JP5444061B2 - Temperature-sensitive color change color memory toner and cartridge containing the same, image forming apparatus, cartridge set, and image forming apparatus set - Google Patents

Description

  The present invention relates to a temperature-sensitive color-changing color memory toner, a cartridge containing the toner, an image forming apparatus, a cartridge set, and an image forming apparatus set. Specifically, the thermosensitive color-changing color memory toner capable of forming a copy that can be displayed and displayed only in one state in a specific temperature range, and a cartridge containing the same, an image forming apparatus, a cartridge set, The present invention relates to an image forming apparatus set.

Conventionally, attempts have been made to incorporate a reversible thermochromic material having color memory into a toner (see, for example, Patent Document 1).
Although the copy to which the toner is applied has a function of selectively viewing one of the two states before and after the color change, when the formed image is erased, a cloudy afterimage is visually recognized.
Although the white turbid afterimage is difficult to be visually recognized when the copy (paper) is white, the afterimage is remarkably visually recognized in a colored copy, which may impair practicality.

JP 2000-330321 A

The present invention is to solve the problems in the conventional toner, that is,
Temperature-sensitive color-changing color memory toner in which a white cloudy afterimage is not visually recognized when the formed image is erased even when an image is formed on a colored copy as well as a white copy And a cartridge, an image forming apparatus, a cartridge set, and an image forming apparatus set that contain the cartridge.

The present invention relates to (i) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a temperature-sensitive color-changing property comprising a reaction medium for controlling the color reaction of (a) and (b). A microcapsule pigment having an average particle diameter of 0.01 to 0.49 μm encapsulating a color memory composition and a binder resin, wherein the microcapsule pigment has a large hysteresis with respect to a color density-temperature curve. shows the characteristic exhibits photochromic coloring state and decolored state, in the process of temperature rise be in a colored state, it begins decolorized to reach a temperature t _3, a temperature t ₄ or more than the temperature t ₃ become completely decolorized state in frequency, in the process of temperature in the decolored state is lowered, the the temperature t ₃ reaches a lower temperature t _2, colored begins, lower than the temperature t ₂ the temperature t ₁ the following temperature Completely colored in the area The temperature t ₂ and shows the hysteresis characteristics of the colored state or decolorized state at a temperature range is selectively visible between the temperature t _3, the temperature t ₁ is in the range of -50 to 0 ° C., a temperature t No. ₄ requires a temperature-sensitive color-changing color memory toner in the range of 50 to 150 ° C.
Further, in the microcapsule pigment, particles of 1.0 μm or more are 30% by volume or less in the total microcapsule pigment, and the average particle diameter of the microcapsule pigment is in the range of 0.01 to 0.45 μm. The microcapsule pigment exhibits a hysteresis width (ΔH) of 50 ° C. to 100 ° C. with respect to the color density-temperature curve, the temperature t _{4 of the} microcapsule pigment is a temperature exceeding the softening point of the toner, It is a requirement that the softening point (S) of the toner and the temperature t _{4 of the} microcapsule pigment satisfy the following formula (1).
60 ° C. ≦ S + 3 ° C. <t ₄ (1)
Further, a cartridge containing the temperature-sensitive color-changing color memory toner in a container, an image forming apparatus containing the temperature-sensitive color-changing color memory toner, an image forming apparatus containing the cartridge, the cartridge, and a shaft An ink composition containing a colorant that is erased by heating is contained in a cylinder, and the cartridge is composed of a writing instrument provided with a pen body at a writing tip, and the image forming apparatus and the shaft cylinder are erased by heating. An image forming apparatus set including a writing instrument that contains an ink composition containing a colorant and is provided with a pen body at the writing tip is required.

  The present invention relates to a temperature-sensitive color-changing color-memory toner that is rich in practical use and does not allow a white turbid afterimage to be visually recognized at an erased portion when an image formed on a colored copy is erased, and a cartridge containing the toner An image forming apparatus, a cartridge set, and an image forming apparatus set can be provided.

It is a graph which shows the color change behavior of the microcapsule pigment which included the temperature-sensitive color-change color memory composition. It is a longitudinal cross-sectional view of one Example of the writing instrument of this invention. It is a longitudinal cross-sectional view of the other Example of the writing instrument of this invention. It is a longitudinal cross-sectional view of the other Example of the writing instrument of this invention. It is a longitudinal cross-sectional view of the other Example of the writing instrument of this invention. It is a longitudinal cross-sectional view of the other Example of the writing instrument of this invention. It is a longitudinal cross-sectional view of the other Example of the writing instrument of this invention.

The temperature-sensitive color-changing color memory composition comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound that colors the compound, and (c) the (i) and (b). Is a composition containing at least three components of a reaction medium for controlling the color reaction of the color, and the shape of the curve plotting the change of the color density due to the temperature change raises the temperature from the lower temperature side than the color change temperature range. Contrary to the case, the color changes following a path that is largely different from the case where the color change temperature range is lowered from the high temperature side, and the color development state in the low temperature range below the complete color development temperature (t ₁ ) or the complete color erasing temperature (t ₄ ) A composition that can selectively store the decolored state in the above high temperature range in a specific temperature range [temperature range between t _{2 and} t ₃ (substantially two-phase holding temperature range)], A microcapsule pigment encapsulating the composition can be applied.
By encapsulating the temperature-sensitive color-changing color memory composition in a microcapsule, even when it comes into contact with a chemically active substance such as an acidic substance, a basic substance, or a peroxide, or other solvent components, its function Of course, the heat-resistant stability can be maintained, and the temperature-sensitive color-changing color memory composition can be maintained in the same composition under the various use conditions and have the same effects. it can.

The hysteresis characteristic in the color density-temperature curve of the microcapsule pigment encapsulating the temperature-sensitive color-changing color memory composition will be described.
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 (hereinafter referred to as a complete decoloring temperature) that reaches a completely decolored state, and B is a temperature t ₃ (hereinafter referred to as a decoloring start temperature). C is a point indicating a density at a temperature t ₂ at which color development starts (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 (hereinafter referred to as a complete color development state). This is a point indicating a density at a color development temperature).
Discoloration temperature region is a temperature range between the t ₁ and t _4, both states of the colored state and the decolored state can coexist, a temperature range of between t ₂ and t ₃ is a region having a large difference in color density It is a real discoloration temperature range.
The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). If this ΔH value is small, only one specific state can exist in the normal temperature range among both states before and after the color change. Further, when the ΔH value is large, it is easy to maintain each state before and after the color change.
Specifically, as the color change temperature, the complete color development temperature t ₁ is a temperature that can be obtained only in a freezing room, a cold region, etc., that is, −50 to 0 ° C., preferably −40 to −5 ° C., more preferably −30 to − 10 ° C., and the complete decoloring temperature t _{4 is determined} to be a temperature obtained by a heating tool, that is, 50 to 150 ° C., preferably 60 to 150 ° C., more preferably 70 to 150 ° C., and a ΔH value of 50 to By specifying 100 ° C., it is possible to effectively function to maintain colors exhibited in a normal state (daily life temperature range).

Examples of the electron donating color-forming organic compound as the component (a) include diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides, Fluoranes, stylinoquinolines, diazarhodamine lactones and the like.
Examples of these compounds are given below.
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-diethylaminofluorane,
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-g) pyrimidine-5,1 ′ (3′H) isobenzofuran] -3-one,
2- (Di-n-butylamino) -8- (di-n-butylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3' H) Isobenzofuran] -3-one,
2- (Di-n-butylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) 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-g) pyrimidine-5,1 ' (3′H) isobenzofuran] -3-one,
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-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
3 ′, 6′-bis [phenyl (2-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9 ′-[9H] xanthen] -3-one,
3 ′, 6′-bis [phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9 ′-[9H] xanthen] -3-one,
And 3 ', 6'-bis [phenyl (3-ethylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one.
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 the component (b), a compound group having active protons, a pseudo-acidic compound group (a compound group that is not an acid but acts as an acid in the composition to cause the component (I) to develop color), There is a group of compounds having electron vacancies.
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.
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.
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.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１乃至８の整数を示す。）
前記化合物としては、グルタル酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、ピメリン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステルを例示できる。 Furthermore, as the component (c), a compound represented by the following general formula (1) is preferably used.

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 8).
Examples of the compound include a diester of glutaric acid and 2- (4-benzyloxyphenyl) ethanol, and a diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol.

〔式中、Ｒ_１は水素原子又はメチル基を示し、ｍは０〜２の整数を示し、Ｘ_１、Ｘ_２のいずれか一方は−（ＣＨ_２）_ｎＯＣＯＲ_２又は−（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２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。〕
前記式（２）で示される化合物のうち、Ｒ_１が水素原子の場合、より広いヒステリシス幅を有する可逆熱変色性組成物が得られるため好適であり、更にＲ_１が水素原子であり、且つ、ｍが０の場合がより好適である。
なお、式（２）で示される化合物のうち、より好ましくは下記一般式（３）で示される化合物が用いられる。

式中のＲは炭素数８以上のアルキル基又はアルケニル基を示すが、好ましくは炭素数８〜１８のアルキル基、更に好ましくは炭素数８〜１３のアルキル基である。
前記化合物として具体的には、オクタン酸−４−ベンジルオキシフェニルエチル、ノナン酸−４−ベンジルオキシフェニルエチル、デカン酸−４−ベンジルオキシフェニルエチル、ウンデカン酸−４−ベンジルオキシフェニルエチル、ドデカン酸−４−ベンジルオキシフェニルエチル、トリデカン酸−４−ベンジルオキシフェニルエチルを例示できる。 Moreover, the compound shown by following General formula (2) can also be used as said (c) component.

[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. ]
Among the compounds represented by the formula (2), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and further R ₁ is a hydrogen atom, and , M is more preferably 0.
Of the compounds represented by the formula (2), a compound represented by the following general formula (3) is more preferably used.

R in the formula represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 8 to 18 carbon atoms, and more preferably an alkyl group having 8 to 13 carbon atoms.
Specific examples of the compound include octanoic acid-4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, and dodecanoic acid. Examples thereof include -4-benzyloxyphenylethyl and 4-benzyloxyphenylethyl tridecanoate.

（式中、Ｒは炭素数１１以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ１〜３の整数を示し、Ｘ及びＹはそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ハロゲンを示す。）
前記化合物として具体的には、ウンデカン酸１,１−ジフェニルメチル、ドデカン酸１,１−ジフェニルメチル、トリデカン酸１,１−ジフェニルメチル、テトラデカン酸１,１−ジフェニルメチル、ペンタデカン酸１,１−ジフェニルメチル、ヘキサデカン酸１,１−ジフェニルメチル、ヘプタデカン酸１,１−ジフェニルメチル、オクタデカン酸１,１−ジフェニルメチルを例示できる。 Furthermore, a compound represented by the following general formula (4) can also be used as the component (c).

(In the formula, R represents an alkyl group or alkenyl group having 11 or more carbon atoms, m and n each represent an integer of 1 to 3, X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon, respectively. (The alkoxy group of Formula 1-4 is shown, and a halogen.)
Specific examples of the compound include undecanoic acid 1,1-diphenylmethyl, dodecanoic acid 1,1-diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecanoic acid 1,1- Examples thereof include diphenylmethyl, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, and 1,1-diphenylmethyl octadecanoate.

（式中、Ｒは炭素数１乃至１２のアルキル基又はアルケニル基を示し、ｎは１乃至３の整数を示す。）
前記化合物としては、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとペラルゴン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリル酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとウンデカン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンと吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとイソ吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプロン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとエナント酸とのジエステルを例示できる。 Furthermore, a compound represented by the following general formula (5) can also be used as the component (c).

(In the formula, R represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound include a diester of 1,3-bis (2-hydroxyethoxy) benzene and pelargonic acid, a diester of 1,3-bis (2-hydroxyethoxy) benzene and caprylic acid, and 1,3-bis (2 -Hydroxyethoxy) benzene and capric acid diester, 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid diester, 1,4-bis (2-hydroxyethoxy) benzene and valeric acid diester, Diester of 1,4-bis (2-hydroxyethoxy) benzene and isovaleric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, 1,4-bis (2-hydroxyethoxy) A diester of benzene and enanthic acid can be exemplified.

The form of the microcapsule pigment does not refuse application of a circular cross-section, but a non-circular cross-section is effective.
When the microcapsule pigment has a non-circular cross-sectional shape, the microcapsule pigment is not easily destroyed by pressure or heat load in the toner preparation process or heat fixing process. In addition, it is easy to orient thinly and densely on the surface of the copy paper, and when the pressure of the roll in the heat fixing process is applied, it can be elastically deformed appropriately to relieve the stress, thereby suppressing the capsule wall film from being destroyed. In the heating process, the wall membrane elastically deforms in response to the thermal expansion and contraction of the capsule, thereby suppressing the destruction of the capsule wall membrane and protecting the temperature-sensitive color-change color memory composition of the capsule. Can maintain the desired thermal discoloration function.

The microcapsule pigment has an average particle size of 0.01 to 0.49 μm, preferably 0.01 to 0.45 μm, and more preferably 0.1 to 0.45 μm.
When the average particle diameter exceeds 0.49 μm, the ratio of microcapsule pigments that diffusely reflect light increases, so a reversible thermochromic composition encapsulated in microcapsule pigments in a thermochromic image formed on a copy is obtained. The color is changed from colored to colorless, and as a result, the dried coating film on the copy in a state where the image is erased becomes cloudy and easily recognized as an afterimage.
If the average particle diameter is less than 0.01 μm, the afterimage is difficult to be visually recognized, but the color density of the image before erasure is not sufficient because of poor color developability.
In the system satisfying the average particle diameter of the microcapsule pigment in the range of 0.01 to 0.49 μm, the microcapsule pigment exceeding 1.0 μm, which easily diffuses light, is 30% by volume or less in the total microcapsule pigment, By adjusting the volume to preferably 20% by volume or less, more preferably 15% by volume or less, it is possible to further prevent the dried coating film (image) on the copy at the time of erasure from becoming cloudy and make it difficult to visually recognize the afterimage. it can.
Furthermore, when the average particle size of the reversible thermochromic microcapsule pigment is 0.01 to 0.45 μm, particles exceeding 1.0 μm in the microcapsule pigment are 20% by volume or less in the total microcapsule pigment, When adjusted to preferably 15% by volume or less, more preferably 10% by volume or less, the dried coating film (image) on the copy at the time of decoloring can be prevented from becoming clouded, and the afterimage can be made difficult to visually recognize. .
Similarly, when the average particle size of the reversible thermochromic microcapsule pigment is 0.1 to 0.45 μm, particles exceeding 1.0 μm in the microcapsule pigment are similarly 20% by volume or less in the total microcapsule pigment, preferably When the content is adjusted to 15% by volume or less, more preferably 10% by volume or less, the dried coating film (image) on the copy at the time of decoloring can be prevented from becoming cloudy and the afterimage can be made difficult to visually recognize.
The particle size and particle size distribution are measured using a laser diffraction / scattering particle size distribution measuring device [manufactured by Horiba, Ltd .; LA-300].
Here, it is preferable that the reversible thermochromic composition: wall film = 7: 1 to 1: 1 (mass ratio), preferably 6: 1 to 1: 1.
When the ratio of the reversible thermochromic composition to the wall film is larger than the above range, the thickness of the wall film becomes too thin, and the resistance to pressure and heat tends to decrease, and the ratio of the wall film to the reversible thermochromic composition When the value is larger than the above range, color density and sharpness during color development tend to be reduced.

As a method for encapsulating the temperature-sensitive color-changing color memory composition, an encapsulation method such as an interfacial polymerization method, an interfacial polycondensation method, an in situ method, or a coacervate method is applied. In order to obtain a capsule pigment, an interfacial polymerization method or an interfacial polycondensation method, which hardly causes aggregation and coalescence, is preferably used. Furthermore, after the encapsulation is completed, unnecessary coarse particles can be removed by diluting the capsule suspension with water as desired and filtering out the coarse particles using filters.
As the filters, a filter medium such as stainless steel net, synthetic resin monofilament net, synthetic resin multifilament net, ultrafine fiber filter, cotton cloth, non-woven fabric, needle felt, filter paper or the like can be used singly or in combination.

A toner component such as a general-purpose binder resin is applied to the temperature-sensitive color-changing color memory toner of the present invention.
The content of the microcapsule pigment in the toner is 3 to 50% by mass, preferably 3 to 40% by mass, and more preferably 5 to 40% by mass. If it is less than 3% by mass, the color density at the time of color development is insufficient, and if it exceeds 50% by mass, the proportion of the binder resin is too small, and the toner fixing property tends to be hindered.
The particle size of the temperature-sensitive color-changing color memory toner is 1 to 15 μm, preferably 3 to 15 μm, more preferably 3 to 10 μm.
When the particle size is less than 1 μm, the fluidity of the toner is deteriorated, and problems such as background stains tend to occur. When the particle size exceeds 15 μm, the sharpness of the image may be impaired.

Examples of the binder resin include styrene resin, vinyl chloride resin, rosin-modified maleic acid resin, chlorinated paraffin, polychlorinated paraffin, phenol resin, epoxy resin, polyester resin, polyamide resin, polyacrylic acid resin, low molecular weight polyethylene. , Low molecular weight polypropylene, ionomer resin, polyurethane resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral, polyurea resin, terpene resin, polyol resin, hydrogenated petroleum resin, etc. It can be used alone or in combination of two or more.
Of the resins, a polyester resin having a low temperature fixability is preferably used.
As the polyester resin, those having a glass transition temperature (Tg) of 30 ° C to 80 ° C, preferably 40 ° C to 70 ° C are suitably used. When the glass transition temperature is less than 30 ° C., blocking resistance (storability) may be lowered, and when it exceeds 80 ° C., low-temperature fixability may be impaired.
The softening point of the polyester resin is 105 ° C to 135 ° C, preferably 105 ° C to 130 ° C. If it is less than 105 ° C., blocking resistance (storability) may be deteriorated, and if it exceeds 130 ° C., low-temperature fixability may be impaired.
When a polyester resin and another resin are used in combination as the binder resin, the content of the polyester resin in the binder resin is preferably 50% by weight or more and 98% by weight or less. If it is less than 50% by weight, the low-temperature fixability is poor, and if it exceeds 98% by weight, the offset resistance tends to be impaired.

Moreover, a mold release agent, a charge control agent, a fluidity improver, a magnetic material, etc. can be added as needed.
Examples of the releasing agent include waxes, and examples thereof include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, and dialkyl ketones.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long-chain hydrocarbon include paraffin wax and sazol wax.
The melting point of the wax is preferably a temperature below the temperature t ₄ of the microcapsule pigment.
The said mold release agent may be used individually by 1 type, and may use 2 or more types together.
The charge control agent is preferably a colorless or nearly white material. For example, alkoxy-based amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide, phosphorus alone or a compound thereof, tungsten alone Or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like.
As the fluidity improver, organic fine powder or inorganic fine powder can be used. Fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, zinc stearate, calcium stearate, stearin Fatty acid metal salts such as lead acid, metal oxides such as iron oxide, aluminum oxide, titanium oxide and zinc oxide, silica and silica surface treated with silane coupling agent, titanium coupling agent, silicone oil, etc. Is mentioned.
Examples of the magnetic material include metals such as iron, cobalt, and nickel, and magnetic powders such as alloys and metal oxides thereof.

The temperature-sensitive color-changing color memory toner of the present invention is formed by kneading a microcapsule pigment with a binder resin and other components and then setting the particle size to a predetermined value.
The softening point of the toner is 50 to 120 ° C., preferably 60 to 100 ° C., more preferably 60 to 80 ° C. When the softening point is less than 50 ° C., blocking in the developing machine tends to occur.
Incidentally, the complete decoloring temperature t ₄ of the microcapsule pigment _is preferably a temperature exceeding the softening point of the toner. This is because, when the toner is transferred to a recording paper such as paper, and the toner is softened and fixed by applying a heating tool such as a heat roller, the complete color erasing temperature exceeds the softening point of the toner. This is because the microcapsule pigment is not decolored and, therefore, is excellent in image forming property of a copy using the temperature-sensitive color-changing color memory toner of the present invention.
In addition, the copies may, by heating to complete decoloring temperature t ₄ or more, the image is decolored, it is possible to repeatedly copy, it is possible to reuse the recording paper.
In order to obtain a copy excellent in image forming property, it is preferable that the softening point (S) of the toner and the temperature t _{4 of the} microcapsule pigment satisfy the following formula (1). ) Is more preferable.
60 ° C. ≦ S + 3 ° C. <t ₄ (1)
60 ° C. ≦ S + 5 ° C. <t ₄ (2)

The toner can be stored directly in the image forming apparatus for practical use, or can be stored in a cartridge and set in the image forming apparatus for practical use.
As the cartridge for storing the toner, an electrostatic latent image carrier that carries an electrostatic latent image, and the electrostatic latent image carried on the electrostatic latent image carrier are developed using a developer to form a visible image. And a developing unit for forming the cartridge, and further includes a charging unit, a transferring unit, a cleaning unit, a discharging unit, and the like as necessary.
The cartridge is detachable from an image forming apparatus such as a facsimile or a printer.

  In addition, the cartridge and an ink composition containing a colorant that can be erased by heating in the shaft cylinder are combined, and a writing instrument having a pen body at a writing tip is combined to obtain a cartridge set, or the image forming apparatus An image forming apparatus set can also be obtained by combining an ink composition containing a colorant that is decolored by heating in a shaft cylinder and a writing instrument provided with a pen body at the writing tip.

As the colorant contained in the ink composition of the writing instrument, the same as above (a) an electron donating color-forming organic compound, (b) an electron accepting compound, (c) the above (a), (b) A microcapsule pigment encapsulating a temperature-sensitive color-changing color memory composition comprising a reaction medium for controlling the color reaction is used.
The microcapsule pigment exhibits a large hysteresis characteristic with respect to a color density-temperature curve and exhibits a tautomerism between a colored state and a colorless state, and the pigment reaches a temperature t ₃ in the process of increasing the temperature from the colored state. In the process of starting decoloring and becoming completely colorless in the temperature range above temperature t ₄ higher than temperature t ₃ , and in the process of decreasing temperature from the colorless state, when temperature t ₂ lower than temperature t ₃ is reached, coloring begins, a completely colored state at a temperature range lower than t ₂ and below a temperature t ₁ , and exhibiting a hysteresis characteristic in which a colored state and a colorless state are alternatively maintained in a temperature range between the temperature t ₂ and the temperature t ₃ ; A pigment having a temperature t ₁ in the range of −50 to 0 ° C. and a temperature t _{4 in} the range of 50 to 150 ° C. is preferably used.
The temperature t ₁ is a temperature that can be obtained only in a freezing room, a cold district or the like, that is, −50 to 0 ° C., preferably −40 to −5 ° C., more preferably −30 to −10 ° C., and a complete decoloring temperature. t ₄ is specified as a temperature obtained by a friction body or a heating tool, that is, 50 to 150 ° C., preferably 60 to 150 ° C., more preferably 70 to 150 ° C., and ΔH value is specified to 50 to 100 ° C. Thus, it is possible to effectively function to maintain colors exhibited in a normal state (daily life temperature range).
Incidentally, the complete decoloring temperature _{t 4} the temperature obtained by the frictional heat, i.e. 50 to 95 ° C., preferably 55 to 90 ° C., more preferably by specifying the range of 60 to 85 ° C., which is formed on the writing surface The handwriting can be erased sufficiently by the frictional heat generated by the friction of the friction body several times.
Complete decoloring If the temperature t ₄ is a temperature exceeding 95 ° C., since the frictional heat resulting in friction due to the friction body is less likely to reach the complete decoloring temperature, easily becomes difficult to erase, friction number or increased, or Since the load tends to be excessively rubbed, the writing surface may be damaged.
When obtaining the cartridge set and an image forming apparatus sets, than complete decoloring temperature t ₄ of the microcapsule pigment contained in the toner, lowering the complete decoloring temperature t ₄ of the microcapsule pigment contained in a writing instrument ink Thus, only the handwriting formed by the writing tool by the frictional heat can be erased. In this case, the temperature difference between the complete decoloration temperature t ₄ of the microcapsule pigment contained in the toner and the complete decoloration temperature t ₄ of the microcapsule pigment contained in the ink of the writing instrument is 10 ° C. or more, preferably 15 ° C. or more. More preferably, it is 20 ° C. or higher.

The microcapsule pigment has an average particle size of 0.01 to 0.49 μm, preferably 0.01 to 0.45 μm, and more preferably 0.1 to 0.45 μm.
When the average particle diameter exceeds 0.49 μm, the ratio of the microcapsule pigment that diffuses light is increased. As a result, the dried coating film (handwriting) on the copy in a state where the handwriting is erased becomes cloudy and is easily visually recognized as an afterimage.
If the average particle size is less than 0.01 μm, the afterimage is difficult to be visually recognized, but the color density of the handwriting before erasure is not sufficient because the color developability is poor.
In the system satisfying the average particle diameter of the microcapsule pigment in the range of 0.01 to 0.49 μm, the microcapsule pigment exceeding 1.0 μm, which easily diffuses light, is 30% by volume or less in the total microcapsule pigment, By adjusting the volume to preferably 20% by volume or less, more preferably 15% by volume or less, it is possible to further prevent the dried coating film (handwriting) on the copy at the time of erasure from becoming cloudy and make it difficult to visually recognize the afterimage. it can.
Furthermore, when the average particle size of the reversible thermochromic microcapsule pigment is 0.01 to 0.45 μm, particles exceeding 1.0 μm in the microcapsule pigment are 20% by volume or less in the total microcapsule pigment, When adjusted to preferably 15% by volume or less, more preferably 10% by volume or less, it is possible to prevent the dried coating film (handwriting) on the copy at the time of decoloring from becoming cloudy and make it difficult to visually recognize the afterimage. .
Similarly, when the average particle size of the reversible thermochromic microcapsule pigment is 0.1 to 0.45 μm, the particles exceeding 1.0 μm in the microcapsule pigment are preferably 20% by volume or less in the total microcapsule pigment, preferably Is 15% by volume or less, more preferably 10% by volume or less, so that the dried coating film (handwriting) on the copy at the time of decoloring can be prevented from becoming cloudy and the afterimage can be made difficult to visually recognize. .

  Examples of the ink composition containing a colorant that is decolored by heating include shear-thinning ink containing shear-thinning agent, and cohesiveness obtained by suspending microcapsule pigments in a loosely-aggregated state with a water-soluble polymer flocculant. Ink can be mentioned. Furthermore, an ink in which the specific gravity difference between the microcapsule pigment and the vehicle is adjusted to 0.05 or less can also be mentioned.

By adding the shear thinning agent, it is possible to suppress aggregation and sedimentation of the microcapsule pigment, and it is possible to suppress bleeding of the handwriting, so that good handwriting can be formed.
Furthermore, when the writing instrument filled with the ink is in the form of a ballpoint pen, ink leakage from the gap between the ball and the tip when not in use is prevented, or the ink flows backward when the writing tip is left upward (upright state). Can be prevented.
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, guar gum, locust bean gum and derivatives thereof , Hydroxyethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000, mainly composed of alkyl esters of methacrylic acid, thickening agent having gelling ability extracted from seaweed such as glucomannan, agar and carrageenan Sugars, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polio Shi ethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ether, nonionic HLB value, such as fatty acid amide is 8-12 surfactants, salts of dialkyl or dialkenyl sulfosuccinic acid. Examples thereof include a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.

Examples of the water-soluble polymer flocculant include polyvinyl pyrrolidone, polyethylene oxide, water-soluble polysaccharides, water-soluble cellulose derivatives and the like. Specific examples of water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, and specific examples of water-soluble cellulose derivatives include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, etc. Can be mentioned.
Any water-soluble polymer flocculant that exhibits a gentle bridging action between pigment particles can be applied to the ink, and among these, a water-soluble cellulose derivative works most effectively.
The polymer flocculant can be blended in an amount of 0.05 to 20% by mass based on the total amount of the ink composition.

Water and, if necessary, a water-soluble organic solvent can be added to the ink.
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, 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-pyrrolide And the like can be given.

  In addition, when the ink is filled in 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, thiophosphorous acid tri (alkoxycarbonylmethyl ester), Thiophosphorous acid triesters such as thiophosphorous acid tri (alkoxycarbonylethyl ester), phosphoric acid monoester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether or phosphorus of polyoxyethylene alkyl aryl ether It is preferable to prevent wear of the ball seat by adding a lubricant such as an acid diester or a metal salt, ammonium salt, amine salt or alkanolamine salt thereof.

In addition, resins such as acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin can be added as necessary to impart fixing properties and viscosity to the paper surface.
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 nitrite, saponin, etc. Rust preventive agent, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (Methylsulfonyl) pyridine and other preservatives or antifungal agents, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin, sorbit, man Knit, Pi Wetting agents such as sodium phosphate, defoamers, dispersing agents, a surfactant may be added a fluorine-based surfactant or a nonionic improve the ink permeability.

The ink composition is put to practical use by filling a writing instrument such as a marking pen, a ballpoint pen, or a brush pen with a tip attached to a writing tip.
When filling the marking pen, the structure and shape of the marking pen itself are not particularly limited. For example, a marking pen tip such as a fiber tip, a felt tip, or a plastic tip is attached to the writing tip and the inside of the shaft tube. A structure in which ink is impregnated into a stored fiber bundle and ink is supplied to the writing tip, ink is stored directly in the shaft cylinder, and ink flow adjustment member or fiber bundle made up of fiber bundle A marking pen with a structure that supplies a predetermined amount of ink to the writing tip through an adjusting member, a marking pen that contains ink directly inside the shaft cylinder, and supplies a predetermined amount of ink to the writing tip by a valve mechanism It is done.
When filling the ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited.For example, the ink occlusion body composed of a bundle of fibers accommodated in the shaft tube is impregnated with ink, and the writing tip portion attached with the ballpoint pen tip is used. A structure for supplying ink, a structure in which ink is directly stored in the shaft cylinder, and a predetermined amount of ink is supplied to the writing tip portion via an ink flow rate adjusting member composed of a comb groove-shaped ink flow rate adjusting member or a fiber bundle, A ball pen having a structure in which an ink storage tube filled with ink is provided in the shaft cylinder, the ink storage tube communicates with a ballpoint pen tip, and a liquid stopper for backflow prevention is provided on the end surface of the ink. .

The ballpoint pen tip is a ball holder formed by cutting with a tip holding a ball in a ball holding portion formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, a metal material drill or the like. Examples include a chip holding a ball in the holding portion, a chip holding a ball by providing a resin ball receiving seat inside a metal or plastic molded body, and the like.
The tip may be configured to bias the ball forward by a spring body.
The ball may be about 0.1 to 3.0 mm in diameter, such as cemented carbide, stainless steel, ruby, ceramic, resin, rubber, etc., preferably 0.3 to 1.5 mm, more preferably 0. 3 to 1.0 mm are used.

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.
The ball-point pen tip and the ink containing tube are fitted directly or via a connecting member, and a ball-point pen refill is formed by filling the ink composition and, if necessary, the ink backflow prevention body composition.

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 backflow prevention body can be used in combination.

The tip of the ballpoint pen tip can be fixed with a resin film for preventing the tip of the tip from drying, and the tip of the tip of the ball, the ball holding portion, and the gap between the ball and the ball holding portion are fixed. Accordingly, it is possible to prevent the tip end of the chip from drying and volatilization of the medium in the ink.
As the resin for forming the resin film, a thermoplastic resin, a thermosetting resin, or an ultraviolet curable resin is used.

The ballpoint pen refill can be accommodated in a shaft tube to obtain a cap-type ballpoint pen.
Further, the ballpoint pen refill can be accommodated in a shaft cylinder to obtain a retractable ballpoint pen. The ballpoint pen refill is stored in the shaft cylinder with the tip exposed to the outside air, and the operation of the retracting mechanism is performed. Thus, the writing tip protrudes from the shaft tube opening.
Examples of the appearance mechanism include a knock type, a rotary type, and a slide type.
The knock type has a knock portion on the rear end portion of the shaft tube and the side surface of the shaft tube, and by pressing the knock portion, the writing tip portion of the ballpoint pen refill is projected and retracted from the front end opening portion of the shaft tube, or on the shaft tube. The structure which makes the writing tip part of a ball-point pen refill appear and disappear from the axial cylinder front-end opening part by pressing the provided clip part can be illustrated.
The rotary type has a rotating part at the rear part of the shaft cylinder, and can be exemplified by a configuration in which the writing tip part of the ballpoint pen refill is projected and retracted from the front end part of the shaft cylinder by turning the rotating part.
The slide type has a slide part on the side surface of the shaft cylinder, and the sliding tip of the writing point of the ballpoint pen refill is projected and retracted from the front end opening of the shaft cylinder by operating the slide, or the clip part provided on the shaft cylinder is slid. By doing so, it is possible to exemplify a configuration in which the writing tip of the ballpoint pen refill is projected and retracted from the opening at the front end of the shaft cylinder.
The retractable ballpoint pen is a compound type retractable ballpoint pen in which a plurality of ballpoint pen refills are accommodated in a shaft cylinder, and the writing tip of one of the ballpoint pen refills protrudes and retracts from the opening at the front end of the shaft cylinder by operation of the retractable mechanism. May be.

The handwriting obtained by writing on the writing surface using the writing instrument can be decolored by heating.
Examples of the heating means include a method using a drier or rubbing with a finger, but it is preferable to erase the color by rubbing using a friction body.
As the friction body, an elastic body such as an elastomer or a plastic foam which is rich in elasticity and can generate appropriate frictional heat at the time of friction is suitable, but plastic molded body, stone material, wood, metal, cloth, etc. There may be.
Examples of the material of the friction body include silicone resin, SBS resin (styrene-butadiene-styrene copolymer), SEBS resin (styrene-ethylene-butylene-styrene block copolymer), polyester resin, and the like.
The friction body may be an arbitrary-shaped member (friction body) that is separate from the writing instrument, but is excellent in portability by providing a friction member on the writing instrument.
In the case of a writing instrument having a cap, the location where the friction member is provided is not particularly limited. For example, when the cap itself is formed of a friction member, the shaft tube itself is formed of a friction member, or a clip is provided. The clip itself can be formed of a friction member, or the friction member can be provided at the tip end (top) of the cap or the rear end of the shaft cylinder (the portion where the writing tip is not provided).
In the case of a retractable writing instrument, the location where the friction member is provided is not particularly limited, but for example, the shaft cylinder itself is formed with a friction member, or when the clip is provided, the clip itself is formed with a friction member, A friction member can be provided in the vicinity of the shaft tube opening, the rear end portion of the shaft tube (the portion where the writing tip portion is not provided) or the knock portion.

Examples are shown below. In addition, the part in an Example is a mass part.
Example 1
Preparation of reversible thermochromic microcapsule pigment (i) 4.5 parts 2- (2-chloroamino) -6-dibutylaminofluorane as component (2) 2,2-bis (4'-hydroxyphenyl) as component (b) ) A temperature-sensitive color-changing color memory composition comprising 5.0 parts of hexafluoropropane and 50 parts of a diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol as component (c) is uniformly heated and dissolved. , Emulsify and disperse a solution prepared by mixing 25.0 parts of aromatic polyisocyanate prepolymer and 50.0 parts of a co-solvent as a wall film material into 8% polyvinyl alcohol aqueous solution so as to form fine droplets while heating. After stirring, 2.5 parts of a water-soluble aliphatic modified amine was added, and stirring was further continued to obtain a microcapsule pigment suspension.
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 0.45 μm, a complete color erasing temperature of 77 ° C., a complete color development temperature of −30 ° C., and changes from black to colorless according to temperature change.

Preparation of temperature-sensitive color-change color memory toner 15 parts of the microcapsule pigment, 100 parts of a polyester resin having a softening point of 70 ° C. as a binder resin, and 3 parts of low-molecular-weight polyethylene as a release agent are mixed with a biaxial extruder. Was kneaded at a kneading temperature of 90 ° C., cooled and solidified, and pulverized and classified to obtain a temperature-sensitive color-change color memory toner having a particle diameter of 7 μm. The softening point of the toner particles was 73 ° C.

Making a copy
The temperature-sensitive color-changing color-memory toner (which has been cooled in advance to develop a microcapsule pigment) was accommodated in a cartridge.
The cartridge was set in a laser printer and copied onto a gray recording paper to form a temperature-sensitive color-change image to obtain a temperature-sensitive color-change copy.
A black temperature-sensitive discoloration image is visually recognized at room temperature (25 ° C.), and the temperature-sensitive discoloration image is erased by heating to 77 ° C. or higher. Returning to (recording paper on which nothing was copied), no cloudy afterimage was visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 2
Preparation of reversible thermochromic microcapsule pigment The component (a) of the thermochromic color-memory composition is replaced with 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano. 1.5 parts of [2,3-g] pyrimidine-5,1 ′ (3′H) -isobenzofuran] -3-one and (ro) component as 2,2-bis (4′-hydroxyphenyl) hexafluoro A microcapsule pigment was obtained in the same manner as in Example 1 except that 5.0 parts of propane and the component (c) were changed to 50 parts of diester of pimelic acid and 2- (4-benzyloxyphenyl) ethanol.
The microcapsule pigment has an average particle size of 0.45 μm, a complete color erasing temperature of 78 ° C., a complete color development temperature of −30 ° C., and changes from pink to colorless according to temperature change.

Preparation of Temperature Sensitive Color Changing Color Memory Toner A temperature sensitive color changing color memory toner was obtained in the same manner as in Example 1 using the microcapsule pigment.

Preparation of Copy The temperature-sensitive color-changing color-memory toner (which has been preliminarily cooled to develop a microcapsule pigment) was accommodated in a cartridge.
The cartridge was set in a laser printer and copied onto a pale yellow recording paper to form a temperature-sensitive color change image to obtain a temperature-sensitive color change copy.
In the copied material, a pink temperature-sensitive discoloration image is visually recognized at room temperature (25 ° C.), and the temperature-sensitive discoloration image is erased by heating to 78 ° C. or more before use at room temperature (25 ° C.). Returning to the state (recording paper on which nothing was copied), no cloudy afterimage was visible at the location where the temperature-sensitive discolored image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 3
Preparation of reversible thermochromic microcapsule pigment The component (a) of the thermochromic color memory composition is changed to 4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzene. 3.0 parts of amine, (ro) component 10.0 parts 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, (ha) component pimelic acid and 2- (4-benzyloxyphenyl) ethanol A microcapsule pigment was obtained in the same manner as in Example 1 except that the diester was changed to 50 parts.
The microcapsule pigment has an average particle size of 0.45 μm, a complete color erasing temperature of 76 ° C., a complete color development temperature of −30 ° C., and changes from yellow to colorless according to temperature change.

Preparation of Temperature Sensitive Color Changing Color Memory Toner A temperature sensitive color changing color memory toner was obtained in the same manner as in Example 1 using the microcapsule pigment.

Preparation of Copy The temperature-sensitive color-changing color-memory toner (which has been preliminarily cooled to develop a microcapsule pigment) was accommodated in a cartridge.
The cartridge was set in a laser printer and copied onto a light green recording paper to form a temperature-sensitive color-change image to obtain a temperature-sensitive color-change copy.
In the copy, a yellow temperature-sensitive discolored image is visually recognized at room temperature (25 ° C.), and the temperature-sensitive discolored image is decolored by heating to 76 ° C. or higher. Returning to (recording paper on which nothing was copied), no cloudy afterimage was visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 4
Preparation of reversible thermochromic microcapsule pigment The component (a) of the thermochromic color-memory composition is changed to 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3). -Yl) -4-azaphthalide 1 part, (ro) component 5.0 parts 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, (c) component pimelic acid and 2- (4-benzyloxy) A microcapsule pigment was obtained in the same manner as in Example 1 except that 50 parts of diester with phenyl) ethanol was used.
The microcapsule pigment has an average particle size of 0.45 μm, a complete decolorization temperature of 79 ° C., a complete color development temperature of −30 ° C., and changes color from blue to colorless according to temperature change.

Preparation of Temperature Sensitive Color Changing Color Memory Toner A temperature sensitive color changing color memory toner was obtained in the same manner as in Example 1 using the microcapsule pigment.

Preparation of Copy The temperature-sensitive color-changing color-memory toner (which has been preliminarily cooled to develop a microcapsule pigment) was accommodated in a cartridge.
The cartridge was set in a laser printer and copied onto a light pink recording paper to form a temperature-sensitive color change image to obtain a temperature-sensitive color change copy.
A blue temperature-sensitive color-change image is visually recognized at room temperature (25 ° C.), and the temperature-sensitive color-change image is erased by heating to 79 ° C. or higher. Returning to (recording paper on which nothing was copied), no cloudy afterimage was visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 5
Preparation of reversible thermochromic microcapsule pigment: (i) component of thermosensitive color-changing color memory composition is 4.5 parts of 2- (2-chloroamino) -6-dibutylaminofluorane, and (b) component is 2 , 2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 parts, (c) Component was changed to 50 parts diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid A microcapsule pigment was obtained in the same manner as in Example 1.
The microcapsule pigment has an average particle size of 0.4 μm, a complete color erasing temperature of 80 ° C., a complete color development temperature of −25 ° C., and changes color from black to colorless with temperature change.

Preparation of Temperature Sensitive Color Changing Color Memory Toner A temperature sensitive color changing color memory toner was obtained in the same manner as in Example 1 using the microcapsule pigment.

Preparation of Copy The temperature-sensitive color-changing color-memory toner (which has been preliminarily cooled to develop a microcapsule pigment) was accommodated in a cartridge.
The cartridge was set in a laser printer and copied onto a gray recording paper to form a temperature-sensitive color-change image to obtain a temperature-sensitive color-change copy.
In the copied material, a black temperature-sensitive discoloration image is visually recognized at room temperature (25 ° C.), and the temperature-sensitive discoloration image is erased by heating to 80 ° C. or more, and the state before use at room temperature (25 ° C.). Returning to (recording paper on which nothing was copied), no cloudy afterimage was visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 6
The component (a) of the thermochromic color-memory composition is changed to 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine- 1.5 parts of 5,1 '(3'H) -isobenzofuran] -3-one, (b) component 5.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, (c) A microcapsule pigment was obtained in the same manner as in Example 1 except that the component was changed to 50 parts of a diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid.
The microcapsule pigment has an average particle size of 0.40 μm, a complete color erasing temperature of 80 ° C., a complete color development temperature of −25 ° C., and changes from pink to colorless according to temperature change.

Preparation of Temperature Sensitive Color Changing Color Memory Toner A temperature sensitive color changing color memory toner was obtained in the same manner as in Example 1 using the microcapsule pigment.

Preparation of Copy The temperature-sensitive color-changing color-memory toner (which has been preliminarily cooled to develop a microcapsule pigment) was accommodated in a cartridge.
The cartridge was set in a laser printer and copied onto a pale yellow recording paper to form a temperature-sensitive color change image to obtain a temperature-sensitive color change copy.
In the copied material, a pink temperature-sensitive color change image is visually recognized at room temperature (25 ° C.), and the temperature-sensitive color change image is erased by heating to 80 ° C. or more before use at room temperature (25 ° C.). Returning to the state (recording paper on which nothing was copied), no cloudy afterimage was visible at the location where the temperature-sensitive discolored image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 7
The component (a) of the temperature-sensitive color-change color memory composition is changed to 3.0 parts of 4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine, (b) The component was changed to 10.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and the component (c) was changed to 50 parts of a diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid. A microcapsule pigment was obtained in the same manner as in Example 1 except that.
The microcapsule pigment has an average particle size of 0.40 μm, a complete color erasing temperature of 79 ° C., a complete color development temperature of −25 ° C., and changes color from yellow to colorless according to temperature change.

Preparation of Temperature Sensitive Color Changing Color Memory Toner A temperature sensitive color changing color memory toner was obtained in the same manner as in Example 1 using the microcapsule pigment.

Preparation of Copy The temperature-sensitive color-changing color-memory toner (which has been preliminarily cooled to develop a microcapsule pigment) was accommodated in a cartridge.
The cartridge was set in a laser printer and copied onto a light green recording paper to form a temperature-sensitive color-change image to obtain a temperature-sensitive color-change copy.
A yellow temperature-sensitive discolored image is visually recognized at room temperature (25 ° C.), and the temperature-sensitive discolored image is decolored by heating to 79 ° C. or higher, and is in a state before use at room temperature (25 ° C.). Returning to (recording paper on which nothing was copied), no cloudy afterimage was visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 8
1 part of 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide is used as component (a) of the temperature-sensitive color-change color memory composition. The component (b) is 5.0 parts of 2,2-bis (4′-hydroxyphenyl) hexafluoropropane, and the component (c) is a diester 50 of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid. A microcapsule pigment was obtained in the same manner as in Example 1 except that the content was changed to part.
The microcapsule pigment has an average particle size of 0.40 μm, a complete color erasing temperature of 82 ° C., a complete color development temperature of −25 ° C., and changes from blue to colorless with temperature change.

Preparation of Temperature Sensitive Color Changing Color Memory Toner A temperature sensitive color changing color memory toner was obtained in the same manner as in Example 1 using the microcapsule pigment.

Preparation of Copy The temperature-sensitive color-changing color-memory toner (which has been preliminarily cooled to develop a microcapsule pigment) was accommodated in a cartridge.
The cartridge was set in a laser printer and copied onto a light pink recording paper to form a temperature-sensitive color change image to obtain a temperature-sensitive color change copy.
In the copy, a blue temperature-sensitive discoloration image is visually recognized at room temperature (25 ° C), and the temperature-sensitive discoloration image is erased by heating to 82 ° C or higher, and the state before use at room temperature (25 ° C). Returning to (recording paper on which nothing was copied), no cloudy afterimage was visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 9
Each temperature-sensitive color-change color memory toner obtained in Examples 1 to 4 was accommodated in a cartridge.
The cartridge was set in a laser printer, and a landscape photograph was copied on a gray recording paper to form a temperature-sensitive discoloration image to obtain a thermochromic copy.
In the copy, a multicolor temperature-sensitive discoloration image is visually recognized at room temperature (25 ° C.), and the temperature-sensitive discoloration image is erased by heating to 79 ° C. or more before use at room temperature (25 ° C.). Returning to the state (recording paper on which nothing was copied), no cloudy afterimage was visible at the location where the temperature-sensitive discolored image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 10
Each temperature-sensitive color-changing color memory toner obtained in Examples 5 to 8 was accommodated in a cartridge.
The cartridge was set in a laser printer, a photograph of a person was copied on a gray recording paper to form a temperature-sensitive color-change image, and a temperature-sensitive color-change copy was obtained.
In the copy, a multicolor temperature-sensitive discoloration image is visually recognized at room temperature (25 ° C), and the temperature-sensitive discoloration image is erased by heating to 82 ° C or higher before use at room temperature (25 ° C). Returning to the state (recording paper on which nothing was copied), no cloudy afterimage was visible at the location where the temperature-sensitive discolored image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 11
Writing instrument production (see Figure 2)
(I) 1,2-Benz-6- (N-ethyl-N-isoamylamino) fluorane (1.0 part), 1,3-dimethyl-6-diethylaminofluorane (2.0 parts), (B) component 4.5 parts of 4,4 '-(2-methylpropylidene) bisphenol, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, (c) 4-benzyloxyphenyl caprate as component A microcapsule pigment suspension containing a temperature-sensitive color-changing color memory composition composed of 50.0 parts of ethyl was obtained.
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 0.45 μm, a complete color erasing temperature of 57 ° C., a complete color development temperature of −25 ° C., and changes color from red to colorless according to temperature change.
25.7 parts of the microcapsule pigment (preliminarily cooled to -25 ° C. or less to cause the microcapsule pigment to develop a red color), 0.2 part of succinoglycan (shear thinning agent), 5.5 parts of urea , 7.5 parts of glycerin, 0.2 part of modified silicone antifoam, 0.1 part of antifungal agent, 1.0 part of lubricant, 1.0 part of triethanolamine, and 58.8 parts of water A reversible thermochromic aqueous ink composition was prepared.
The ink 4 was sucked and filled into a polypropylene pipe (ink containing pipe 21) and connected to the ball-point pen tip 3 through a resin holder 22.
Next, an ink backflow prevention body 5 (liquid stopper) having a viscoelastic property mainly composed of polybutene was filled from the rear part of the polypropylene pipe, and a tail plug 23 was fitted to the rear part of the pipe to obtain a refill 2. Further, the refill 2 was assembled in a shaft cylinder 6 (comprised of a front shaft cylinder and a rear shaft cylinder), and after a cap 7 was fitted, a deaeration process was performed by a centrifugal process to obtain a writing instrument 1 (ballpoint pen).
The ball-point pen tip has a hard metal ball having a diameter of 0.5 mm held by a ball holding portion formed by cutting a metal material with a drill, and the ball is attached to the front by a spring body. It is the one that made it.
Further, a friction member 8 made of SEBS resin is provided at the end of the rear shaft cylinder.

The writing instrument and the cartridge obtained in Example 1 were combined to obtain a cartridge set.
The cartridge was set in a laser printer and copied onto a gray recording paper to form a temperature-sensitive color-change image to obtain a temperature-sensitive color-change copy.
A black temperature-sensitive discoloration image was visually recognized on the copied material at room temperature (25 ° C.), and red characters (handwriting) could be written using the ballpoint pen.
When a friction member was used to rub a part of the handwriting, the color disappeared and became colorless, and a cloudy afterimage was not visually recognized at a portion where a temperature-sensitive discoloration image was formed.
Then, the copy is heated to 77 ° C. or more to erase the temperature-sensitive discoloration image and handwriting, and returns to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C.). A cloudy afterimage was not visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 12
Writing instrument production (see Figure 3)
(A) 4,5,6,7-Tetrachloro-3- [4- (dimethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl as component ) -1 (3H) -isobenzofuranone 2.0 parts, (b) component 4,4 '-(2-ethylhexane-1,1-diyl) diphenol 3.0 parts, 2,2-bis ( 4'-hydroxyphenyl) -hexafluoropropane 5.0 microcapsule pigment suspension containing a thermochromic color memory composition comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) A turbid liquid was obtained.
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 0.4 μm, a complete color erasing temperature of 55 ° C., a complete color development temperature of −25 ° C., and changes from blue to colorless according to temperature change.
20.0 parts of the microcapsule pigment (previously cooled to −25 ° C. or less to develop a blue color), 0.5 part of hydroxyethyl cellulose, 0.2 part of a polymer dispersant, 1.0 part of a preservative, polyvinyl 0.5 parts of alcohol, 25.0 parts of glycerin, 0.02 part of antifoaming agent and 52.78 parts of water were mixed to obtain a reversible thermochromic aqueous ink composition.
The ink composition 10 is impregnated with a polyester resin sliver covered with a synthetic resin film, impregnated with the ink composition, accommodated in a shaft cylinder 6 made of polypropylene resin, and polyester fiber resin processing at the tip of the shaft cylinder via a holder 22. The marking pen tip 3 (bullet type) was assembled in a connected state, and a cap 7 was attached to obtain a writing instrument 1 (marking pen).
SEBS resin is provided as a friction member 8 at the rear end of the shaft tube.

The writing instrument was combined with the image forming apparatus containing the toner obtained in Example 2 to obtain an image forming apparatus set.
A temperature-sensitive color-change image was formed by copying on a gray-colored recording paper using the image forming apparatus to obtain a temperature-sensitive color-change copy.
The copy had a pink temperature-sensitive discoloration image at room temperature (25 ° C.), and blue characters (handwriting) could be written using the marking pen.
When a friction member was used to rub a part of the handwriting, the color disappeared and became colorless, and a cloudy afterimage was not visually recognized at a portion where a temperature-sensitive discoloration image was formed.
Then, the copy is heated to 78 ° C. or higher to erase the temperature-sensitive discolored image and handwriting, and returns to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C.). A cloudy afterimage was not visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 13
Writing instrument production (see Fig. 4)
(I) As a component, 4.5 parts of 2- (2-chloroamino) -6-dibutylaminofluorane, (b) As a component, 4.5 parts of 4,4 '-(2-methylpropylidene) bisphenol, 2, Micro containing a thermochromic color-memory composition comprising 7.5 parts of 2-bis (4'-hydroxyphenyl) hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as the component (c) A capsule pigment suspension was obtained.
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 0.4 μm, a complete color erasing temperature of 57 ° C., a complete color development temperature of −25 ° C., and changes from black to colorless according to temperature change.
25.7 parts of the microcapsule pigment (preliminarily cooled to -25 ° C. or less to cause the black color of the microcapsule pigment), 0.2 part of succinoglycan (shear thinning agent), 5.5 parts of urea , 7.5 parts of glycerin, 0.2 part of modified silicone antifoam, 0.1 part of antifungal agent, 1.0 part of lubricant, 1.0 part of triethanolamine, and 58.8 parts of water A reversible thermochromic aqueous ink composition was prepared.
The ink 4 is filled in a polypropylene shaft cylinder 6 having an inner diameter of 7.0 mm and an outer diameter of 10 mm, to which the ballpoint pen tip 3 is fixed, and then filled with a viscoelastic ink backflow prevention body 5 mainly composed of polybutene. A friction member 8 made of SEBS resin was fitted to the rear portion of the shaft tube.
Further, after the cap 7 was fitted, the writing instrument 1 (ballpoint pen) was obtained by performing a deaeration process by a centrifugal process.
The ball-point pen tip has a ball holding portion formed by cutting a metal material with a drill and holds a cemented carbide ball having a diameter of 0.7 mm, and the ball is attached to the front by a spring body. It is the one that made it.

The writing instrument and the image forming apparatus containing the cartridge obtained in Example 1 were combined to obtain an image forming apparatus set.
A temperature-sensitive color-change image was formed by copying on a gray-colored recording paper using the image forming apparatus to obtain a temperature-sensitive color-change copy.
A black temperature-sensitive discoloration image was visually recognized on the copy at room temperature (25 ° C.), and black characters (handwriting) could be written using the ballpoint pen.
When a friction member was used to rub a part of the handwriting, the color disappeared and became colorless, and a cloudy afterimage was not visually recognized at a portion where a temperature-sensitive discoloration image was formed.
Next, the copy is heated to 77 ° C. or more to erase the temperature-sensitive discoloration image and handwriting, and returned to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C.). A cloudy afterimage was not visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 14
Writing instrument production (see Fig. 5)
(I) As a component, 4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine (3.0 parts), (b) As a component, 2,2-bis (4 Suspension of microcapsule pigment containing a thermosensitive color-changing color memory composition comprising 10.0 parts of '-hydroxyphenyl) -hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) A liquid was obtained.
The suspension was centrifuged to isolate the microcapsule pigment.
The average particle diameter of the microcapsule pigment is 0.45 μm, the complete color erasing temperature is 59 ° C., and the complete color development temperature is −25 ° C., and the color changes from yellow to colorless according to the temperature change.
25.0 parts of the above microcapsule pigment (previously cooled to −25 ° C. or less and colored yellow), 0.5 part of hydroxyethyl cellulose, 0.2 part of a polymer dispersant, 1.0 part of a preservative, polyvinyl 0.5 parts of alcohol, 25.0 parts of glycerin, 0.02 part of antifoaming agent and 47.78 parts of water were mixed to obtain a reversible thermochromic aqueous ink composition.
The ink 4 and the stirrer 9 (SUS-304 ferritic stainless steel ball, 3 mm in diameter) are incorporated in the shaft cylinder 6, and the marking pen tip 3 [chisel type fiber pen body (pore The rate was about 53%)] and a cap 7 was attached to obtain a direct liquid writing instrument 1 (marking pen).
A valve mechanism 11 is provided in the shaft cylinder, and the valve mechanism includes a valve seat, a valve body, and a metal spring that urges the valve body to press against the valve seat. The valve opens with the pressure applied to the pen body at the time.
SEBS resin is provided as a friction member 8 at the rear end of the shaft tube.

The writing instrument and the cartridge obtained in Example 4 were combined to obtain a cartridge set.
The cartridge was set in a laser printer and copied onto a gray recording paper to form a temperature-sensitive color-change image to obtain a temperature-sensitive color-change copy.
The copy had a blue temperature-sensitive color-change image visually recognized at room temperature (25 ° C.), and a yellow highlight could be formed on the image using the marking pen.
When a part of the highlight was rubbed with a friction member, the color disappeared and became colorless, and a cloudy afterimage was not visually recognized at the portion where the temperature-sensitive discoloration image was formed.
When the copy is heated to 79 ° C or higher, the temperature-sensitive discoloration image and highlights are erased, and return to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C). A cloudy afterimage was not visually recognized at the location where the temperature-change color image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 15
Writing instrument production (see Fig. 6)
(I) 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine-5,1 '(3'H)- Isobenzofuran] -3-one 1.5 parts, (b) component 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 parts, (c) component pimelic acid and 2- (4- A microcapsule pigment suspension containing a thermochromic color-memory composition comprising 50 parts of a diester with benzyloxyphenyl) ethanol was obtained.
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 0.4 μm, a complete decolorization temperature of 78 ° C., a complete color development temperature of −20 ° C., and changes from pink to colorless according to temperature change.
25.7 parts of the above microcapsule pigment (previously cooled to −20 ° C. or less to cause the microcapsule pigment to develop a pink color), 0.2 part of succinoglycan (shear thinning agent), urea 5.5 Parts, 7.5 parts of glycerin, 0.2 parts of modified silicone antifoam, 0.1 part of antifungal agent, 1.0 part of lubricant, 1.0 part of triethanolamine, and 58.8 parts of water. A reversible thermochromic water-based ink composition was prepared.
The ink 4 was sucked and filled into a polypropylene pipe (ink containing pipe 21) and connected to the ball-point pen tip 3 through a resin holder 22.
Next, an ink backflow prevention body 5 (liquid stopper) having a viscoelastic property mainly composed of polybutene was filled from the rear part of the polypropylene pipe, and a tail plug 23 was fitted to the rear part of the pipe to obtain a refill 2. Further, the refill 2 was assembled in a shaft cylinder 6 (comprised of a front shaft cylinder and a rear shaft cylinder), and after a cap 7 was fitted, a deaeration process was performed by a centrifugal process to obtain a writing instrument 1 (ballpoint pen).
The ball-point pen tip has a hard metal ball having a diameter of 0.5 mm held by a ball holding portion formed by cutting a metal material with a drill, and the ball is attached to the front by a spring body. It is the one that made it.

The writing instrument and the cartridge obtained in Example 5 were combined to obtain a cartridge set.
The cartridge was set in a laser printer and copied onto a gray recording paper to form a temperature-sensitive color-change image to obtain a temperature-sensitive color-change copy.
A black temperature-sensitive discoloration image was visually recognized on the copied material at room temperature (25 ° C.), and pink characters (handwriting) could be written using the ballpoint pen.
When the copy is heated to 80 ° C. or higher, the temperature-sensitive discoloration image and handwriting are erased, and return to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C.). A cloudy afterimage was not visually recognized at the location where the discolored image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 16
Writing instrument production (see Figure 7)
(A) 4,5,6,7-Tetrachloro-3- [4- (dimethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl as component ) -1 (3H) -isobenzofuranone 2.0 parts, (b) component 4,4 '-(2-ethylhexane-1,1-diyl) diphenol 3.0 parts, 2,2-bis ( 4'-hydroxyphenyl) -hexafluoropropane 5.0 microcapsule pigment suspension containing a thermochromic color memory composition comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) A turbid liquid was obtained.
The suspension was centrifuged to isolate the microcapsule pigment.
The microcapsule pigment has an average particle size of 0.45 μm, a complete color erasing temperature of 55 ° C., a complete color development temperature of −25 ° C., and changes from blue to colorless with temperature change.
25.7 parts of the microcapsule pigment (preliminarily cooled to -25 ° C. or less to cause the microcapsule pigment to develop a blue color), 0.2 part of succinoglycan (shear thinning agent), 5.5 parts of urea , 7.5 parts of glycerin, 0.2 part of modified silicone antifoam, 0.1 part of antifungal agent, 1.0 part of lubricant, 1.0 part of triethanolamine, and 58.8 parts of water A reversible thermochromic aqueous ink composition was prepared.
The ink 4 was sucked and filled into a polypropylene pipe (ink containing pipe 21) and connected to the ball-point pen tip 3 through a resin holder 22.
Next, an ink backflow prevention body (liquid stopper) having viscoelasticity mainly composed of polybutene was filled from the rear part of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to obtain a refill 2.
The ball-point pen refill was incorporated into the shaft tube 6 to obtain a retractable writing instrument 1 (ballpoint pen).
The writing instrument is housed in the shaft cylinder in a state in which the tip provided on the ballpoint pen refill is exposed to the outside air, and the shaft is driven by the operation of a clip-shaped protrusion / displacement mechanism (slide mechanism) provided on the side surface of the shaft cylinder. In this structure, the tip protrudes from the opening at the front end of the cylinder.
A friction member 8 made of SEBS resin is provided at the rear end portion of the shaft cylinder.

The writing instrument and the cartridge obtained in Example 8 were combined to obtain a cartridge set.
The cartridge was set in a laser printer and copied onto a gray recording paper to form a temperature-sensitive color-change image to obtain a temperature-sensitive color-change copy.
A blue temperature-sensitive discoloration image was visually recognized on the copy at room temperature (25 ° C.), and blue characters (handwriting) could be written using the ballpoint pen.
When a friction member was used to rub a part of the handwriting, the color disappeared and became colorless, and a cloudy afterimage was not visually recognized at a portion where a temperature-sensitive discoloration image was formed.
When the copy is heated to 82 ° C. or higher, the temperature-sensitive discolored image and handwriting are erased, and return to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C.). A cloudy afterimage was not visually recognized at the location where the discolored image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 17
The temperature-sensitive color-changing color memory toners of Examples 1 to 4 (those that had been preliminarily cooled to develop the color of the microcapsule pigment) were accommodated in cartridges.
The writing instrument obtained in Example 13 and the cartridge were combined to obtain a cartridge set.
The cartridge was set in a laser printer and copied onto a gray recording paper to form a colorful temperature-sensitive color change image to obtain a temperature-sensitive color change copy.
A black handwriting could be formed on the copy using the writing instrument.
When a friction member was used to rub a part of the handwriting, the color disappeared and became colorless, and a cloudy afterimage was not visually recognized at a portion where a temperature-sensitive discoloration image was formed.
Next, the copy is heated to 79 ° C. or more to erase the temperature-sensitive discoloration image and handwriting, and returns to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C.). A cloudy afterimage was not visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 18
The temperature-sensitive color-changing color-memory toners of Examples 5 to 8 (those that had been preliminarily cooled to develop a microcapsule pigment) were accommodated in cartridges.
The writing instrument obtained in Example 16 and the cartridge were combined to obtain a cartridge set.
The cartridge was set in a laser printer and copied onto a gray paper to form a colorful temperature-sensitive color change image to obtain a temperature-sensitive color change copy.
A blue handwriting could be formed on the copy using the writing instrument.
When a friction member was used to rub a part of the handwriting, the color disappeared and became colorless, and a cloudy afterimage was not visually recognized at a portion where a temperature-sensitive discoloration image was formed.
Next, the copy is heated to 82 ° C. or more to erase the temperature-sensitive discoloration image and handwriting, and returns to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C.). A cloudy afterimage was not visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 19
A cartridge set was obtained by combining the cartridge obtained in Example 1 and the writing instrument obtained in Examples 11 to 14.
The cartridge was set in a laser printer and copied onto a gray recording paper to form a black temperature-sensitive color change image to obtain a temperature-sensitive color-change copy.
It was possible to form red, blue, black, and yellow handwriting on the copy using the writing instrument.
When a friction member was used to rub a part of the handwriting, the color disappeared and became colorless, and a cloudy afterimage was not visually recognized at a portion where a temperature-sensitive discoloration image was formed.
When the copy is heated to 77 ° C or higher, the temperature-sensitive discolored image and handwriting are erased, and return to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C). A cloudy afterimage was not visually recognized at the location where the discolored image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

Example 20
The temperature-sensitive color-changing color memory toners of Examples 1 to 4 (those that had been preliminarily cooled to develop the color of the microcapsule pigment) were accommodated in cartridges.
The writing instrument obtained in Examples 11 to 14 and the cartridge were combined to obtain a cartridge set.
The cartridge was set in a laser printer and copied onto a gray recording paper to form a colorful temperature-sensitive color change image to obtain a temperature-sensitive color change copy.
It was possible to form red, blue, black, and yellow handwriting on the copy using the writing instrument.
When a friction member was used to rub a part of the handwriting, the color disappeared and became colorless, and a cloudy afterimage was not visually recognized at a portion where a temperature-sensitive discoloration image was formed.
Next, the copy is heated to 79 ° C. or more to erase the temperature-sensitive discoloration image and handwriting, and returns to the state before use (recording paper on which nothing is copied) at room temperature (25 ° C.). A cloudy afterimage was not visually recognized at the location where the temperature-sensitive discoloration image was formed.
Again, by setting the recording paper in the laser printer and performing copying, a temperature-sensitive discolored image was formed to obtain a copy, and the recording paper could be used repeatedly.

t ₁ Complete color development temperature of microcapsule pigment encapsulating thermochromic color memory composition t ₂ Color development start temperature of microcapsule pigment encapsulating thermochromic color memory composition t ₃ Thermosensitivity color memory Decoloration start temperature of microcapsule pigment encapsulating curable composition t ₄ Complete decolorization temperature of microcapsule pigment encapsulating thermochromic color-memory composition ΔH Hysteresis width 1 Writing instrument 2 Refill 21 Ink receiving tube 22 Holder 23 Tail plug 3 Chip 4 Ink 5 Ink backflow prevention body 6 Shaft cylinder 7 Cap 8 Friction member 9 Stirring body 10 Ink occlusion body 11 Valve mechanism

Claims (15)

(I) an electron-donating color-forming organic compound, (b) an electron-accepting compound, (c) a thermosensitive color-changing color memory composition comprising a reaction medium for controlling the color reaction of (a) and (b) above. A microcapsule pigment having an average particle size of 0.01 to 0.49 μm in which a product is encapsulated and a binder resin, and the microcapsule pigment exhibits a large hysteresis characteristic with respect to a color density-temperature curve. exhibit tautomerism of the colored state and decolored state, in the process of temperature rise be in a colored state, it begins decolorized to reach a temperature t _3, completely at a temperature t ₄ above temperature range than the temperature t ₃ becomes colorless state, in the process of temperature in the decolored state is lowered, the the temperature t ₃ reaches a lower temperature t _2, begins to color, completely at low temperatures t ₁ following temperature range than the temperature t ₂ Colored state, the temperature t ₂ and colored state or decolorized state at a temperature range between the temperature t ₃ represents the hysteresis characteristic is alternatively visible, the temperature t ₁ is in the range of -50 to 0 ° C., the temperature t ₄ is 50 Temperature-sensitive color-change color memory toner in the range of ˜150 ° C.   2. The temperature-sensitive color-changing color memory toner according to claim 1, wherein the microcapsule pigment has a particle size of 1.0 μm or more of 30% by volume or less in the total microcapsule pigment.   The temperature-sensitive color-changing color memory toner according to claim 1 or 2, wherein the microcapsule pigment has an average particle size in the range of 0.01 to 0.45 µm.   The temperature-sensitive color-changing color memory toner according to claim 1, wherein the microcapsule pigment exhibits a hysteresis width (ΔH) of 50 ° C. to 100 ° C. with respect to a color density-temperature curve. Thermochromic coloring color-memory toner according to any one of claims 1 to 4 temperature t ₄ is a temperature above the softening point of the toner of the microencapsulated pigment. The softening point of the toner and (S), said microcapsule thermochromic coloring color-memory toner according to claim 5, wherein the temperature t ₄ satisfies the following formula (1) of the pigment.
60 ° C. ≦ S + 3 ° C. <t ₄ (1)   A cartridge containing the temperature-sensitive color-changing color memory toner according to any one of claims 1 to 6 in a container.   An image forming apparatus containing the temperature-sensitive color-changing color memory toner according to claim 1.   An image forming apparatus containing the cartridge according to claim 7.   A cartridge set comprising the cartridge according to claim 7 and a writing instrument in which an ink composition containing a colorant that is decolored by heating is contained in a shaft cylinder and a pen body is provided at a writing tip. The colorant that is decolored by heating comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b). A microcapsule pigment having an average particle diameter of 0.01 to 0.49 μm in which a temperature-sensitive color-change color memory composition is encapsulated, and the microcapsule pigment exhibits a large hysteresis characteristic with respect to a color density-temperature curve, and a colored state exhibit tautomerism of colorless state and, in the process of temperature in the colored state is increased, to reach a temperature t ₃ begins to decoloring, completely decolored at a temperature t ₄ above temperature range than the temperature t ₃ In the process of decoloring and decreasing in temperature, when the temperature reaches a temperature t ₂ lower than the temperature t ₃ , the color starts to be developed, and the color is completely developed in a temperature range below the temperature t ₁ lower than the temperature t _2. And the temperature t ₂ Shows a hysteresis characteristic in which a colored state or a decolored state is alternatively visually recognized in a temperature range between the temperature t ₃ and the temperature t ₃ , the temperature t ₁ is in the range of −50 to 0 ° C., and the temperature t ₄ is 50 to 150 The cartridge set according to claim 10, which is in the range of ° C. The temperature t ₄ is in the range of 50 to 95 ° C., and comprises comprises a friction body according to claim 11 cartridge set according.   10. An image forming apparatus set comprising: the image forming apparatus according to claim 8; and a writing instrument that contains an ink composition containing a colorant that is decolored by heating in a shaft tube and has a pen body at a writing tip. The colorant that is decolored by heating comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b). A microcapsule pigment having an average particle diameter of 0.01 to 0.49 μm in which a temperature-sensitive color-change color memory composition is encapsulated, and the microcapsule pigment exhibits a large hysteresis characteristic with respect to a color density-temperature curve, and a colored state exhibit tautomerism of colorless state and, in the process of temperature in the colored state is increased, to reach a temperature t ₃ begins to decoloring, completely decolored at a temperature t ₄ above temperature range than the temperature t ₃ In the process of decoloring and decreasing in temperature, when the temperature reaches a temperature t ₂ lower than the temperature t ₃ , the color starts to be developed, and the color is completely developed in a temperature range below the temperature t ₁ lower than the temperature t _2. And the temperature t ₂ Shows a hysteresis characteristic in which a colored state or a decolored state is alternatively visually recognized in a temperature range between the temperature t ₃ and the temperature t ₃ , the temperature t ₁ is in the range of −50 to 0 ° C., and the temperature t ₄ is 50 to 150 The image forming apparatus set according to claim 13, wherein the image forming apparatus set is in a range of ° C. The image forming apparatus set according to claim 14, wherein the temperature t ₄ is in a range of 50 to 95 ° C. and includes a friction body.

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