a metal material with a drill, and the ball is biased forward by a spring body. The cap is formed by fixing SEBS resin as a friction member on the top.

A pink character (handwriting) was formed by writing on the paper using the ballpoint pen.
The handwriting had a pink color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−6 ° C.) and not higher than the complete decoloring temperature (58 ° C.).
When the character is abraded with a rubbing member fixed to the cap, the character is decolored and colorless, and this state is maintained at a temperature not lower than the color development start temperature (−6 ° C.) and not higher than the complete color erasing temperature (58 ° C.). Was holding.
In addition, the character could be formed again with the ball-point pen at the location where the handwriting was erased, and the handwriting could be formed at the location where the handwriting was repeatedly erased.

Example 4
Preparation of thermosensitive color-change color memory microcapsule pigment (i) As component (4), 3.0 parts by weight of 4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine The temperature-sensitive discoloration comprising 10.0 parts by weight of 2,2-bis (4′-hydroxyphenyl) hexafluoropropane as component (b) and 50.0 parts by weight of 4-benzyloxyphenylethyl caprate as component (c) The color color memory composition was uniformly heated and dissolved, and a solution prepared by mixing 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 40.0 parts by weight of a co-solvent as a wall film material was added to an aqueous 8% polyvinyl alcohol solution. After emulsifying and dispersing to form fine droplets, stirring at 70 ° C. for about 1 hour, adding 2.5 parts by weight of water-soluble aliphatic modified amine, and further stirring for 6 hours, temperature-sensitive discoloration color A chromatic memory microcapsule pigment suspension was obtained.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The hysteresis width (ΔH) of the microcapsule pigment is 69.5 ° C., the complete color development temperature (T ₁ ) is −25 ° C., the color development start temperature (T ₂ ) is −15 ° C., and the color disappearance start temperature (T ₃ ). Is 40 ° C., complete decoloring temperature (T ₄ ) is 59 ° C., and changes from yellow to colorless with temperature change.

Preparation of temperature-sensitive color-changing color memory ink 25.7 parts by weight of the microcapsule pigment, 0.2 parts by weight of succinoglycan (shear thinning agent), 5.5 parts by weight of urea, 7.5 parts by weight of glycerin, Nonionic permeability imparting agent [manufactured by San Nopco Co., Ltd., trade name: Nopco SW-WET-366] 0.03 parts by weight, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.15 parts by weight, preservative [Zeneca Co., Ltd., trade name: Proxel XL-2] 0.1 parts, lubricant [Daiichi Kogyo Seiyaku Co., Ltd. Prisurf A212C] 0.5 parts by weight A temperature-sensitive color-changing color memory ink comprising 0.5 parts by weight of triethanolamine and 59.82 parts by weight of water was prepared.

Preparation of a writing instrument 0.97 g of the ink (previously cooled to −25 ° C. or less and allowed to color the microcapsule pigment in yellow and then allowed to stand at room temperature) is sucked and filled into a polypropylene pipe having an inner diameter of 4.4 mm, It connected with the ball-point pen tip through the resin holder.
Next, an ink backflow prevention body (liquid stopper) having viscoelasticity mainly composed of polybutene was filled from the rear part of the polypropylene pipe to obtain a ballpoint pen refill.
The ballpoint pen tip has a 0.7 mm diameter stainless steel ball held in a ball holding portion formed by cutting a metal material with a drill, and the ball is biased forward by a spring body. The cap is formed by fixing SEBS resin as a friction member on the top.

A yellow character (handwriting) was formed by writing on the paper using the ballpoint pen.
The handwriting had a yellow color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−15 ° C.) and not higher than the complete color erasing temperature (59 ° C.).
When the character is rubbed with a scraping member fixed to the cap, the character is decolored to become colorless, and this state is maintained at a temperature not lower than the color development start temperature (−15 ° C.) and not higher than the complete color erasing temperature (59 ° C.). Was holding.
In addition, the character could be formed again with the ball-point pen at the location where the handwriting was erased, and the handwriting could be formed at the location where the handwriting was repeatedly erased.

Example 5
Preparation of temperature-sensitive color-changing color memory microcapsule pigment (I) As component, 3.2 parts by weight of 1,3-dimethyl-6-diethylaminofluorane, 1.3 parts by weight of 1,2-benz-6-ethylisoamylfluorane Parts, (b) 1,1-bis (4'-hydroxyphenyl) 2-methylpropane 4.0 parts by weight, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 6.0 parts by weight, (C) A temperature-sensitive color-changing color memory composition comprising 50.0 parts by weight of 4-benzyloxyphenylethyl laurate as a component is uniformly heated and dissolved, and an aromatic polyvalent isocyanate prepolymer 30. A solution prepared by mixing 0 part by weight and 40.0 parts by weight of a co-solvent is emulsified and dispersed in 8% polyvinyl alcohol aqueous solution to form fine droplets, and stirring is continued at 70 ° C. for about 1 hour. Thereafter, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued for 6 hours to obtain a temperature-sensitive color-changing color memory microcapsule pigment suspension.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has a hysteresis width (ΔH) of 67 ° C., a complete color development temperature (T ₁ ) of −6 ° C., a color development start temperature (T ₂ ) of 0 ° C., and a decolorization start temperature (T ₃ ) of 58 ° C. The complete color erasing temperature (T ₄ ) is 70 ° C., and the color changes from blue to colorless with temperature change.

Preparation of temperature-sensitive color-changing color memory ink 25.7 parts by weight of the above microcapsule pigment, 0.33 parts by weight of xanthan gum (shear thinning agent), 10.0 parts by weight of urea, 10.0 parts by weight of glycerin, nonionic Permeability imparting agent [manufactured by San Nopco Co., Ltd., trade name: Nopco SW-WET-366] 0.6 parts by weight, modified silicone antifoaming agent [manufactured by San Nopco Co., Ltd., trade name: Nopco 8034] 0.1 Parts by weight, preservative [Zeneca Co., Ltd., trade name: Proxel XL-2] 0.1 parts by weight, lubricant [Daiichi Kogyo Seiyaku Co., Ltd., Prisurf A212C] 0.5 parts by weight, triethanolamine A temperature-sensitive color-changing color memory ink comprising 0.5 parts by weight and water 52.17 parts by weight was prepared.

Preparation of a writing instrument 0.97 g of the ink (previously cooled to −6 ° C. or lower to allow the microcapsule pigment to develop a blue color and then allowed to stand at room temperature) into a polypropylene pipe having an inner diameter of 4.4 mm, It connected with the ball-point pen tip through the resin holder.
Next, an ink backflow prevention body (liquid stopper) having viscoelasticity mainly composed of polybutene was filled from the rear part of the polypropylene pipe to obtain a ballpoint pen refill.
The ballpoint pen tip has a stainless steel ball having a diameter of 0.6 mm held by a ball holding portion formed by cutting a metal material with a drill, and the ball is biased forward by a spring body. The cap is formed by fixing SEBS resin as a friction member on the top.

Blue letters (handwriting) were formed by writing on the paper using the ballpoint pen.
The handwriting exhibited a blue color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (0 ° C.) and not higher than the complete decoloring temperature (70 ° C.).
When the character is abraded with a rubbing member fixed to the cap, the character is decolored and colorless, and this state is maintained at a temperature not lower than the color development start temperature (0 ° C.) and not higher than the complete color erasing temperature (70 ° C.). Was.
In addition, the character could be formed again with the ball-point pen at the location where the handwriting was erased, and the handwriting could be formed at the location where the handwriting was repeatedly erased.

Example 6
Preparation of temperature-sensitive color-changing color memory microcapsule pigment (i) 2,5-part by weight of 1,3-dimethyl-6-diethylaminofluorane as component, 2,2-bis (4'-hydroxyphenyl) as component (b) ) From 5.0 parts by weight of hexafluoropropane, 4.0 parts by weight of 1,1-bis (4′-hydroxyphenyl) n-decane, and from 50.0 parts by weight of 4-benzyloxyphenylethyl laurate as component (c) 8% of a solution in which 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 40.0 parts by weight of a co-solvent were mixed as a wall film material by uniformly heating and dissolving the resulting temperature-sensitive color-changing color memory composition. After emulsifying and dispersing in water in polyvinyl alcohol so as to form fine droplets and stirring for about 1 hour at 70 ° C., 2.5 parts by weight of a water-soluble aliphatic modified amine is added, and stirring is continued for another 6 hours Thus, a temperature-sensitive color-change color-memory microcapsule pigment suspension was obtained.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment. The hysteresis width (ΔH) of the microcapsule pigment is 63 ° C., the complete color development temperature (T ₁ ) is −8 ° C., the color development start temperature (T ₂ ) is −1 ° C., and the color disappearance start temperature (T ₃ ) is 52 ° C. ° C., complete decoloring temperature (T ₄ ) is 65 ° C., and changes from orange to colorless with temperature change.

Preparation of temperature-sensitive color-changing color memory ink 25.7 parts by weight of the above microcapsule pigment, 0.33 parts by weight of xanthan gum (shear thinning agent), 10.0 parts by weight of urea, 10.0 parts by weight of glycerin, nonionic Permeability imparting agent [manufactured by San Nopco Co., Ltd., trade name: Nopco SW-WET-366] 0.6 parts by weight, modified silicone antifoaming agent [manufactured by San Nopco Co., Ltd., trade name: Nopco 8034] 0.1 Parts by weight, preservative [Zeneca Co., Ltd., trade name: Proxel XL-2] 0.1 parts by weight, lubricant [Daiichi Kogyo Seiyaku Co., Ltd., Prisurf A212C] 0.5 parts by weight, triethanolamine A temperature-sensitive color-changing color memory ink comprising 0.5 parts by weight and water 52.17 parts by weight was prepared.

Preparation of a writing instrument 0.97 g of the ink (previously cooled to −8 ° C. or lower and allowed to stand at room temperature after coloring the microcapsule pigment in orange) was sucked and filled in 0.97 g of a polypropylene pipe having an inner diameter of 4.4 mm, It connected with the ball-point pen tip through the resin holder.
Next, from the rear part of the polypropylene 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 the cylinder was assembled and the cap was fitted, a deaeration process was performed by a centrifugal process to obtain a ballpoint pen.
The ballpoint pen tip has a stainless steel ball having a diameter of 0.6 mm held at the tip end of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. The cap is biased forward by the body, and the cap is formed by fixing SEBS resin as a friction member on the top.

An orange character (handwriting) was formed by writing on the paper surface using the ballpoint pen.
The handwriting had an orange color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−1 ° C.) and not higher than the complete decoloring temperature (65 ° C.).
When the character is abraded with a rubbing member fixed to the cap, the character is decolored and colorless, and this state is maintained at a temperature not lower than the color development start temperature (−1 ° C.) and not higher than the complete color erasing temperature (65 ° C.). Was holding.
In addition, the character could be formed again with the ball-point pen at the location where the handwriting was erased, and the handwriting could be formed at the location where the handwriting was repeatedly erased.

Example 7
Preparation of temperature-sensitive color-changing color-memory microcapsule pigment (i) 4.5 parts by weight of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (1,) 1,1- Bis (4'-hydroxyphenyl) n-decane 4.5 parts by weight, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 7.5 parts by weight, (c) 4-benzyloxyphenyl caprate as component A temperature-sensitive color-changing color memory composition comprising 50.0 parts by weight of ethyl is uniformly heated and dissolved, and 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 40.0 parts by weight of a co-solvent are used as wall film materials. The mixed solution is emulsified and dispersed in 8% aqueous polyvinyl alcohol solution so as to form fine droplets. After stirring at 70 ° C. for about 1 hour, 2.5 parts by weight of a water-soluble aliphatic modified amine is added. Stirring was continued for 6 hours to obtain a temperature-sensitive color-change color-memory microcapsule pigment suspension.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has a hysteresis width (ΔH) of 63 ° C., a complete color development temperature (T ₁ ) of −20 ° C., a color development start temperature (T ₂ ) of −9 ° C., and a decolorization start temperature (T ₃ ) of 40 ° C. The complete decoloring temperature (T ₄ ) is 57 ° C., and the color changes from black to colorless with temperature change.

Preparation of temperature-sensitive color-changing color memory ink 25.7 parts by weight of the microcapsule pigment, 0.2 parts by weight of succinoglycan (shear thinning agent), 5.5 parts by weight of urea, 7.5 parts by weight of glycerin, Nonionic permeability imparting agent [manufactured by San Nopco Co., Ltd., trade name: Nopco SW-WET-366] 0.03 parts by weight, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.15 parts by weight, preservative [Zeneca Co., Ltd., trade name: Proxel XL-2] 0.1 parts, lubricant [Daiichi Kogyo Seiyaku Co., Ltd. Prisurf A212C] 0.5 parts by weight A temperature-sensitive color-changing color memory ink comprising 0.5 parts by weight of triethanolamine and 59.82 parts by weight of water was prepared.

Preparation of writing instrument 0.97 g of the ink (previously cooled to −20 ° C. or lower and allowed to stand at room temperature after coloring the microcapsule pigment in black) was sucked and filled in 0.97 g of a polypropylene pipe having an inner diameter of 4.4 mm, It connected with the ball-point pen tip through the resin holder.
Next, from the rear part of the polypropylene 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 the cylinder was assembled and the cap was fitted, a degassing process was performed by centrifugation to obtain a ballpoint refill.
The ball-point pen refill was accommodated in the shaft cylinder, and a knock member at the rear end of the shaft cylinder was pressed to obtain a knock-type ball pen in which the ball-point pen tip was drawn out from the tip of the shaft cylinder.
The ball-point pen tip has a stainless steel ball having a diameter of 0.7 mm held at the tip end of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. It is energized forward by the body.

Black characters (handwriting) were formed by writing on the paper using the ballpoint pen.
The handwriting was black at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−9 ° C.) and not higher than the complete color erasing temperature (57 ° C.).
When the character is abraded with a SEBS resin abrading member, the character is decolored and colorless, and this state is maintained at a temperature not lower than the color development start temperature (−9 ° C.) and not higher than the complete color erasing temperature (57 ° C.). Was holding.
In addition, the character could be formed again with the ball-point pen at the location where the handwriting was erased, and the handwriting could be formed at the location where the handwriting was repeatedly erased.

Example 8
Preparation of thermosensitive color-changing color memory microcapsule pigment (a) 2- (butylamino) -8- (diphenylamino) -4-methylspiro [5H- [1] benzopyrano [2-3-g] pyrimidine- as component (a) 5,1 (3'H) -isobenzofuran] -3-one 2.0 parts by weight, (ro) component 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 parts by weight, Uniform temperature-sensitive color-changing color memory composition comprising 3.0 parts by weight of 1-bis (4'-hydroxyphenyl) n-decane and 50.0 parts by weight of 4-benzyloxyphenylethyl caprate as component (c) A solution prepared by mixing 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 40.0 parts by weight of a co-solvent as a wall film material was dissolved into fine droplets in an 8% aqueous polyvinyl alcohol solution. The mixture was emulsified and dispersed, and stirred at 70 ° C. for about 1 hour. Then, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued for 6 hours. A suspension was obtained.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has a hysteresis width (ΔH) of 65 ° C., a complete color development temperature (T ₁ ) of −16 ° C., a color development start temperature (T ₂ ) of −8 ° C., and a decolorization start temperature (T ₃ ) of 48. ° C., complete decoloring temperature (T ₄ ) is 58 ° C., and changes from pink to colorless with temperature change.

Preparation of temperature-sensitive color-changing color memory ink 18.8 parts by weight of the microcapsule pigment, 0.2 parts by weight of anhydrous sodium carbonate, hydroxyethyl cellulose [manufactured by Union Carbide Japan Co., Ltd., trade name: Serosize WP-09B] 4 parts by weight, glycerin 5.0 parts by weight, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.02 parts by weight, preservative [manufactured by Zeneca Co., Ltd., trade name : Proxel XL-2] A thermochromic color memory ink comprising 1.0 part and 74.58 parts by weight of water was prepared.

Fabrication of a writing instrument A fiber-focused ink occlusion body in which the ink (previously cooled to -16 ° C. or lower and the microcapsule pigment is colored pink and left at room temperature) is coated with a polyester sliver with a synthetic resin film. 2.0 g of (porosity of about 89%) was impregnated and accommodated in the shaft tube, and a bullet-type fiber pen body (porosity of about 53%) was attached to the tip of the shaft tube to obtain a marking pen.
The marking pen is provided with a detachable cap, and the cap is formed by fixing SEBS resin as a scraping member on the top.

The marking pen was used to write on the paper to form pink characters (handwriting).
The handwriting had a pink color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−8 ° C.) and not higher than the complete color erasing temperature (58 ° C.).
When the character is rubbed with a scraping member fixed to the cap, the character is decolored to become colorless, and this state is maintained at a temperature not lower than the color development start temperature (−8 ° C.) and not higher than the complete erasing temperature (58 ° C.). Was holding.
In addition, the character could be formed again with the marking pen at the place where the handwriting was erased, and the handwriting could be formed at the place where the handwriting was repeatedly erased.

Example 9
Preparation of thermosensitive color-change color memory microcapsule pigment a (a) 2,5-part by weight of 1,3-dimethyl-6-diethylaminofluorane as component, 2,2-bis (4'-hydroxy) as component (b) Phenyl) hexafluoropropane 5.0 parts by weight, 1,1-bis (4'-hydroxyphenyl) n-decane 3.0 parts by weight, and (c) component 4-benzyloxyphenylethyl caprate 50.0 parts by weight A solution in which 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 40.0 parts by weight of a co-solvent are mixed as a wall film material is uniformly dissolved in a temperature-sensitive color-changing color memory composition comprising 8 After emulsifying and dispersing in fine water in a polyvinyl alcohol solution to form fine droplets, stirring was continued at 70 ° C. for about 1 hour, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued for 6 hours. A temperature-sensitive color-change color-memory microcapsule pigment suspension was obtained.
The suspension was centrifuged to isolate thermochromic color memory microcapsule pigment a.
The microcapsule pigment has a hysteresis width (ΔH) of 62.5 ° C., a complete color development temperature (T ₁ ) of −20 ° C., a color development start temperature (T ₂ ) of −9 ° C., and a decolorization start temperature (T ₃ ). Is 42 ° C. and the complete color erasing temperature (T ₄ ) is 54 ° C., and the color changes from orange to colorless with temperature change.

Preparation of thermosensitive color-changing color memory microcapsule pigment b (A) 2.5 parts by weight of 3,3-bis- (2-ethoxy-4-diethylaminiamino) 4-azaphthalide as component (2) 2 as component (B) , 2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 parts by weight, 1,1-bis (4'-hydroxyphenyl) n-decane 3.0 parts by weight, and (c) capric acid 4- A temperature-sensitive color-changing color memory composition comprising 50.0 parts by weight of benzyloxyphenylethyl is uniformly heated and dissolved, and 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer as a wall film material, 40.0% of a co-solvent The mixed solution is emulsified and dispersed in 8% aqueous polyvinyl alcohol so as to form fine droplets, and after stirring at 70 ° C. for about 1 hour, 2.5 parts by weight of a water-soluble aliphatic modified amine is added. The mixture was further stirred for 6 hours to obtain a temperature-sensitive color-change color memory microcapsule pigment suspension.
The suspension was centrifuged to isolate thermochromic color memory microcapsule pigment b. The microcapsule pigment has a hysteresis width (ΔH) of 62.5 ° C., a complete color development temperature (T ₁ ) of −20 ° C., a color development start temperature (T ₂ ) of −9 ° C., and a decolorization start temperature (T ₃ ). Is 42 ° C. and the complete color erasing temperature (T ₄ ) is 54 ° C., and the color changes from blue-green to colorless.

Preparation of temperature-sensitive color-changing color memory ink 18.8 parts by weight of the above microcapsule pigment a, hydroxyethyl cellulose [manufactured by Union Carbide Japan Co., Ltd., trade name: cellosize WP-09B], 0.4 parts by weight, glycerin 5.0 parts by weight Parts, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.02 parts by weight, preservative [manufactured by Zeneca Co., Ltd., trade name: Proxel XL-2] 1.0 Temperature-sensitive color-change color memory ink A comprising 74 parts by weight of water and 74.78 parts by weight of water was prepared.
Separately from this, 18.8 parts by weight of microcapsule pigment b, hydroxyethyl cellulose (manufactured by Union Carbide Japan Co., Ltd., trade name: Cellosize WP-09B), 0.4 parts by weight, glycerin 5.0 parts by weight, modified silicone-based pigment 0.02 part by weight of a foaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B], 1.0 part of an antiseptic [manufactured by Zeneca Co., Ltd., trade name: Proxel XL-2], 74.78 water A thermochromic color memory ink B consisting of parts by weight was prepared.

Fabrication of a writing instrument A fiber-focused ink occlusion body in which the ink A (previously cooled to −20 ° C. or lower and the microcapsule pigment is colored orange and left at room temperature) is coated with a polyester sliver with a synthetic resin film. (Porosity of about 89%) is impregnated with 1.0 g, accommodated in one of the shaft cylinders provided with a partition at the center of the interior, and a bullet type fiber pen body (porosity of about 53%) is attached to the tip of the shaft cylinder It was.
In addition, a fiber-focused ink occlusion body in which ink B (cooled to −20 ° C. or less in advance to develop a microcapsule pigment in blue-green color and allowed to stand at room temperature) covered with a polyester sliver with a synthetic resin film ( (A porosity of about 89%) was impregnated with 1.0 g, accommodated in the other end of the shaft tube, and a bullet type fiber pen (porosity of about 53%) was attached to the tip of the shaft tube to obtain a double-headed marking pen. .
The marking pen is provided with a detachable cap, and the cap is formed by fixing SEBS resin as a scraping member on the top.

An orange character (handwriting) and a blue-green character (handwriting) were formed by writing on the paper using the marking pen.
The handwriting exhibited orange and bluish green at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−9 ° C.) and not higher than the complete decoloring temperature (54 ° C.).
When the character is abraded with a scraping member fixed to the cap, the character is decolored and colorless, and this state is maintained at a temperature not lower than the color development start temperature (−9 ° C.) and not higher than the complete color erasing temperature (54 ° C.). Was holding.
In addition, the character could be formed again with the marking pen at the place where the handwriting was erased, and the handwriting could be formed at the place where the handwriting was repeatedly erased.

Application example 1
A writing instrument set was obtained by combining the thermochromic writing instruments obtained in Example 2 and Example 4.
A blue character (handwriting) was formed by writing on the paper surface using the ballpoint pen obtained in Example 2.
The handwriting exhibited a blue color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−6 ° C.) and not higher than the complete decoloring temperature (60 ° C.).
When the character is rubbed with a scraping member fixed to the cap, the character is decolored to become colorless, and this state is maintained at a temperature not lower than the color development start temperature (−6 ° C.) and not higher than the complete color erasing temperature (60 ° C.). Was holding.
Further, yellow characters (handwriting) were formed by writing on the paper surface using the ballpoint pen obtained in Example 4 at the location where the handwriting was decolored.
The handwriting had a yellow color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the color development start temperature (−15 ° C.) and not higher than the complete color erasing temperature (59 ° C.).
When the character is rubbed with a scraping member fixed to the cap, the character is decolored to become colorless, and this state is maintained at a temperature not lower than the color development start temperature (−15 ° C.) and not higher than the complete color erasing temperature (59 ° C.). Was holding.
In addition, the blue or yellow character could be formed again with the ball-point pen at the place where the handwriting was erased, and the handwriting could be formed at the place where the handwriting was repeatedly erased.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the temperature-sensitive color-change color memory property composition used for this invention. It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the temperature-sensitive color-change color memory property composition used for this 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 (12)

(A) Electron-donating color-forming organic compound, (b) electron-accepting compound, (c) temperature-sensitive color change comprising a homogeneous solution of a reaction medium that controls the color reaction of (a) and (b) above. The microcapsule pigment includes a color memory composition and at least a microcapsule pigment, a solvent, and a resin. The microcapsule pigment exhibits a hysteresis width (ΔH) of 40 ° C. to 70 ° C. with respect to a color density-temperature curve. Heat obtained by filling a temperature-sensitive color-changing color-memory ink composition having a color temperature (T ₄ ) of 45 to 95 ° C. and a color development start temperature (T ₂ ) of 0 ° C. or less and changing from colored to colorless. Erasable writing instrument. (A) Electron-donating color-forming organic compound, (b) electron-accepting compound, (c) temperature-sensitive color change comprising a homogeneous solution of a reaction medium that controls the color reaction of (a) and (b) above. The microcapsule pigment includes a color memory composition and at least a microcapsule pigment, a solvent, and a resin. The microcapsule pigment exhibits a hysteresis width (ΔH) of 40 ° C. to 70 ° C. with respect to a color density-temperature curve. The color temperature (T ₄ ) is 45 to 95 ° C., the color development start temperature (T ₂ ) is 0 ° C. or less, and a temperature-sensitive color-changing color memory ink composition that changes from colored to colorless is filled. A heat-erasable writing instrument having a re-writing property capable of erasing a handwriting formed from the ink composition with a rubbing member and repeatedly forming a handwriting with the ink composition at an erasing portion.   The heat erasable writing instrument according to claim 1 or 2, wherein the hysteresis width (ΔH) is 50 to 70 ° C. The heat erasable writing instrument according to any one of claims 1 to 3, wherein the complete color erasing temperature (T ₄ ) is 50 to 90 ° C. Heat erasability writing instrument according to any one of claims 1 to 4 coloring starting temperature (T ₂₎ is -3 ° C. or less. The heat erasable writing instrument according to any one of claims 1 to 5, wherein the complete color development temperature (T ₁ ) is -30 ° C or higher. The heat erasable writing instrument according to any one of claims 1 to 6, wherein the reaction medium (c) is an ester compound represented by the following general formula (1).

(In the formula, R represents an alkyl group or alkenyl group having 4 or more carbon atoms.)   The heat erasable writing instrument according to any one of claims 1 to 7, further comprising a ballpoint pen tip at a writing tip.   The heat erasable writing instrument according to any one of claims 1 to 8, comprising a rubbing member.   The heat erasable writing instrument according to claim 9, further comprising a cap that covers the writing tip, and a rubbing member fixed to the tip of the cap.   The heat erasable writing instrument according to claim 9, wherein a rubbing member is fixed to the tip of the shaft tube.   The heat erasable writing instrument according to any one of claims 9 to 11, wherein the rubbing member is a SEBS resin.

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