JP2022008266A - Aqueous ink composition for writing utensil and writing utensil storing the same - Google Patents

Abstract

To provide an aqueous ink composition for writing utensils which suppresses localization by floating or precipitating a coloring agent in an ink composition to make handwriting dark or pale, and enables formation of good handwriting excellent in color development property without making the handwriting pale when stimulation such as vibration from the outside is applied to a writing utensil storing an ink composition using a coloring agent having a large specific gravity in an erected state, and the writing utensil is stored over a long period of time, and a writing utensil storing the same.SOLUTION: An aqueous ink composition for writing utensils contains a coloring agent selected from a pigment or resin particles, and a vehicle containing at least water, a cationic polymer having a specific structure and an acrylic polymer dispersant.SELECTED DRAWING: None

Description

The present invention relates to a water-based ink composition for writing tools and a writing tool containing the composition. More specifically, the present invention relates to a water-based ink composition for a writing tool capable of suppressing a difference in shade of handwriting and forming a good handwriting having excellent color development, and a writing tool containing the composition.

Conventionally, inks using water as a main solvent (water-based inks) have been known and are widely used because of their low odor and high safety. Further, since it is excellent in light resistance and water resistance, a water-based pigment ink using a pigment as an ink colorant is widely used. Usually, the pigment has unstable dispersion stability in water or an aqueous medium, and the pigment may float or settle and be localized in the ink. Therefore, an ink composition in which the dispersion stability of a pigment in an aqueous ink is improved by using various dispersants and additives is disclosed (see, for example, Patent Documents 1 to 3).
Patent Document 1 discloses a water-based ink composition for writing instruments using a reversible thermochromic microcapsule pigment and a vehicle composed of water, a polymer flocculant, a dispersant and the like.
Patent Document 2 discloses an aqueous pigment ink composition for writing instruments containing a pigment, a dispersant, water, a water-soluble solvent, and an alkylpyrrolidone having an alkyl group having 4 to 20 carbon atoms.
Patent Document 3 discloses an aqueous ink composition comprising a pigment, an aqueous medium, and a copolymer of an N-vinylpyrrolidone derivative and an acrylic acid derivative or a methacrylic acid derivative as a dispersant.
In the above-mentioned water-based ink composition (water-based pigment ink composition), the pigment can be stably dispersed in the ink composition by using a dispersant or by using a dispersant in combination with a specific additive. Therefore, a writing instrument containing such an ink composition can suppress darkening and lightening of the brush stroke. However, it is difficult to completely suppress the floating or settling of the pigment in the above-mentioned ink composition, and in particular, a writing instrument containing an ink composition using a pigment having a large specific gravity has a writing tip facing upward (in particular, the writing tip is in an upward state (). If an external stimulus such as vibration is applied or the product is stored for a long period of time in an upright state), the pigment may settle and the ink may not be uniformly ejected from the tip of the writing, resulting in lightening of the writing marks. rice field.

Japanese Unexamined Patent Publication No. 11-335613 Japanese Unexamined Patent Publication No. 8-283646 Japanese Unexamined Patent Publication No. 9-59554

INDUSTRIAL APPLICABILITY The present invention will provide a water-based ink composition for a writing instrument capable of suppressing the colorant from floating or precipitating and being localized in the ink composition to darken or lighten the handwriting, and a writing instrument containing the same. Is to be.

（式中、ｎ１は０又は１の整数を示し、Ｘ_１は、塩酸、アミド硫酸、酢酸のいずれかを示し、ｎは自然数を示す。また、質量平均分子量は５００～２００，０００の範囲にある。）

（式中、ｎ２ａ及びｎ２ｂは、それぞれ独立に、０又は１の整数を示し、Ｘ_２ａ及びＸ_２ｂは、それぞれ独立に、塩酸、アミド硫酸、酢酸のいずれかを示し、ｍ及びｎは、それぞれ独立に自然数を示す。また、質量平均分子量は５００～２００，０００の範囲にある。）

（式中、ｎ３ａ及びｎ３ｂは、それぞれ独立に、０又は１の整数を示し、Ｘ_３ａ及びＸ_３ｂは、それぞれ独立に、塩酸、アミド硫酸、酢酸のいずれかを示し、ｍ及びｎは、それぞれ独立に自然数を示す。また、質量平均分子量は５００～２００，０００の範囲にある。）

（式中、Ｒ_１は、水素原子、又は、炭素数１～３の直鎖若しくは分岐のアルキル基を示し、ｎ４は０又は１の整数を示し、Ｘ_４は、塩酸、アミド硫酸、酢酸のいずれかを示し、ｎは自然数を示す。また、質量平均分子量は５００～２００，０００の範囲にある。）

（式中、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１～３の直鎖又は分岐のアルキル基を示し、Ｘ_５は、塩素原子、ＣＨ_３ＳＯ_４、Ｃ_２Ｈ_５ＳＯ_４のいずれかを示す。また、質量平均分子量は１０，０００～３００，０００の範囲にある。）
さらには、ｎ２ａ及びｎ２ｂが、０若しくは１の整数である、又は、ｎ３ａ及びｎ３ｂが、０又は１の整数であること、Ｘ_２ａ及びＸ_２ｂが同一である、又は、Ｘ_３ａ及びＸ_３ｂが同一であること、前記カチオン性高分子とアクリル系高分子分散剤の質量比が、１：２．５～１：１６であること、２０℃において、ＢＬ型回転粘度計による回転速度３０ｒｐｍでの粘度が１～２０ｍＰａ・ｓであること、前記着色剤の平均粒子径が、０．０１～５μｍの範囲にあること、前記顔料が、（イ）電子供与性呈色性有機化合物と、（ロ）電子受容性化合物と、（ハ）前記（イ）、（ロ）成分の呈色反応をコントロールする反応媒体とから少なくともなる可逆熱変色性組成物を内包した可逆熱変色性マイクロカプセル顔料であること、前記（ハ）成分が、前記可逆熱変色性組成物全量に対して６０～９０質量％の範囲にあり、質量平均分子量が２５０以上であり、且つ、２０℃において、水を基準物質とした場合の完全発色状態の前記可逆熱変色性マイクロカプセル顔料の比重が、１．０５～１．２０であること、前記アクリル系高分子分散剤が、側鎖にカルボキシ基を有する櫛形高分子分散剤であること、前記ビヒクルが、９０～１８５の原子量を有する６族元素の酸素酸又はその塩からなる比重調整剤を含んでなることを要件とする。
さらには、前記筆記具用水性インキ組成物を収容してなる筆記具、前記筆記具が、毛細間隙が形成された、樹脂加工体又は樹脂成形体からなるマーキングペンチップを備えてなること、前記筆記具の軸筒内に、繊維集束体からなるインキ吸蔵体を内蔵してなり、且つ、前記インキ吸蔵体と前記マーキングペンチップが連結されてなるマーキングペンであって、前記インキ吸蔵体に、前記筆記具用水性インキ組成物が含侵されてなるマーキングペンであること、前記筆記具による筆跡を摩擦熱で変色する摩擦部材を備えてなることを要件とする。 The present invention comprises a vehicle containing a colorant selected from pigments or resin particles, at least water, a cationic polymer selected from the following formulas (1) to (5), and an acrylic polymer dispersant. A water-based ink composition for writing tools is a requirement.

(In the formula, n1 indicates 0 or an integer of 1, X ₁ indicates any of hydrochloric acid, amidosulfuric acid, and acetic acid, n indicates a natural number, and the mass average molecular weight is in the range of 500 to 200,000. be.)

(In the formula, n2a and n2b independently indicate an integer of 0 or 1, X _2a and X _2b independently indicate either hydrochloric acid, amidosulfate, or acetic acid, and m and n respectively. It independently shows a natural number, and its mass average molecular weight is in the range of 500 to 200,000.)

(In the formula, n3a and n3b independently indicate an integer of 0 or 1, X _3a and X _3b independently indicate either hydrochloric acid, amidosulfate, or acetic acid, and m and n respectively. It independently shows a natural number, and its mass average molecular weight is in the range of 500 to 200,000.)

(In the formula, R ₁ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, n4 represents an integer of 0 or 1, and X ₄ represents hydrochloric acid, amidosulfate, or acetic acid. Either is indicated, n indicates a natural number, and the mass average molecular weight is in the range of 500 to 200,000.)

(In the formula, R ₂ and R ₃ each independently represent a linear or branched alkyl group having 1 to 3 carbon atoms, and X ₅ is a chlorine atom, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ . In addition, the mass average molecular weight is in the range of 10,000 to 300,000.)
Furthermore, n2a and n2b are integers of 0 or 1, or n3a and n3b are integers of 0 or 1, X _2a and X _2b are the same, or X _3a and X _3b are. They must be the same, the mass ratio of the cationic polymer to the acrylic polymer dispersant is 1: 2.5 to 1:16, and at 20 ° C., at a rotation speed of 30 rpm by a BL type rotational viscometer. The viscosity is 1 to 20 mPa · s, the average particle size of the colorant is in the range of 0.01 to 5 μm, and the pigment is (a) an electron-donating color-developing organic compound and (b). ) A reversible thermochromic microcapsule pigment containing at least a reversible thermochromic composition comprising an electron-accepting compound and (c) a reaction medium for controlling the coloration reaction of the components (a) and (b). That is, the component (c) is in the range of 60 to 90% by mass with respect to the total amount of the reversible thermochromic composition, the mass average molecular weight is 250 or more, and water is used as a reference substance at 20 ° C. When the color is completely developed, the reversible thermochromic microcapsule pigment has a specific gravity of 1.05 to 1.20, and the acrylic polymer dispersant has a comb-shaped polymer dispersion having a carboxy group in the side chain. It is a requirement that the vehicle contains a specific gravity adjusting agent consisting of an oxygen acid of a Group 6 element having an atomic weight of 90 to 185 or a salt thereof.
Further, a writing tool accommodating the water-based ink composition for writing tools, the writing tool is provided with a marking pen tip made of a resin processed body or a resin molded body in which pore gaps are formed, and a shaft of the writing tool. A marking pen in which an ink storage body made of a fiber bundle is built-in, and the ink storage body and the marking pen tip are connected to each other, and the ink storage body is water-based for the writing tool. It is a requirement that the marking pen is impregnated with the ink composition and that the pen is provided with a friction member that discolors the writing marks of the writing tool by frictional heat.

INDUSTRIAL APPLICABILITY According to the present invention, an ink composition using a colorant having a large specific gravity is suppressed from the fact that the colorant floats or precipitates and is localized in the ink composition to darken or lighten the handwriting. When the housed writing instrument is in an upright position and is subjected to external stimuli such as vibration or stored for a long period of time, the handwriting does not fade and a good handwriting with excellent color development can be formed. An ink composition for a writing instrument and a writing instrument can be provided.

It is a graph explaining the hysteresis characteristic in the color density | temperature curve of the heat decolorizing type reversible thermochromic composition. It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the heat decolorizing type reversible thermochromic composition having color memory. It is a graph explaining the hysteresis characteristic in the color density | temperature curve of the reversible thermochromic composition of a heating color development type. It is explanatory drawing which shows one Example of the writing instrument of this invention. It is explanatory drawing which shows the other embodiment of the writing instrument of this invention. FIG. 5 is a sectional view taken along line AA of the resin-processed pen body in the writing tool of FIG. It is explanatory drawing which shows the other embodiment of the writing instrument of this invention.

The water-based ink composition for writing tools of the present invention (hereinafter, may be referred to as "water-based ink composition", "ink composition", or "ink") is a colorant selected from pigments or resin particles, and at least water. A vehicle containing a cationic polymer selected from the above formulas (1) to (5) and an acrylic polymer dispersant. Hereinafter, each component constituting the water-based ink composition of the present invention will be described.

The water-based ink composition of the present invention contains pigments or resin particles as a colorant.
The pigment is not particularly limited as long as it can be dispersed in an aqueous medium, and examples thereof include inorganic pigments, organic pigments, brilliant pigments, fluorescent pigments, and phosphorescent pigments. Further, examples thereof include microcapsule pigments in which the above-mentioned pigments, dyes, or functional materials such as heat-discoloring materials and photo-discoloring materials are encapsulated in microcapsules.
Examples of the resin particles include pigments, dyes, or resin particles containing a functional material such as a heat-discoloring material or a photo-discoloring material.

Examples of the inorganic pigment include carbon black, rutile-type or anatase-type titanium oxide, zinc oxide, iron black, yellow iron oxide, petals, ultramarine and the like.

Examples of organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, thioindigo pigments, and anthraquinone pigments. Examples thereof include quinophthalone pigments, diketopyrrolopyrrole pigments, slene pigments, indigo pigments, phthalone pigments, methine / azomethine pigments, and metal complex pigments.

Further, it is also possible to use an aqueous dispersion pigment or the like which is finely and stably dispersed in an aqueous medium by using a surfactant or a resin in advance.
Specifically, as an aqueous dispersion pigment, C.I. I. Pigment Blue 15: 3B [manufactured by Sanyo Dye Co., Ltd., product name: Sandye Super Blue GLL-E (solid content: 24%)], C.I. I. Pigment Red 146 [manufactured by Sanyo Dye Co., Ltd., product name: Sandye Super Pink FBL (solid content: 21.5%)], C.I. I. Pigment Yellow 81 [manufactured by Dainichiseika Kogyo Co., Ltd., product name: TC Yellow FG (solid content: about 30%)], C.I. I. Pigment Red 220/166 [manufactured by Dainichiseika Kogyo Co., Ltd., product name: TC Red FG (solid content: about 35%)] and the like can be exemplified.
Examples of the resin for dispersing the pigment include polyamide, polyurethane, polyester, epoxy resin, melamine resin, phenol resin, silicone resin, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, and polystyrene. Examples thereof include acrylic acid resin, maleic acid resin, gum arabic, cellulose, dextran, casein, derivatives thereof, and copolymers of the above-mentioned resins.

Examples of the brilliant pigment include a metallic glossy pigment in which the surface of a core material such as a glass piece is coated with gold, silver, etc., a natural mica, a synthetic mica, and a metal oxide such as titanium oxide on the surface of a core material such as flaky aluminum oxide. Metal pigments obtained by peeling off a metal vapor deposition film such as aluminum formed on a base material such as pearl pigments, cholesteric liquid crystal pigments, metal powder pigments, films, etc. coated with, and aluminum, etc. on colorless transparent or colored transparent films. Examples thereof include metal pigments having a metal vapor deposition film formed and powder-treated.

Examples of the fluorescent pigment include synthetic resin fine particle fluorescent pigments in which various fluorescent dyes are solid-solved in a resin matrix.

As the phosphorescent pigment, a general-purpose pigment is used as long as it has the property of absorbing and accumulating light rays such as the sun and electric lamps, and gradually emitting light in a dark place to emit light (this is called afterglow). For example, CaS / Bi-based, CaSrS / Bi-based, ZnS / Cu-based, ZnCdS / Cu-based, SrAl2O4 / rare earth metal-based, and the like can be exemplified.

The above-mentioned pigments can be used alone or in admixture of two or more, preferably 1 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 10 to 35% in the total amount of the ink composition. It is blended in the range of mass%. If the blending ratio of the pigment exceeds 50% by mass, the ink ejection property of the writing instrument containing the ink composition is lowered, and the writing performance is likely to be impaired. On the other hand, if the blending ratio is less than 1% by mass, it becomes difficult to obtain a suitable handwriting concentration as a writing tool.
When the above pigment is used as the colorant, a pigment dispersant can be used if necessary. Examples of the pigment dispersant include anionic and nonionic surfactants, anionic polymers such as polyacrylic acid and styrene acrylic acid, and nonionic polymers such as PVP and PVA.

Further, the pigment applied to the present invention includes a pigment, a dye, or a microcapsule pigment in which a functional material such as a heat-discoloring material or a photo-discoloring material is encapsulated in a microcapsule. By encapsulating pigments, dyes, functional materials and the like in microcapsules, they are isolated and protected from the external environment, and the light resistance and water resistance of the inclusions can be improved.

Examples of the microcapsule pigment containing the pigment or dye include microcapsule pigments containing a colored substance obtained by dispersing or dissolving the pigment or dye in an oily medium.
As the pigment, the above-mentioned inorganic pigment, organic pigment, brilliant pigment, fluorescent pigment, phosphorescent pigment and the like can be used.
As the dye, conventionally known oil-soluble dyes, disperse dyes and the like can be used.

Examples of the oil-soluble dye include C.I. I. Solvent Black 7, C.I. I. Solvent Black 123, C.I. I. Solvent Blue 2, C.I. I. Solvent Blue 25, C.I. I. Solvent Blue 55, C.I. I. Solvent Blue 70, C.I. I. Solvent Red 8, C.I. I. Solvent Red 49, C.I. I. Solvent Red 100, C.I. I. Solvent Violet 8, C.I. I. Solvent Violet 21, C.I. I. Solvent Green 3, C.I. I. Solvent Yellow 21, C.I. I. Solvent Yellow 44, C.I. I. Solvent Yellow 61, C.I. I. The Solvent Orange 37 and the like can be exemplified.
Examples of the disperse dye include C.I. I. Disperse Yellow 82, C.I. I. Disperse Yellow 3, C.I. I. Disperse Yellow 54, C.I. I. Disperse Red 191 and C.I. I. Disperse Red 60, C.I. I. Disperse Violet 57 and the like can be exemplified.

Examples of the oily medium include esters such as monobasic acid esters, dibasic acid monoesters, dibasic acid diesters, partial or complete esters of polyhydric alcohols, aromatic hydrocarbons such as alkylbenzene and alkylnaphthalene, and higher grades. Examples thereof include alcohols, ketones, and ethers.
The above oil-based medium may be used alone or in admixture of two or more.

As the thermochromic material, (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) the above-mentioned (a) and (b) components determine the occurrence temperature of the color reaction. Examples thereof include a reversible thermochromic composition comprising a reaction medium.
The reversible thermochromic composition is described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-229398, etc., before and after a predetermined temperature (discoloration point) as a boundary. Discoloration occurs in the temperature range above the high temperature side discoloration point, and the color develops in the temperature range below the low temperature side discoloration point. The state of is maintained as long as the heat or cold required for the state to develop is applied, but when the heat or cold is no longer applied, the state returns to the state exhibited in the normal temperature range, and the hysteresis width (ΔH) is A heat-decoloring type (decolorizes by heating and develops color by cooling) reversible thermochromic composition having relatively small characteristics (ΔH = 1 to 7 ° C.) can be used (see FIG. 1).

Further, the hysteresis width described in JP-A No. 4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, etc. The shape of the curve, which shows a large characteristic (ΔH = 8 to 70 ° C.) and plots the change in color density due to temperature change, is higher than the discoloration temperature range, contrary to the case where the temperature is raised from the lower temperature side than the discoloration temperature range. The color changes by following a path that is significantly different from the case of descending from the side, and the color development state in the temperature range of the complete color development temperature t ₁ or less, or the decolorization state in the high temperature range of the complete decolorization temperature t ₄ or more, Heat decolorization type with color memory in a specific temperature range [temperature range between color development start temperature t ₂ and decolorization start temperature t ₃ (substantial two-phase holding temperature range)] (decolorization by heating and color development by cooling) It is also possible to use a reversible thermochromic composition (see FIG. 2).

The components (a), (b), and (c) will be specifically described below.
The component (a), that is, the electron-donating color-developing organic compound is a component that determines a color, and is a compound that donates electrons to the component (b), which is a color developer, to develop a color.
Examples of the electron-donating color-developing organic compound include a phthalide compound, a fluorine compound, a stirinoquinoline compound, a diazarodamine lactone compound, a pyridine compound, a quinazoline compound, and a bisquinazoline compound. preferable.
Examples of the phthalide compound include diphenylmethanephthalide compound, phenylindrill phthalide compound, indolylphthalide compound, diphenylmethane azaphthalide compound, phenylindolyl azaphthalide compound, and derivatives thereof. Phenylindrill azaphthalide compounds and derivatives thereof are preferred.
Examples of the fluorin compound include an aminofluorane compound, an alkoxyfluorane compound, and derivatives thereof.

Examples of the electron-donating color-developing organic compound include, for example.
3,3-Bis (4-dimethylaminophenyl) -6-dimethylaminophthalide,
3- (4-Diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) phthalide,
3,3-bis (1-n-butyl-2-methylindole-3-yl) phthalide,
3,3-Bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- (2-n-Hexyloxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- (2-Acetamide-4-diethylaminophenyl) -3- (1-propyl-2-methylindole-3-yl) -4-azaphthalide,
3,6-bis (diphenylamino) fluorane,
3,6-Bis (N-Phenyl-N-p-Trillamino) Fluoran,
3,6-dimethoxyfluoran,
3,6-di-n-butoxyfluolane,
2-Methyl-6- (N-ethyl-N-p-trillamino) fluorane,
3-Chloro-6-cyclohexylaminofluorane,
2-Methyl-6-cyclohexylaminofluorane,
2-Chloroamino-6-di-n-butylaminofluorane,
2- (2-Chloroanilino) -6-di-n-butylaminofluorane,
2- (3-Trifluoromethylanilino) -6-diethylaminofluorane,
2- (3-Trifluoromethylanilino) -6-di-n-pentylaminofluorane,
2-Dibenzylamino-6-diethylaminofluorane,
2- (N-Methylanilino) -6- (N-ethyl-Np-trillamino) fluorane,
1,3-dimethyl-6-diethylaminofluorane,
2-Chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methoxy-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-anilino-3-methoxy-6-di-n-butylaminofluorane,
2-Xylidino-3-methyl-6-diethylaminofluorane,
2-Anilino-3-methyl-6- (N-ethyl-N-p-trillamino) fluorane,
6-diethylamino-1,2-benzofluorane,
6- (N-ethyl-N-isobutylamino) -1,2-benzofluorine,
6- (N-Ethyl-N-isoamylamino) -1,2-benzofluorine,
2- (3-Methoxy-4-dodecoxystylyl) quinoline,
2-diethylamino-8-diethylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -isobenzofuran] -3'-on,
2-Di-n-butylamino-8-di-n-butylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -isobenzofuran] -3'-On,
2-Di-n-butylamino-8-diethylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -isobenzofuran] -3'-on ,
2-Di-n-butylamino-8- (N-ethyl-N-isoamylamino) -4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -Isobenzofuran] -3'-on,
2-Di-n-butylamino-8-di-n-pentylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -isobenzofuran] -3'-on,
4,5,6,7-Tetrachloro-3- (4-dimethylamino-2-methoxyphenyl) -3- (1-n-butyl-2-methylindole-3-yl) -1 (3H) -iso Benzofuranone,
4,5,6,7-Tetrachloro-3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -1 (3H) -isobenzofuranone,
4,5,6,7-Tetrachloro-3- (4-diethylamino-2-ethoxyphenyl) -3- (1-n-pentyl-2-methylindole-3-yl) -1 (3H) -isobenzo Furanon,
4,5,6,7-Tetrachloro-3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindole-3-yl) -1 (3H) -isobenzofuranone,
3', 6'-bis [phenyl (2-methylphenyl) amino] spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
3', 6'-bis [phenyl (3-methylphenyl) amino] spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
3', 6'-bis [phenyl (3-ethylphenyl) amino] spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-dimethylaminophenyl) pyridine,
2,6-bis (2', 4'-diethyloxyphenyl) -4- (4'-dimethylaminophenyl) pyridine,
2- (4'-Dimethylaminophenyl) -4-methoxyquinazoline,
4,4'-Ethylenedioxy-bis [2- (4-diethylaminophenyl) quinazoline]
Etc. can be exemplified.
As the fluorans, in addition to the compound having a substituent on the phenyl group forming the xanthene ring, the phenyl group forming the xanthene ring has a substituent and the phenyl group forming the lactone ring also has a substituent (for example). , An alkyl group such as a methyl group, a halogen atom such as a chlorine atom), and the like may be a blue or black compound.

The component (b), that is, the electron-accepting compound is a compound that receives electrons from the component (a) and functions as a color developer of the component (a).
Examples of the electron-accepting compound include a group of compounds having an active proton, a group of pseudo-acidic compounds [a group of compounds that are not acids but act as acids in a reversible thermochromic composition to develop color of component (a)], and electrons. Examples thereof include compounds selected from a group of compounds having pores. Among the above components (b), a compound selected from the group of compounds having an active proton is preferable.

The group of compounds having an active proton includes compounds having a phenolic hydroxyl group and derivatives thereof, carboxylic acids and derivatives thereof, acidic phosphate esters and derivatives thereof, azol-based compounds and derivatives thereof, 1,2,3-triazole and the like. Examples thereof include derivatives thereof, cyclic carbosulfoimides, halohydrins having 2 to 5 carbon atoms, sulfonic acids and derivatives thereof, and inorganic acids. As the carboxylic acid and its derivative, an aromatic carboxylic acid and its derivative, or an aliphatic carboxylic acid having 2 to 5 carbon atoms and its derivative thereof are preferable.
Pseudo-acidic compounds include metal salts of compounds having phenolic hydroxyl groups, metal salts of carboxylic acids, metal salts of acidic phosphoric acid esters, metal salts of sulfonic acid, aromatic carboxylic acid anhydrides, and aliphatic carboxylic acid anhydrides. , Aromatic carboxylic acid and sulfonic acid mixed anhydride, cycloolefin dicarboxylic acid anhydride, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, halogenated alcohols and the like.
Examples of the compound group having electron vacancies include borates, boric acid esters, inorganic salts and the like.

Among the above-mentioned components (b), a compound having a phenolic hydroxyl group is preferable because it can more effectively exhibit the thermal discoloration property.
Compounds having a phenolic hydroxyl group include a wide range of compounds from monophenol compounds to polyphenol compounds, and further include bisphenol compounds, trisphenol compounds, phenol-aldehyde condensed resins and the like. The compound having a phenolic hydroxyl group preferably has at least two or more benzene rings. Further, the compound having a phenolic hydroxyl group may have a substituent such as an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and an ester or amide group thereof, a halogen atom and the like.

Metals contained in metal salts such as compounds having a phenolic hydroxyl group include, for example, sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum. Etc. can be exemplified.

The compounds of the component (b) are illustrated below.
Examples of the compound having one phenolic hydroxyl group include, for example.
Phenol,
o-cresol,
m-cresol,
p-cresol,
4-Ethylphenol,
4-n-propylphenol,
4-n-butylphenol,
2-tert-butylphenol,
3-tert-butylphenol,
4-tert-butylphenol,
4-n-Pentylphenol,
4-tert-Pentylphenol,
4-n-octylphenol,
4-tert-octylphenol,
4-n-nonylphenol,
4-n-dodecylphenol,
3-n-pentadecylphenol,
4-n-stearylphenol,
1- (4-Hydroxyphenyl) decane-1-one,
4-Chlorophenol,
4-bromophenol,
4-Trifluoromethylphenol,
4-Methylthiophenol,
4-Nitrophenol,
2-Phenylphenol,
4-Phenylphenol,
2-Benzylphenol,
2-Benzyl-4-chlorophenol,
4-cumylphenol,
4-Hydroxybenzophenone,
4-Chloro-4'-hydroxybenzophenone,
4-Fluoro-4'-hydroxybenzophenone,
4-Cyclohexylphenol,
2-Hydroxybenzyl alcohol,
3-Hydroxybenzyl alcohol,
4-Hydroxybenzyl alcohol,
4- (2-Hydroxyethyl) phenol,
3-Methoxyphenol,
4-ethoxyphenol,
4-n-propoxyphenol,
4-n-butoxyphenol,
4-n-Heptyloxyphenol,
4- (2-Methoxyethyl) phenol,
α-Naphthol,
β-naphthol,
2,3-dimethylphenol,
2,4-dimethylphenol,
2,6-dimethylphenol,
2,6-di-tert-butylphenol,
2,4-dichlorophenol,
2,4-difluorophenol,
Thymol,
3-Methyl-4-methylthiophenol,
2-tert-butyl-5-methylphenol,
2,6-bis (hydroxymethyl) -4-methylphenol,
2,3,5-trimethylphenol,
2,6-bis (hydroxymethyl) -4-tert-octylphenol,
6-Hydroxy-1,3-benzoxathiol-2-one,
2,4-Bis (Phenylsulfonyl) Phenol,
2,4-Bis (Phenylsulfonyl) -5-Methylphenol,
2,4-Bis (4-methylphenylsulfonyl) phenol,
2-Phenylphenol,
4-Phenylphenol,
2,6-diphenylphenol,
3-Benzylbiphenyl-2-ol,
3,5-Dibenzylbiphenyl-4-ol,
4-Cyano-4'-hydroxybiphenyl,
1-Hydroxybenzotriazole,
1-Hydroxy-5-methylbenzotriazole,
1-Hydroxy-5-chlorobenzotriazole,
1-Hydroxy-5-methoxybenzotriazole,
1-Hydroxy-4-benzoylaminobenzotriazole,
1-Hydroxy-4,5,6,7-tetrachlorobenzotriazole,
1,4-Hydroxybenzotriazole,
1-Hydroxy-5-nitrobenzotriazole,
1-Hydroxy-5-Phenylbenzotriazole,
1-Hydroxy-5-benzylbenzotriazole,
1-Hydroxy-5-ethylbenzotriazole,
1-Hydroxy-5-n-octylbenzotriazole,
1-Hydroxy-5-n-butylbenzotriazole,
4-Hydroxybenzoate n-butyl,
4-Hydroxybenzoate n-octyl,
4-Hydroxybenzoate 2-heptadecafluorooctylethane,
Benzyl 4-hydroxybenzoate,
4-Hydroxybenzoate benzyl ester,
4-Hydroxybenzoate-o-methylbenzyl,
4-Hydroxybenzoate-m-methylbenzyl,
4-Hydroxybenzoate-p-methylbenzyl,
4-Hydroxybenzoate-p-ethylbenzyl,
4-Hydroxybenzoate-p-propylbenzyl,
4-Hydroxybenzoic acid-p-tert-butylbenzyl,
Phenylethyl 4-hydroxybenzoate,
4-Hydroxybenzoate-o-methylphenylethyl,
4-Hydroxybenzoate-m-methylphenylethyl,
4-Hydroxybenzoate-p-methylphenylethyl,
4-Hydroxybenzoate-p-ethylphenylethyl,
4-Hydroxybenzoate-p-propylphenylethyl,
Examples thereof include 4-hydroxybenzoic acid-p-tert-butylphenylethyl and the like.

Examples of the compound having 2 phenolic hydroxyl groups include, for example.
Resorcin,
2-Methylresorcin,
4-n-hexyl resorcin,
4-n-octylresorcin,
4-tert-octylresorcin,
4-Benzoyl resorcin,
4-Nitroresorcin,
Methyl β-resorcinol,
Benzyl β-resorcinate,
2-Chloro-4-pentanoylresorcin,
6-Chloro-4-pentanoylresorcin,
2-Chloro-4-hexanoylresorcin,
6-Chloro-4-hexanoylresorcin,
2-Chloro-4-propanoylresorcin,
6-Chloro-4-propanoylresorcin,
2,6-Dichloro-4-propanoylresorcin,
6-Fluoro-4-propanoylresorcin,
2-Chloro-4-phenylacetylresorcin,
6-Chloro-4-phenylacetylresorcin,
2-Chloro-4-β-Phenylpropanoylresorcin,
6-Chloro-4-β-Phenylpropanoylresorcin,
2-Chloro-4-phenoxyacetylresorcin,
6-Chloro-4-phenoxyacetylresorcin,
4-Benzoyl-2-chlororesorcin,
6-Chloro-4-m-Methylbenzoylresorcin,
4- [1', 3', 4', 9'a-tetrahydro-6'-hydroxyspiro (cyclohexane-1,9'-[9H] -xanthene) -4'a- [2H] -yl] -1 ， 3-Benzenediol ，
Hydroquinone,
Methyl hydroquinone,
Trimethylhydroquinone,
Catechol,
4-tert-Butylcatechol,
1,6-Dihydroxynaphthalene,
2,7-Dihydroxynaphthalene,
1,5-Dihydroxynaphthalene,
2,6-Dihydroxynaphthalene,
2,4-Dihydroxybenzophenone,
4,4'-Dihydroxybenzophenone,
2,4-Dihydroxy-2'-methylbenzophenone,
2,4-Dihydroxy-3'-methylbenzophenone,
2,4-Dihydroxy-4'-methylbenzophenone,
2,4-Dihydroxy-4'-ethylbenzophenone,
2,4-Dihydroxy-4'-n-propylbenzophenone,
2,4-Dihydroxy-4'-isopropylbenzophenone,
2,4-Dihydroxy-4'-n-butylbenzophenone,
2,4-Dihydroxy-4'-isobutylbenzophenone,
2,4-Dihydroxy-4'-tert-butylbenzophenone,
2,4-Dihydroxy-4'-n-pentylbenzophenone,
2,4-Dihydroxy-4'-n-hexylbenzophenone,
2,4-Dihydroxy-4'-n-heptylbenzophenone,
2,4-Dihydroxy-4'-n-octylbenzophenone,
2,4-Dihydroxy-4'-n-decylbenzophenone,
2,4-Dihydroxy-2', 3'-dimethylbenzophenone,
2,4-Dihydroxy-2', 4'-dimethylbenzophenone,
2,4-Dihydroxy-2', 5'-dimethylbenzophenone,
2,4-Dihydroxy-2', 6'-dimethylbenzophenone,
2,4-Dihydroxy-3', 4'-dimethylbenzophenone,
2,4-Dihydroxy-3', 5'-dimethylbenzophenone,
2,4-Dihydroxy-2', 4', 6'-trimethylbenzophenone,
2,4-Dihydroxy-2'-methoxybenzophenone,
2,4-Dihydroxy-3'-methoxybenzophenone,
2,4-Dihydroxy-4'-methoxybenzophenone,
2,4-Dihydroxy-2'-ethoxybenzophenone,
2,4-Dihydroxy-4'-ethoxybenzophenone,
2,4-Dihydroxy-4'-n-propoxybenzophenone,
2,4-Dihydroxy-4'-isopropoxybenzophenone,
2,4-Dihydroxy-4'-n-butoxybenzophenone,
2,4-Dihydroxy-4'-isobutoxybenzophenone,
2,4-Dihydroxy-4'-n-pentyloxybenzophenone,
2,4-Dihydroxy-4'-n-hexyloxybenzophenone,
2,4-Dihydroxy-4'-n-heptyloxybenzophenone,
2,4-Dihydroxy-4'-n-octyloxybenzophenone,
2,4-Dihydroxy-4'-n-nonyloxybenzophenone,
2,4-Dihydroxy-2', 3'-dimethoxybenzophenone,
2,4-Dihydroxy-2', 4'-dimethoxybenzophenone,
2,4-Dihydroxy-2', 5'-dimethoxybenzophenone,
2,4-Dihydroxy-2', 6'-dimethoxybenzophenone,
2,4-Dihydroxy-3', 4'-dimethoxybenzophenone,
2,4-Dihydroxy-3', 5'-dimethoxybenzophenone,
2,4-Dihydroxy-3', 4'-diethoxybenzophenone,
2,4-Dihydroxy-2', 3', 4'-trimethoxybenzophenone,
2,4-Dihydroxy-2', 3', 6'-trimethoxybenzophenone,
2,4-Dihydroxy-3', 4', 5'-trimethoxybenzophenone,
Examples thereof include 2,4-dihydroxy-3', 4', 5'-triethoxybenzophenone and the like.

Further, as a bisphenol compound, for example,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) propane,
1,1-bis (4-hydroxyphenyl) n-butane,
1,1-bis (4-hydroxyphenyl) n-pentane,
1,1-bis (4-hydroxyphenyl) n-hexane,
1,1-bis (4-hydroxyphenyl) n-heptane,
1,1-bis (4-hydroxyphenyl) n-octane,
1,1-bis (4-hydroxyphenyl) n-nonane,
1,1-bis (4-hydroxyphenyl) n-decane,
1,1-bis (4-hydroxy-3-methylphenyl) decane,
1,1-bis (4-hydroxyphenyl) n-dodecane,
1,1-bis (4-hydroxyphenyl) -2-methylpropane,
1,1-bis (4-hydroxyphenyl) -3-methylbutano,
1,1-bis (4-hydroxyphenyl) -3-methylpentane,
1,1-bis (4-hydroxyphenyl) -2,3-dimethylpentane,
1,1-bis (4-hydroxyphenyl) -2-ethylbutane,
1,1-bis (4-hydroxyphenyl) -2-ethylhexane,
1,1-bis (4-hydroxyphenyl) -3,7-dimethyloctane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3-methyl) cyclohexane,
Diphenolic acid,
1-Phenyl-1,1-bis (4-hydroxyphenyl) methane,
2,2-Bis (4-hydroxyphenyl) propane,
2,2-Bis (4-hydroxyphenyl) n-butane,
2,2-Bis (4-hydroxyphenyl) n-pentane,
2,2-Bis (4-hydroxyphenyl) n-hexane,
2,2-bis (4-hydroxyphenyl) n-heptane,
2,2-Bis (4-hydroxyphenyl) n-octane,
2,2-bis (4-hydroxyphenyl) n-nonane,
2,2-Bis (4-hydroxyphenyl) n-decane,
2,2-Bis (4-hydroxyphenyl) n-dodecane,
2,2-Bis (4-hydroxyphenyl) -6,10,14-trimethylpentadecane,
1-Phenyl-1,1-bis (4-hydroxyphenyl) ethane,
2,2-Bis (4-hydroxyphenyl) methylpropionate,
2,2-Bis (4-hydroxyphenyl) butyl propionate,
2,2-Bis (4-hydroxy-3-methylphenyl) methylpropionate,
2,2-Bis (4-hydroxyphenyl) ethyl propionate,
2,2-Bis (4-hydroxyphenyl) -4-methylpentane,
2,2-Bis (4-hydroxyphenyl) -4-methylhexane,
2,2-Bis (4-hydroxyphenyl) hexafluoropropane,
2,2-Bis (3,5-Dihydroxymethyl-4-hydroxyphenyl) Hexafluoropropane,
2,2-Bis (4-hydroxy-3-methylphenyl) propane,
2,2-Bis (4-hydroxy-3-methylphenyl) butane,
2,2-Bis (4-hydroxy-3-isopropylphenyl) propane,
2,2-bis (3-sec-butylphenyl-4-hydroxy) propane,
2,2-Bis (4-hydroxy-3-phenylphenyl) propane,
2,2-Bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-Bis (3-fluoro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dihydroxymethyl-4-hydroxyphenyl) propane,
9,9-bis (4-hydroxy-3-methylphenyl) fluorene,
1,3-Bis [2- (4-Hydroxyphenyl) -2-propyl] benzene,
1,4-Bis [2- (4-Hydroxyphenyl) -2-propyl] benzene,
3,3-Bis (4-hydroxyphenyl) oxindole,
3,3-bis (4-hydroxy-3-methylphenyl) oxindole,
Bis (2-hydroxyphenyl) methane,
Bis (2-hydroxy-5-methylphenyl) methane,
Bis (2-hydroxy-3-hydroxymethyl-5-methyl) methane,
4,4'-[1,4-phenylenebis (1-methylethylidene)] bis (2-methylphenol),
1,1-bis (4-hydroxy-3-phenylphenyl) cyclohexane,
3,3-Ethylene oxydiphenol,
1,4-Bis (4-hydroxybenzoart) -3-methylbenzene,
4,4 ″ -dihydroxy-3 ″ -methyl-p-terphenyl,
4,4 ″ -dihydroxy-3 ″ -isopropyl-p-terphenyl,
2,2-Dimethyl-1,3-bis (4-hydroxybenzoyloxy) propane,
2,2'-biphenol,
4,4'″ -dihydroxy-p-quaterphenyl,
4,4-Dihydroxydiphenyl ether,
Bis (4-hydroxyphenylthioethyl) ether bis (4-hydroxyphenyl) sulfone,
4-Benzyloxy-4'-hydroxydiphenyl sulfone,
4- (4-Methylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (4-Ethylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (4-n-propylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (4-Isopropylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (4-n-Butylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (4-Isobutylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (4-sec-Butylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (4-tert-butylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (3-Methylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (3-Ethylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (3-n-propylbenzyloxy) -4'-hydroxydiphenyl sulfone,
4- (3-Isopropylbenzyloxy) -4'-dihydroxyphenylsulfone,
4- (3-n-Butylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (3-Isobutylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (3-sec-Butylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (3-tert-Butylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (2-Methylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (2-Ethylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (2-n-propylbenzyloxy) -4'-hydroxydiphenyl sulfone,
4- (2-Isopropylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (2-n-Butylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (2-Isobutylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (2-sec-Butylbenzyloxy) -4'-hydroxydiphenylsulfone,
4- (2-tert-butylbenzyloxy) -4'-hydroxydiphenylsulfone,
2,4'-Dihydroxydiphenyl sulfone,
3,4'-Dihydroxydiphenyl sulfone,
4-Hydroxydiphenyl sulfone,
4-Methyl-4'-hydrokidiciphenyl sulfone,
4-Ethyl-4'-hydroxydiphenyl sulfone,
4-n-propyl-4'-hydroxydiphenyl sulfone,
4-Isopropyl-4'-hydroxydiphenyl sulfone,
4-Chloro-4'-hydroxydiphenyl sulfone,
4-Fluoro-4'-hydroxydiphenyl sulfone,
4-Chloro-2-methyl-4'-hydroxydiphenyl sulfone,
4-Methoxy-4'-hydroxydiphenyl sulfone,
4-ethoxy-4'-hydroxydiphenyl sulfone,
4-n-propoxy-4'-hydroxydiphenyl sulfone,
4-Isopropoxy-4'-hydroxydiphenyl sulfone,
4-n-Butyloxy-4'-hydroxydiphenyl sulfone,
4-isobutoxy-4'-hydroxydiphenyl sulfone,
4-sec-butoxy-4'-hydroxydiphenyl sulfone,
4-tert-Butyl-4'-hydroxydiphenyl sulfone,
4-n-Pentyloxy-4'-hydroxydiphenyl sulfone,
4-Isopentyloxy-4'-hydroxydiphenyl sulfone,
4- (1-propenyloxy) -4'-hydroxydiphenyl sulfone,
4- (2-propenyloxy) -4'-hydroxydiphenyl sulfone,
4-Benzyloxy-4'-hydroxydiphenyl sulfone,
4- (β-Phenoxyethoxy) -4'-hydroxydiphenyl sulfone,
4- (β-Phenoxypropoxyl) -4'-hydroxydiphenyl sulfone,
Bis (2-allyl-4-hydroxydiphenyl) sulfone,
Bis [4-hydroxy-3- (2-propenyl) phenyl] sulfone,
Bis (3,5-dibromo-4-hydroxyphenyl) sulfone,
Bis (3,5-dichloro-4-hydroxyphenyl) sulfone,
Bis (3-phenyl-4-hydroxyphenyl) sulfone,
Bis (4-hydroxy-3-n-propylphenyl) sulfone,
Bis (4-hydroxy-3-methylphenyl) sulfone,
3,4-Dihydroxydiphenyl sulfone,
3', 4'-dihydroxy-4-methyldiphenyl sulfone,
3,4,4'-trihydroxydiphenyl sulfone,
Bis (3,4-dihydroxyphenyl) sulfone,
2,3,4-trihydroxydiphenylsulfone,
4-Isopropoxy-4'-hydroxydiphenyl sulfone,
4-n-propoxy-4'-hydroxydiphenyl sulfone,
4-allyloxy-4'-hydroxydiphenyl sulfone,
4-Benzyloxy-4'-hydroxydiphenyl sulfone,
4- (2-propenyloxy) -4'-hydroxydiphenyl sulfone,
3-Benzyl-4-benzyloxy-4'-hydroxydiphenyl sulfone,
3-Phenethyl-4-phenethyloxy-4'-hydroxydiphenyl sulfone,
3-Methylbenzyl-4-methylbenzyloxy-4'-hydroxydiphenylsulfone,
4-Benzyloxy-3'-benzyl-4'-hydroxydiphenylsulfone,
4-Phenethyloxy-3'-Phenethyl-4'-Hydroxydiphenylsulfone,
4-Methylbenzyloxy-3'-methylbenzyl-4'-hydroxydiphenylsulfone,
α, α'-bis {4- (p-hydroxyphenyl sulfone) phenoxy} -p-xylene,
4,4'-{Oxybis (ethylene oxide-p-phenylene sulfonyl)} diphenol,
Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide,
Bis (3,5-dimethyl-4-hydroxyphenyl) sulfide,
Bis (3-ethyl-4-hydroxyphenyl) sulfide,
Bis (3,5-diethyl-4-hydroxyphenyl) sulfide,
Bis (4-hydroxy-3-n-propylphenyl) sulfide,
Bis (3,5-di-n-propyl-4-hydroxyphenyl) sulfide,
Bis (3-tert-butyl-4-hydroxyphenyl) sulfide,
Bis (3,5-di-tert-butyl-4-hydroxyphenyl) sulfide,
Bis (4-hydroxy-3-n-pentylphenyl) sulfide,
Bis (3-n-hexyl-4-hydroxyphenyl) sulfide,
Bis (3-n-heptyl-4-hydroxyphenyl) sulfide,
Bis (5-tert-octyl-2-hydroxyphenyl) sulfide,
Bis (2-hydroxy-3-tert-octylphenyl) sulfide,
Bis (2-hydroxy-5-n-octylphenyl) sulfide,
Bis (5-chloro-2-hydroxyphenyl) sulfide,
Bis (3-cyclohexyl-4-hydroxyphenyl) sulfide,
Bis (4-hydroxyphenylthioethoxy) methane,
1,5- (4-Hydroxyphenylthio) -3-oxypentane,
Examples thereof include 1,8-bis (4-hydroxyphenylthio) -3,6-dioxaoctane.

Examples of the compound having three phenolic hydroxyl groups include pyrogallol, phloroglucinol, phloroglucinol carboxylic acid, gallic acid, octyl gallate, and dodecyl gallate.

Further, as a trisphenol compound, for example,
4,4', 4 "-Methyllysine Trisphenol,
4,4', 4 "-Methyllysine Tris (2-methylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2,3,5-trimethylphenol),
4,4'-[(4-Hydroxyphenyl) methylene] bis (2-methylphenol),
4,4'-[(4-Hydroxyphenyl) methylene] bis (2,6-dimethylphenol),
4,4'-[(4-Hydroxy-3-methoxyphenyl) methylene] bisphenol,
4,4'-[(4-Hydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
4,4', 4 "-Etlysine Trisphenol,
4,4', 4 "-ethylidinetris (2-methylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol,
2,4-Bis [(2-Hydroxy-5-methylphenyl) Methyl] -6-cyclohexylphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} methylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} propyridene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} butylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} pentylden] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} hexylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} heptylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} isobutylidene] bisphenol,
4,4'-[1- {4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl} neopentylidene] bisphenol,
2,2'-[1- {4- [1- (2-Hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bisphenol,
3,3'-[1- {4- [1- (3-Hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bisphenol,
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-fluorophenol),
4,4'-[1- {4- [1- (3-Chloro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-chlorophenol),
4,4'-[1- {4- [1- (3-bromo-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-bromophenol),
4,4'-[1- {4- [1- (4-Hydroxy-3-methylphenyl) -1-methylethyl] phenyl} etylidene] bis (2-methylphenol),
4,4'-[1- {4- [1- (3-Ethyl-4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] bis (2-ethylphenol),
4,4'-[1- {4- [1- (3-tert-butyl-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-tert-butylphenol),
4,4'-[1- {4- [1- (4-Hydroxy-3-trifluoromethylphenyl) -1-methylethyl] phenyl} etylidene] bis (2-trifluoromethylphenol),
1,1-bis (4-hydroxyphenyl) -4- (4-hydroxy-α-ethyl) benzylcyclohexane,
4,4'-[(3-ethoxy-4-hydroxyphenyl) methylene] bisphenol,
4,4'-[(3-Hydroxyphenyl) methylene] bis (2,6-dimethylphenol),
2,2'-[(4-Hydroxyphenyl) methylene] bis (3,5-dimethylphenol),
4,4'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (2,6-dimethylphenol),
2,2'-[(2-Hydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
4,4'-[(3-Hydroxyphenyl) methylene] bis (2,3,6-trimethylphenol),
4,4'-[(4-Hydroxyphenyl) methylene] bis (2,3,6-trimethylphenol),
4,4'-[(3-Hydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[(4-Hydroxyphenyl-3-methoxy) methylene] bis (2-cyclohexyl-5-methylphenol),
1,1-bis (4-hydroxyphenyl) -4-hydroxyphenylcyclohexane,
4,4'-[3- (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-phenyl) propylidene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2-methylphenol),
2,4', 4 ″ -Methyllysine trisphenol,
4,4'-[(2-Hydroxyphenyl) methylene] bis (3-methylphenol),
4,4'-[4- (4-Hydroxyphenyl) -sec-butylidene] bis (4-hydroxyphenol),
2,2'-[(3-Hydroxyphenyl) methylene] bis (3,5-dimethylphenol),
4,4'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (2,5-dimethylphenol),
4,4'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (2,6-dimethylphenol),
2,2'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (3,5-dimethylphenol),
2,2'-[(3-Hydroxy-4-methoxyphenyl) methylene] bis (3,5-dimethylphenol),
2,2'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (3,5-dimethylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2-isopropylphenol),
4,4'-[(3-Hydroxyphenyl) methylene] bis (2-isopropylphenol),
4,4'-[(4-Hydroxyphenyl) methylene] bis (2-isopropylphenol),
2,2'-[(3-Hydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
2,2'-[(4-Hydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
2,2'-[(4-3-ethoxy-4-hydroxyphenyl) methylene] bis (3,5-dimethylphenol),
1,1-bis (4-hydroxy-3-methylphenyl) -4- (4-hydroxyphenyl) cyclohexane,
4,4'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (2-isopropylphenol),
4,4'-[(3-Hydroxy-4-methoxyphenyl) methylene] bis (2-isopropylphenol),
4,4'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (2-isopropylphenol),
2,2'-[(2-Hydroxy-3-methoxyphenyl) methylene] bis (3,5,6-trimethylphenol,
2,2'-[(3-Hydroxy-4-methoxyphenyl) methylene] bis (3,5,6-trimethylphenol),
2,2'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (3,5,6-trimethylphenol),
4,4'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (2-isopropylphenol),
2,2'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
4,4'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (2,3,6-trimethylphenol),
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane,
4,4'-[(4-Hydroxy-3-methoxyphenyl) methylene] bis (2-tert-butyl-5-methylphenol),
4,4'-[(2-Hydroxyphenyl) methylene] bis (2-cyclohexylphenol),
4,4'-[(3-Hydroxyphenyl) methylene] bis (2-cyclohexylphenol),
4,4'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (2-tert-butyl-6-methylphenol),
4,4'-[(3-Methoxy-2-hydroxyphenyl) methylene] bis (2-cyclohexylphenol),
4,4'-[(3-Hydroxy-4-methoxyphenyl) methylene] bis (2-cyclohexylphenol),
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxylophenyl) -1-methylethyl] phenyl} etylidene] bis (2-tert-butylphenol),
4,4'-[1- {4- [1- (3,5-dimethyl-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2,6-dimethylphenol),
4,4'-[(3-ethoxy-4-hydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[(3-cyclohexyl-4-hydroxyphenyl) ethylidene] bis (2-cyclohexylphenol),
4,4'-[(5-cyclohexyl-4-hydroxy-2-methoxyphenyl) ethylidene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[1- {4- [1- (3-cyclohexyl-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-cyclohexylphenol),
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bisphenol,
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2-methylphenol),
4,4'-[1- {4- [1- (3-Fluoro-4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis (2,6-dimethylphenol),
2,6-bis [(5-fluoro-2-hydroxyphenyl) methyl] -4-methylphenol,
2,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -4-methylphenol,
2,6-bis [(4-hydroxyphenyl) methyl] -4-methylphenol,
2,6-bis [(4-hydroxyphenyl) methyl] -4-ethylphenol,
2,4-Bis [(4-Hydroxy-3-methylphenyl) methyl] -6-methylphenol,
2,6-bis [(4-hydroxy-3-methylphenyl) methyl] -4-methylphenol,
2,6-bis [(4-hydroxy-3-methylphenyl) methyl] -4-ethylphenol,
2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-ethylphenol,
2,6-bis [(3,5-dimethyl-2-hydroxyphenyl) methyl] -4-methylphenol,
2,6-bis [(2,4-dimethyl-6-hydroxyphenyl) methyl] -4-methylphenol,
2,4-Bis [(4-Hydroxyphenyl) methyl] -6-cyclohexylphenol,
2,6-bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -3,4-dimethylphenol,
2,6-bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -4-ethylphenol,
2,6-bis [(4-hydroxy-2,3,6-trimethylphenyl) methyl] -4-methylphenol,
2,4-Bis [(4-Hydroxy-3-methylphenyl) Methyl] -6-cyclohexylphenol,
2,6-bis [(4-hydroxy-3-methylphenyl) methyl] -4-cyclohexylphenol,
2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-cyclohexylphenol,
2,6-bis [(4-hydroxy-2,3,5-trimethylphenyl) methyl] -4-ethylphenol,
2,4-bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -6-cyclohexylphenol,
4,4', 4 "-methyridintris (2,6-dimethylphenol),
α- (4-Hydroxy-3-methylphenyl) -α, α'-bis (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
α'-(4-Hydroxy-3-methylphenyl) -α, α-bis (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
α, α-bis (4-hydroxy-3-methylphenyl) -α'-(4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
α, α'-bis (4-hydroxy-3-methylphenyl) -α- (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
1,1-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) -1-methylpropyl] cyclohexane,
2,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -4-ethylphenol,
1,1'-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) propyl] cyclohexane,
1,1'-bis (4-hydroxy-3-methylphenyl) -4- [1- (4-hydroxyphenyl) propyl] cyclohexane,
1,1'-bis (3,5-dimethyl-4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) propyl] cyclohexane,
1- (4-Hydroxyphenyl) -1- [4,4-bis (4-hydroxyphenyl) cyclohexyl] -4-isopropylcyclohexane,
4,4'-[3- (2,5-dimethyl-4-hydroxyphenyl) butylene] bis (2,5-dimethylphenol),
1,3,5-tri (4-hydroxy-3-phenylphenyl) adamantane,
1,3,5-tri (3-cyclohexyl-4-hydroxyphenyl) adamantane,
2,4-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -6-cyclohexylphenol,
2,6-bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -4-cyclohexylphenol,
2,4-Bis [(3-cyclohexyl-4-hydroxyphenyl) methyl] -6-methylphenol,
2,4-Bis [(4-Hydroxy-2,3,5-trimethylphenyl) methyl] -6-cyclohexylphenol,
2,6-bis [(5-fluoro-2-hydroxyphenyl) methyl] -4-fluorophenol,
2,6-bis [(3-fluoro-4-hydroxyphenyl) methyl] -4-fluorophenol,
2,4-bis [(3-fluoro-4-hydroxyphenyl) methyl] -6-methylphenol,
4,4'-[3- (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-biphenylpropylidene] bis (5-cyclohexyl-2-methylphenol),
4,4'-[3- (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropylidene] bis (2,5-dimethylphenol),
2,4-bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -6-methylphenol,
1,1,2-Tris (4-hydroxyphenyl) ethane,
1,1,3-Tris (4-hydroxyphenyl) propane,
1,1,4-Tris (4-hydroxyphenyl) butane,
1,2,2-Tris (4-hydroxyphenyl) propane,
1,2,2-tris (4-hydroxyphenyl) butane,
1,2,2-Tris (4-hydroxyphenyl) pentane,
1,2,2-Tris (4-hydroxyphenyl) hexane,
1,2,2-tris (4-hydroxyphenyl) heptane,
1,2,2-Tris (4-hydroxyphenyl) octane,
1,2,2-tris (4-hydroxyphenyl) -3-methylbutano,
1,2,2-tris (4-hydroxyphenyl) -3,3-dimethylbutane,
1,2,2-Tris (4-hydroxyphenyl) -4,4-dimethylpentane,
1,3,3-Tris (4-hydroxyphenyl) butane,
1,3,3-Tris (4-hydroxyphenyl) pentane,
1,3,3-Tris (4-hydroxyphenyl) hexane,
1,3,3-Tris (4-hydroxyphenyl) heptane,
1,3,3-Tris (4-hydroxyphenyl) octane,
1,3,3-Tris (4-hydroxyphenyl) nonane,
1,4,4-Tris (4-hydroxyphenyl) pentane,
1,4,4-Tris (4-hydroxyphenyl) hexane,
1,4,4-Tris (4-hydroxyphenyl) heptane,
1,4,4-Tris (4-hydroxyphenyl) octane,
1,4,4-Tris (4-hydroxyphenyl) nonane,
1,4,4-Tris (4-hydroxyphenyl) decane,
1,2,2-Tris (2-hydroxyphenyl) propane,
1,1,2-Tris (3-hydroxyphenyl) propane,
1- (4-Hydroxyphenyl) -2,2-bis (2-hydroxyphenyl) propane,
1,2,2-Tris (3-fluoro-4-hydroxyphenyl) propane,
1,2,2-Tris (3-chloro-4-hydroxyphenyl) propane,
1,2,2-Tris (3-bromo-4-hydroxyphenyl) propane,
2,2-Bis (3-ethyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) propane,
2,2-Bis (3-tert-butyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) propane,
2,2-Bis (2-hydroxy-3-biphenylyl) -1- (4-hydroxyphenyl) propane,
2,2-Bis (3-trifluoromethyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) propane,
2- (3-Methyl-4-hydroxyphenyl) -1,2-bis (4-hydroxyphenyl) propane,
1- (3-Methyl-4-hydroxyphenyl) -2,2-bis (4-hydroxyphenyl) propane,
3- (3-Methyl-4-hydroxyphenyl) -1,3-bis (4-hydroxyphenyl) butane,
1- (3-Methyl-4-hydroxyphenyl) -3,3-bis (4-hydroxyphenyl) butane,
4- (3-Methyl-4-hydroxyphenyl) -1,4-bis (4-hydroxyphenyl) pentane,
1- (3-Methyl-4-hydroxyphenyl) -4,4-bis (4-hydroxyphenyl) pentane,
1,2-bis (3-methyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) propane,
3,3-Bis (3-methyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) butane,
1,3-bis (3-methyl-4-hydroxyphenyl) -3- (4-hydroxyphenyl) butane,
4,4-Bis (3-methyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) pentane,
1,4-Bis (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) pentane,
1,1,2-Tris (3-methyl-4-hydroxyphenyl) ethane,
1,2,2-Tris (3-methyl-4-hydroxyphenyl) propane,
1,1,3-Tris (3-methyl-4-hydroxyphenyl) propane,
1,3,3-Tris (3-methyl-4-hydroxyphenyl) butane,
1,1,4-Tris (3-methyl-4-hydroxyphenyl) butane,
1,4,4-Tris (3-methyl-4-hydroxyphenyl) pentane,
4,4'-[4- (4-Hydroxyphenyl) -sec-butylidene] bis (2-methylphenol)
Etc. can be exemplified.

Examples of the compound having 4 or more phenolic hydroxyl groups include, for example.
Bis [2-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane,
4,6-bis [(4-hydroxyphenyl) methyl) -1,3-benzenediol,
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2,6-dimethylphenol),
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol),
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2-methylphenol),
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2,3,6-trimethylphenol),
1,1,2,2-tetrakis (4-hydroxyphenyl) ethane,
4,4', 4 ", 4'"-(1,1,2,2-ethanetetrayl) Tetrakis (2-methylphenol),
4,4', 4 ", 4'"-(1,1,2,2-ethanetetrayl) Tetrakis (2,6)
-Dimethylphenol),
4,4', 4 ", 4'"-(1,4-phenylene) bis (methidrine) tetrakis (2,6-dimethylphenol),
2,2'-Bis [4,4-bis (4-hydroxy-3-methylphenyl) cyclohexyl] propane,
2,2'-[(3,4-dihydroxyphenyl) methylene] bis (3,5-dimethylphenol),
4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl) -1,3-benzenediol,
2,2'-[(3,4-dihydroxyphenyl) methylene] bis (3,5,6-trimethylphenol),
4,4'-[(3,4-dihydroxyphenyl) methylene] bis (2-cyclohexylphenol),
Bis [4-hydroxy-3- (2-hydroxybenzyl) -5-methylphenyl] methane,
Bis [4-hydroxy-3- (3-hydroxybenzyl) -5-methylphenyl] methane,
Bis [4-hydroxy-3- (4-hydroxybenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (2-hydroxybenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (3-hydroxybenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (3-hydroxy-4-methylbenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (4-hydroxy-3-methylbenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (3-hydroxy-2-methylbenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (2-hydroxy-3-methylbenzyl) -5-methylphenyl] methane,
α, α', α ", α'"-tetrakis (4-hydroxyphenyl) -p-xylene,
Bis [2-hydroxy-3- (4-hydroxy-2,3,5-trimethylbenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (2,5-dimethyl-3-hydroxybenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (2,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (2,5-dimethyl-5-hydroxybenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (2-hydroxy-3,4,6-trimethylbenzyl) -5-methylphenyl] methane,
Bis [2-hydroxy-3- (4-hydroxy-2,3,6-trimethylbenzyl) -5-methylphenyl] methane,
4,4', 4 ", 4'"-Tetrakis (4-hydroxyphenyl) bicyclohexyl,
Bis [4-hydroxy-3- (5-cyclohexyl-4-hydroxy-2-methylbenzyl) -5-methylphenyl] methane,
4,4', 4 ", 4'"-Tetrakis (4-hydroxy-3-methylphenyl) bicyclohexyl,
4,6-bis (3,5-dimethyl-4-hydroxyphenyl) -1,2-benzenediol,
4,4', 4 ", 4'"-Tetrakis (3,5-dimethyl-4-hydroxyphenyl) bicyclohexyl,
1,1-Bis [5-cyclohexyl-4-hydroxy-3- (2-hydroxy-5-methylbenzyl) phenyl] cyclohexane,
1,1-Bis [5-cyclohexyl-4-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) phenyl] cyclohexane,
1,1-bis [5-cyclohexyl-4-hydroxy-3- (5-cyclohexyl-4-hydroxy-2-methylbenzyl) phenyl] cyclohexane,
4,6-bis [1- (4-hydroxyphenyl) ethyl] -1,3-benzenediol,
2,2-Bis [4-hydroxy-3- (4-hydroxy-3-methylbenzyl) -5-methylphenyl] propane,
2,6-bis [(3,5-dimethyl-4-hydroxyphenyl) benzyl] -4- [α-methyl- (3,5-dimethyl-4-hydroxyphenyl) benzyl] phenol,
4,4', 4 ", 4'"-Tetrakis (3-isopropyl-4-hydroxy-phenyl) bicyclohexyl,
4,4'-bis [(3,4-dihydroxyphenyl) methylene] bis (2-isopropylphenol),
2,2'-Bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane,
2,4,6-Tris (4-hydroxybenzyl) -1,3-benzenediol,
4,6-bis (3,5-dimethyl-4-hydroxybenzyl) -1,2,3-benzenetriol,
3,3'-[(2-Hydroxyphenyl) methylene] bis (5-methyl-1,2-benzenediol),
2,6-bis (2,4-dihydroxybenzyl) -4-ethylphenol,
2,4-bis (2,4-dihydroxybenzyl) -6-cyclohexylphenol,
2,6-bis (5-tert-butyl-2,3-dihydroxybenzyl) -4-methylphenol,
2,4,6-Tris (3,5-dimethyl-4-hydroxybenzyl) -1,2-benzenediol,
2,4,6-Tris (3,5-dimethyl-2-hydroxybenzyl) -1,2-benzenediol,
2,6-bis (2,4-dihydroxybenzyl) -3,4-dimethylphenol,
2,6-bis [3- (2-hydroxy-5-methylbenzyl) -2,5-dimethyl-4-hydroxybenzyl] -3,4-dimethylphenol,
4,6-bis (α-methyl-4-hydroxybenzyl) -1,2,3-benzenetriol,
4,4'-[1- {4- [1- (3,5-bis (4-hydroxybenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2,6-bis (2,6-bis) 4-Hydroxybenzyl) Phenol],
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-3-methylbenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-bis (4-hydroxy-3-methylbenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [ 2,6-bis (3,5-dimethyl-4-hydroxybenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-2,3,6-trimethylbenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] Bis [2,6-bis (4-hydroxy-2,3,6-trimethylbenzyl) phenol],
Bis [5- (2,4-dihydroxybenzyl) -4-hydroxy-3-methylphenyl] methane,
Bis [3- (2,4-dihydroxybenzyl) -2,5-dimethyl-4-hydroxyphenyl] methane,
Bis [3- (2,4-dihydroxy-3-methylbenzyl) -2,5-dimethyl-4-hydroxyphenyl] methane,
Bis [5- (4-hydroxybenzyl) -2,3,4-trihydroxyphenyl] methane,
1,1-bis [5- (4-hydroxybenzoyl) -2,3,4-trihydroxyphenyl] ethane,
3,3', 5,5'-Tetrakis (4-hydroxybenzyl) -4,4'-dihydroxybiphenyl,
3,3', 5,5'-Tetrakis (4-hydroxy-3-methylbenzyl) -4,4'-dihydroxybiphenyl,
3,3', 5,5'-Tetrakis (2-hydroxy-5-methylbenzyl) -4,4'-dihydroxybiphenyl,
3,3', 5,5'-Tetrakis (3,5-dimethyl-4-hydroxybenzyl) -4,4'-dihydroxybiphenyl,
Bis [3- (α, α-bis (4-hydroxy-3-methylphenyl) methyl-4-hydroxyphenyl] methane,
Bis [3,5-bis (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane,
4,4', 4 "-ethylidinetris {[2- (2-hydroxy-5-methyl) benzyl] -6-methylphenol},
2,2-Bis [3,5-Bis (2-Hydroxy-5-Methylphenylmethyl) Phenyl] Propane,
Bis [3- (α, α-bis (2,5-dimethyl-4-hydroxyphenyl) methyl-4-hydroxyphenyl] methane,
Bis [5- (3,5-dimethyl-4-hydroxybenzyl) -2,3,4-trihydroxyphenyl] methane,
Bis [3- (2,3,4-trihydroxybenzyl) -2,5-dimethyl-4-hydroxyphenyl] methane,
1,1-bis [3- (2,3,4-trihydroxybenzyl) -5-cyclohexyl-4-hydroxyphenyl] cyclohexane,
1,8,15,22-Tetranonyl-3,5,10,12,17,19,24,26-Octahydroxy [1,1,1,1] -metacyclophane,
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-2-methylbenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-bis (4-hydroxy-2-methylbenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-bis (2-hydroxy-5-methylbenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3-ethyl-4-hydroxybenzyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-Bis (3-ethyl-4-hydroxybenzyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3,5-dimethyl-2-hydroxyphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [ 2,6-bis (3,5-dimethyl-2-hydroxyphenyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-3-isopropylphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-bis (4-hydroxy-3-isopropylphenyl) phenol],
Bis [3- (α, α-bis (3,5-dimethyl-4-hydroxyphenyl) methyl-4-hydroxyphenyl] methane,
Bis [3- (α, α-bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) methyl-4-hydroxyphenyl] methane,
4,4'-[4-Hydroxy-3,5-bis (2-hydroxybenzyl) methylene] bis [2,6-bis (2-hydroxybenzyl)] phenol,
4,4'-[4-Hydroxy-3,5-bis (4-hydroxybenzyl) methylene] bis [2,6-bis (4-hydroxybenzyl)] phenol,
4,4', 4 "-ethylidinetris [2,6-bis (2-hydroxybenzyl) phenol],
4,4', 4 "-ethylidinetris [2,6-bis (4-hydroxybenzyl) phenol],
2,2-bis [3,5-bis (4-hydroxy-3-methylbenzyl) -4-hydroxyphenyl] propane,
1,8,15,22-Tetraethyl-3,5,10,12,17,19,24,26-Octahydroxy [1,1,1,1] -metacyclophane,
α, α', α ", α'"-tetrakis (3,5-dimethyl-4-hydroxyphenyl) -1,4-dimethylbenzene,
4,4'-[1- {4- [1- (3,5-bis (2-hydroxy-5-isopropylphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [2 6-bis (2-hydroxy-5-isopropylphenyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (4-hydroxy-2,3,5-trimethylphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene] Bis [2,6-bis (4-hydroxy-2,3,5-trimethylphenyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3-sec-butyl-4-hydroxyphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [ 2,6-bis (3-sec-butyl-4-hydroxyphenyl) phenol],
4,4'-[1- {4- [1- (3,5-bis (3-tert-butyl-4-hydroxyphenyl) -4-hydroxyphenyl) -1-methylethyl] phenyl} etylidene] bis [ 2,6-bis (3-tert-butyl-4-hydroxyphenyl) phenol],
2,6-bis {[3- (2,4-dihydroxybenzyl) -2,5-dimethyl-4-hydroxy] benzyl} -4-methylphenol,
1,1-Bis [5- (2,4-dihydroxybenzyl) -3-cyclohexyl-4-hydroxyphenyl] cyclohexane,
1,1-Bis [5- (2,3,4-trihydroxybenzyl) -3-cyclohexyl-4-hydroxyphenyl] cyclohexane,
2,2-Bis [4,4', 4 ", 4'"-Tetrakis (3,5-dihydroxymethyl-4-hydroxyphenyl) cyclohexyl] Propane and the like can be exemplified.

Examples of the carboxylic acid and its derivative include, for example.
3,5-di (α-methylbenzyl) salicylic acid,
4- (2-p-Methoxyphenyloxyethoxy) salicylic acid,
4-Hydroxyphenylbenzoic acid,
4-Chlorobenzoic acid,
4- [2- (p-Methoxyphenoxy) ethyloxy] salicylic acid,
4- [3- (p-tolylsulfonyl) propyloxy] salicylic acid,
5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid,
4-octyloxycarbonylaminosalicylic acid,
3,5-Distyrene salicylic acid,
N- (p-Toluenesulfonyl) -glycine,
N- (p-Toluenesulfonyl) -alanine,
N- (p-toluenesulfonyl) -β-alanine,
N-Phenylaminocarbonyl-glycine,
N-Phenylaminocarbonyl-valine,
N- (m-trilaminocarbonyl) -phenylalanine,
N- (m-tolylaminocarbonyl) -cysteine-S-benzyl,
N- (m-tolylaminocarbonyl) -methionine,
N- (m-trilaminocarbonyl) -tyrosine,
N- (p-tolylaminocarbonyl) -phenylalanine,
N- (p-tolylaminocarbonyl) -cysteine-S-benzyl,
N- (p-tolylaminocarbonyl) -methionine,
N- (Phenylaminocarbonyl) -Methionine,
N- (p-tolylaminocarbonyl) -tyrosine,
2-O- (Phenylaminocarbonyl) -Mandelic acid,
2-O- (p-tolylaminocarbonyl) -mandelic acid,
2-O- (m-trilaminocarbonyl) -mandelic acid,
2-O- (o-tolylaminocarbonyl) -mandelic acid,
2-O- (1-naphthylaminocarbonyl) -mandelic acid,
2-O- (3-isopropenyl-α, α-dimethylbenzylaminocarbonyl) -mandelic acid,
2-O- (benzylaminocarbonyl) -mandelic acid,
2-O- (Phenethylaminocarbonyl) -Mandelic Acid,
2-O- (Phenylaminocarbonyl) -Lactic Acid,
2-O- (p-tolylaminocarbonyl) -lactic acid,
2-O- (m-tolylaminocarbonyl) -lactic acid,
2-O- (o-tolylaminocarbonyl) -lactic acid,
2-O- (1-naphthylaminocarbonyl) -lactic acid,
2-O- (3-isopropenyl-α, α-dimethylbenzylaminocarbonyl) -lactic acid,
2-O- (benzylaminocarbonyl) -lactic acid,
2-O- (phenethylaminocarbonyl) -lactic acid and the like can be exemplified.

Examples of the acidic phosphate ester compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, and tetrakoshi. Examples thereof include luacid phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate, and bis (2-ethylhexyl) phosphate.

As the component (b), a compound having a phenolic hydroxyl group is preferable because it can more effectively exhibit thermal discoloration characteristics, but an aromatic carboxylic acid, an aliphatic carboxylic acid having 2 to 5 carbon atoms, and a carboxylic acid metal salt are preferable. , Acidic phosphate ester and a metal salt thereof, and a compound selected from 1,2,3-triazole and its derivatives.

The component (c) of the reaction medium that reversibly causes the electron transfer reaction between the component (a) and the component (b) in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
When a microcapsule pigment containing a reversible thermochromic composition is used as the colorant applied to the present invention, the low molecular weight component (c) evaporates to the outside of the capsule when subjected to high heat treatment, so that the capsule is stably capsuled. A compound having 10 or more carbon atoms is preferably used for retaining the inside.

As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective. For example, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, etc. Examples thereof include heptadecyl alcohol, octadecyl alcohol, eikosyl alcohol, and docosyl alcohol.

As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monovalent carboxylic acid having an aliphatic and an alicyclic or aromatic ring and a monovalent alcohol having an aliphatic and an alicyclic or aromatic ring is effective. Esters, aliphatic and alicyclic esters obtained from any combination of a polyvalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monovalent alcohol having an alicyclic or alicyclic or aromatic ring. Alternatively, esters obtained from any combination of a monovalent carboxylic acid having an aromatic ring and an aliphatic and a polyvalent alcohol having an alicyclic or aromatic ring can be mentioned, for example, ethyl caprylate, octyl caprylate, stearyl caprylate. , Myristyl caprate, docosyl caprice, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n stearate -Butyl, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate , Behenyl behenate, cetyl benzoate, 4-tert-butyl stearyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, disetyl oxalate, disetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate , Dilauryl Azelaite, Di- (n-Nonyl) Sevacinate, Dineopentyl 1,18-octadecylmethylene dicarboxylate, Ethyleneglycol dimyristate, Propropylene glycol dilaurate, Propropylene glycol distearate, Hexylene glycol dipalmitate, 1, 5-Pentanediol distearate, 1,2,6-hexanetrioltrimylstate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprine, xylene glycol distea Examples of rates and the like can be given.

Further, an ester of a saturated fatty acid and a branched fatty alcohol, an ester of an unsaturated fatty acid or a saturated fatty acid having a branch or a substituent and an aliphatic alcohol having a branched or 16 or more carbon atoms, cetyl butyrate, Ester compounds selected from stearyl butyrate and behenyl butyrate are also effective.
Examples of the ester compound include 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl capric acid, 3,5,5-trimethylhexyl laurate, and 3,5,5 palmitic acid. -Trimethylhexyl, stearic acid 3,5,5-trimethylhexyl, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprice, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1 behenic acid -Ethylpropyl, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprice, 2-methylpentyl laurate, 2-Methylbutyl stearate, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate , 1-ethylpentyl caproate, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methyl caprice Pentyl, 2-methylhexyl palmitate, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, 3,7-Dimethyloctyl stearate, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, iso-ercaate Stearyl, cetyl isostearate, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, butyric acid Examples thereof include stearyl and behenyl butyrate.

Further, in order to change the color by showing a large hysteresis characteristic with respect to the color density-temperature curve and to give color memory depending on the temperature change, it is described in Japanese Patent Publication No. 4-17154 and has a temperature of 5 ° C or higher and lower than 50 ° C. A carboxylic acid ester compound exhibiting a ΔT value (melting point-cloud point), for example, a carboxylic acid ester containing a substituted aromatic ring in the molecule, a carboxylic acid containing an unsubstituted aromatic ring, and an aliphatic alcohol having 10 or more carbon atoms. Esters, carboxylic acid esters containing cyclohexyl groups in molecules, esters of fatty acids with 6 or more carbon atoms and unsubstituted aromatic alcohols or phenols, esters of fatty acids with 8 or more carbon atoms and branched aliphatic alcohols, dicarboxylic acids and aromatics Esters with group alcohols or branched aliphatic alcohols, dibenzyl silicate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, disetyl adipate, distearyl adipate, trilaurin, trimyristin, tristea, di Examples thereof include myristin and distea.

Further, an odd aliphatic monohydric alcohol having 9 or more carbon atoms, a fatty acid ester compound obtained from an aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol, and an even number of 10 to 16 carbon atoms. A fatty acid ester compound having a total carbon number of 17 to 23 obtained from an aliphatic carboxylic acid is also effective.
Examples of the fatty acid ester compound include n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, and capryl. Acid n-undecyl, capricate n-tridecyl, caprylate n-pentadecyl, capricate n-heptyl, capricate n-nonyl, capricate n-undecyl, capricate n-tridecyl, capricate n-pentadecyl, laurate n -Pentyl, n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate , N-undecyl myristate, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, palmitin N-pentadecyl acid, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eikosanate, n-undersi eikosanate, n-tridecyl eikosanate, n eikosanate -Pentadecyl, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like can be exemplified.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, for example, 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone. , 2-Dodecanone, 3-Dodecanone, 4-Dodecanone, 5-Dodecanone, 2-Tridecanone, 3-Tridecanone, 2-Tetradecanone, 2-Pentadecanone, 8-Pentadecanone, 2-Hexadecanone, 3-Hexadecanone, 9-Heptadecanone, 2 Examples thereof include pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, lauron, and stearone.
Furthermore, arylalkylketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradeca. Nophenone, 4-n-dodecanoacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurofenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone , N-Heptaphenone, 4-n-pentylacetophenone, cyclohexylphenylketone, benzyl-n-butylketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonafton, cyclopentylphenyl Examples include ketones.

As the ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and for example, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, and didodecyl ether. , Ditridecyl ether, Ditetradecyl ether, Dipentadecyl ether, Dihexadecyl ether, Dioctadecyl ether, Decanediol dimethyl ether, Undecanediol dimethyl ether, Dodecanediol dimethyl ether, Tridecanediol dimethyl ether, Decanediol diethyl ether, Undecanediol diethyl ether Etc. can be exemplified.

Examples of acid amides include acetamide, propionic acid amide, butyric acid amide, caproic acid amide, capric acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide and olein. Acid amides, erucic acid amides, benzamides, caproic acid anilides, capric acid anilides, capric acid anilides, lauric acid anilides, myristic acid anilides, palmitate anilides, stearate anilides, behenic acid anilides, oleic acid anilides, erucate anilides, caprones. Acid N-methylamide, capric acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearate N-methylamide, behenic acid N-methylamide, oleic acid N -Methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearate N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristic acid N-butylamide , Palmitic acid N-butylamide, stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, steaic acid N-octylamide, oleic acid N -Octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearate N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitin Acid amides, distearate amides, dioleic acid amides, trilauric acid amides, trimylistic acid amides, tripalmitic acid amides, tristearic acid amides, trioleic acid amides, succinic acid amides, adipic acid amides, glutarate amides, malonic acid amides. , Azelaic acid amide, maleic acid amide, succinic acid N-methylamide, adipic acid N-methylamide, glutaric acid N-methylamide, malonic acid N-methylamide, azelaic acid N-methylamide, succinic acid N-ethylamide, adipic acid N-ethylamide , Glutal acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipii Examples thereof include acid N-butyramide, glutaric acid N-butyramide, malonic acid N-butylamide, adipic acid N-octylamide, and adipic acid N-dodecylamide.

〔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及び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はそれぞれ独立して、水素原子、炭素数１～４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、ｒ及びｐはそれぞれ独立して、１～３の整数を示す。〕
式（６）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ましく、さらにＲ_１が水素原子であり、且つ、ｍが０の場合がより好ましい。
なお、式（６）で示される化合物のうち、より好ましくは下記式（７）で示される化合物である。

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、好ましくは炭素数１０～２４のアルキル基であり、より好ましくは炭素数１２～２２のアルキル基である。）
式（７）で示される化合物としては、例えば、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、テトラデカン酸４－ベンジルオキシフェニルエチル、ペンタデカン酸４－ベンジルオキシフェニルエチル、ヘキサデカン酸４－ベンジルオキシフェニルエチル、ヘプタデカン酸４－ベンジルオキシフェニルエチル、オクタデカン酸４－ベンジルオキシフェニルエチル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (6).

[In the formula, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and either X ₁ or X ₂ is-(CH ₂ ) _n OCOR ₂ or-(CH ₂ ) _n . COOR ₂ , the other indicates a hydrogen atom, n indicates an integer of 0 to 2, R ₂ indicates an alkyl group or an alkenyl group having 4 or more carbon atoms, and Y ₁ and Y ₂ are independent hydrogen atoms, respectively. It indicates any of an alkyl group, a methoxy group, and a halogen atom having 1 to 4 carbon atoms, and r and p each independently indicate an integer of 1 to 3. ]
Among the compounds represented by the formula (6), 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 The case of 0 is more preferable.
Of the compounds represented by the formula (6), the compound represented by the following formula (7) is more preferable.

(In the formula, R represents an alkyl group or an alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.)
Examples of the compound represented by the formula (7) include 4-benzyloxyphenylethyl octanate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, and dodecane. 4-benzyloxyphenylethyl acid, 4-benzyloxyphenylethyl tridecanoate, 4-benzyloxyphenylethyl tetradecanoate, 4-benzyloxyphenylethyl pentadecanoate, 4-benzyloxyphenylethyl hexadecanoate, 4-benzyloxy heptadecanoate Examples thereof include phenylethyl and 4-benzyloxyphenylethyl octadecanoate.

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ独立して、１～３の整数を示し、Ｘ及びＹはそれぞれ独立して、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、ハロゲン原子のいずれかを示す。）
式（８）で示される化合物としては、例えば、オクタン酸１，１－ジフェニルメチル、ノナン酸１，１－ジフェニルメチル、デカン酸１，１－ジフェニルメチル、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－ジフェニルメチル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (8).

(In the formula, R represents an alkyl group or an alkoxy group having 8 or more carbon atoms, m and n independently represent integers of 1 to 3, and X and Y independently represent hydrogen atoms and carbon atoms. It indicates any of an alkyl group of 1 to 4, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.)
Examples of the compound represented by the formula (8) include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecane, and dodecane. Acid 1,1-diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecanoic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid 1,1- Examples thereof include diphenylmethyl and 1,1-diphenylmethyl octadecanoic acid.

（式中、Ｘは水素原子、炭素数１～４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１～３の整数を示し、ｎは１～２０の整数を示す。）
式（９）で示される化合物としては、例えば、マロン酸と２－〔４－(４－クロロベンジルオキシ）フェニル〕エタノールとのジエステル、こはく酸と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、こはく酸と２－〔４－(３－メチルベンジルオキシ）フェニル〕エタノールとのジエステル、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、グルタル酸と２－〔４－(４－クロロベンジルオキシ）フェニル〕エタノールとのジエステル、アジピン酸と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、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、スベリン酸と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、スベリン酸と２－〔４－(３－メチルベンジルオキシ）フェニル〕エタノールとのジエステル、スベリン酸と２－〔４－(４－クロロベンジルオキシ）フェニル〕エタノールとのジエステル、スベリン酸と２－〔４－(２，４－ジクロロベンジルオキシ）フェニル〕エタノールとのジエステル、アゼライン酸と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、セバシン酸と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、１，１０－デカンジカルボン酸と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、１，１８-オクタデカンジカルボン酸と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、１，１８－オクタデカンジカルボン酸と２－〔４－(２－メチルベンジルオキシ）フェニル〕エタノールとのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (9).

(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 20.)
Examples of the compound represented by the formula (9) include a diester of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl] ethanol, and a diester of oxalic acid and 2- (4-benzyloxyphenyl) ethanol. Diester, diester of succinic acid and 2- [4- (3-methylbenzyloxy) phenyl] ethanol, diester of glutaric acid and 2- (4-benzyloxyphenyl) ethanol, diester of glutaric acid and 2- [4-( 4-Chlorobenzyloxy) phenyl] Diester with ethanol, diester with adipic acid and 2- (4-benzyloxyphenyl) ethanol, diester with pimelic acid and 2- (4-benzyloxyphenyl) ethanol, with suberic acid Diester with 2- (4-benzyloxyphenyl) ethanol, diester with suberic acid and 2- [4- (3-methylbenzyloxy) phenyl] ethanol, diester with suberic acid and 2- [4- (4-chlorobenzyloxy) oxy ) Phenyl] Diester with ethanol, Diester with suberic acid and 2- [4- (2,4-dichlorobenzyloxy) phenyl] ethanol, Diester with azelaic acid and 2- (4-benzyloxyphenyl) ethanol, Sebasin Diester of acid and 2- (4-benzyloxyphenyl) ethanol, diester of 1,10-decandicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, 1,18-octadecanedicarboxylic acid and 2- (4) Examples thereof include a diester with -benzyloxyphenyl) ethanol, a diester with 1,18-octadecanedicarboxylic acid and 2- [4- (2-methylbenzyloxy) phenyl] ethanol, and the like.

（式中、Ｒは炭素数１～２１のアルキル基又はアルケニル基を示し、ｎは１～３の整数を示す。）
式（１０）で示される化合物としては、例えば、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、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル、１，４－ビス（ヒドロキシメトキシ）ベンゼンと酪酸とのジエステル、１，４－ビス（ヒドロキシメトキシ）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）ベンゼンと酢酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとプロピオ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）ベンゼンとカプリル酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (10).

(In the formula, R represents an alkyl group or an alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound represented by the formula (10) include a diester of 1,3-bis (2-hydroxyethoxy) benzene and capric acid, and a diester of 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid. , 1,3-Bis (2-hydroxyethoxy) benzene and lauric acid diester, 1,3-bis (2-hydroxyethoxy) benzene and myristic acid diester, 1,4-bis (hydroxymethoxy) benzene Diester with butyric acid, diester with 1,4-bis (hydroxymethoxy) benzene and isovaleric acid, diester with 1,4-bis (2-hydroxyethoxy) benzene and acetic acid, 1,4-bis (2-hydroxy) Diester of ethoxy) benzene and propionic acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and valerate, diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, 1, Diester of 4-bis (2-hydroxyethoxy) benzene and capric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and capric acid, 1,4-bis (2-hydroxyethoxy) benzene and laurin Examples thereof include a diester with an acid, a diester with 1,4-bis (2-hydroxyethoxy) benzene and myristic acid, and the like.

（式中、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ハロゲン原子のいずれかを示し、ｍは１～３の整数を示し、ｎは１～２０の整数を示す。）
式（１１）で示される化合物としては、例えば、こはく酸と２－フェノキシエタノールとのジエステル、スベリン酸と２－フェノキシエタノールとのジエステル、セバシン酸と２－フェノキシエタノールとのジエステル、１，１０－デカンジカルボン酸と２－フェノキシエタノールとのジエステル、１，１８－オクタデカンジカルボン酸と２－フェノキシエタノールとのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (11).

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, m represents an integer of 1 to 3, and n represents 1 to 20. Indicates an integer of.)
Examples of the compound represented by the formula (11) include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, and 1,10-decandycarboxylic acid. And 2-phenoxyethanol diester, 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol diester and the like can be exemplified.

（式中、Ｒは炭素数４～２２のアルキル基、シクロアルキルアルキル基、シクロアルキル基、炭素数４～２２のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
式（１２）で示される化合物としては、例えば、４－フェニル安息香酸デシル、４－フェニル安息香酸ラウリル、４－フェニル安息香酸ミリスチル、４－フェニル安息香酸シクロヘキシルエチル、４－ビフェニル酢酸オクチル、４－ビフェニル酢酸ノニル、４－ビフェニル酢酸デシル、４－ビフェニル酢酸ラウリル、４－ビフェニル酢酸ミリスチル、４－ビフェニル酢酸トリデシル、４－ビフェニル酢酸ペンタデシル、４－ビフェニル酢酸セチル、４－ビフェニル酢酸シクロペンチル、４－ビフェニル酢酸シクロヘキシルメチル、４－ビフェニル酢酸ヘキシル、４－ビフェニル酢酸シクロヘキシルメチル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (12).

(In the formula, R indicates any of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkoxy group having 4 to 22 carbon atoms, and X is a hydrogen atom and an alkyl having 1 to 4 carbon atoms. A group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, where n indicates 0 or 1).
Examples of the compound represented by the formula (12) include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, 4-. Nonyl biphenylacetate, decyl 4-biphenylacetate, lauryl 4-biphenylacetate, myristyl 4-biphenylacetate, tridecyl 4-biphenylacetate, pentadecyl 4-biphenylacetate, cetyl 4-biphenylacetate, cyclopentyl 4-biphenylacetate, 4-biphenylacetate Examples thereof include cyclohexylmethyl, hexyl 4-biphenylacetate, cyclohexylmethyl 4-biphenylacetate, and the like.

（式中、Ｒは炭素数３～１８のアルキル基又は炭素数３～１８の脂肪族アシル基を示し、Ｘは水素原子、炭素数１～３のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子又はメチル基を示し、Ｚは水素原子、炭素数１～４のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示す。）
式（１３）で示される化合物としては、例えば、４－ブトキシ安息香酸フェノキシエチル、４－ペンチルオキシ安息香酸フェノキシエチル、４－テトラデシルオキシ安息香酸フェノキシエチル、４－ヒドロキシ安息香酸フェノキシエチルとドデカン酸とのエステル、バニリン酸フェノキシエチルのドデシルエーテル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (13).

(In the formula, R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, and X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms. , Y is a hydrogen atom or a methyl group, Z is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom. )
Examples of the compound represented by the formula (13) include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, phenoxyethyl 4-hydroxybenzoate and dodecanoic acid. Examples thereof include an ester with and a dodecyl ether of phenoxyethyl vanillate.

（式中、Ｒは炭素数４～２２のアルキル基、炭素数４～２２のアルケニル基、シクロアルキルアルキル基、シクロアルキル基のいずれかを示し、Ｘは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。）
式（１４）で示される化合物としては、例えば、４－ヒドロキシ安息香酸オクチルの安息香酸エステル、４－ヒドロキシ安息香酸デシルの安息香酸エステル、４－ヒドロキシ安息香酸ヘプチルの４－メトキシ安息香酸エステル、４－ヒドロキシ安息香酸ドデシルの２－メトキシ安息香酸エステル、４－ヒドロキシ安息香酸シクロヘキシルメチルの安息香酸エステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (14).

(In the formula, R indicates any of an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, and a cycloalkyl group, and X is a hydrogen atom, an alkyl group, an alkoxy group, and a halogen. Any of the atoms, Y indicates any of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, and n indicates 0 or 1).
Examples of the compound represented by the formula (14) include an benzoic acid ester of octyl 4-hydroxybenzoate, a benzoic acid ester of decyl 4-hydroxybenzoate, and a 4-methoxybenzoic acid ester of heptyl 4-hydroxybenzoate, 4 Examples thereof include 2-methoxybenzoic acid ester of dodecyl hydroxybenzoate and benzoic acid ester of cyclohexylmethyl 4-hydroxybenzoate.

（式中、Ｒは炭素数３～１８のアルキル基、炭素数６～１１のシクロアルキルアルキル基、炭素数５～７のシクロアルキル基、炭素数３～１８のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～３のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、炭素数１～４のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示す。）
式（１５）で示される化合物としては、例えば、４－ヒドロキシ安息香酸ノニルのフェノキシエチルエーテル、４－ヒドロキシ安息香酸デシルのフェノキシエチルエーテル、４－ヒドロキシ安息香酸ウンデシルのフェノキシエチルエーテル、バニリン酸ドデシルのフェノキシエチルエーテル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (15).

(In the formula, R indicates any of an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkoxy group having 3 to 18 carbon atoms. X indicates any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom, and Y indicates a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, and an ethoxy group. , Indicates one of the halogen atoms.)
Examples of the compound represented by the formula (15) include phenoxyethyl ether of nonyl 4-hydroxybenzoate, phenoxyethyl ether of decyl 4-hydroxybenzoate, phenoxyethyl ether of undecyl 4-hydroxybenzoate, and dodecyl vanillate. Examples thereof include phenoxyethyl ether and the like.

（式中、Ｒは炭素数３～８のシクロアルキル基又は炭素数４～９のシクロアルキルアルキル基を示し、ｎは１～３の整数を示す。）
式（１６）で示される化合物としては、例えば、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンカルボン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (16).

(In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound represented by the formula (16) include a diester of 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanecarboxylic acid, and 1,4-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid. Diester, 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid diester and the like can be exemplified.

（式中、Ｒは炭素数３～１７のアルキル基、炭素数３～８のシクロアルキル基、炭素数５～８のシクロアルキルアルキル基のいずれかを示し、Ｘは水素原子、炭素数１～５のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示し、ｎは１～３の整数を示す。）
式（１７）で示される化合物としては、例えば、４－フェニルフェノールエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４－フェニルフェノールジエチレングリコールエーテルとラウリン酸とのジエステル、４－フェニルフェノールトリエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとオクタン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとノナン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとデカン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとミリスチン酸とのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (17).

(In the formula, R represents any of an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkylalkyl group having 5 to 8 carbon atoms, and X is a hydrogen atom and 1 to 1 carbon atoms. An alkyl group, a methoxy group, an ethoxy group, or a halogen atom of 5 is indicated, and n is an integer of 1 to 3).
Examples of the compound represented by the formula (17) include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenol diethylene glycol ether and lauric acid, and 4-phenylphenol triethylene glycol ether. Diester with cyclohexanecarboxylic acid, diester with 4-phenylphenolethylene glycol ether and octanoic acid, diester with 4-phenylphenolethylene glycol ether and nonanoic acid, diester with 4-phenylphenolethylene glycol ether and decanoic acid, 4 -A diester of phenylphenol ethylene glycol ether and myristic acid can be exemplified.

Further, a reversible thermal discoloration of a heat-coloring type (coloring by heating and decoloring by cooling) using a gallic acid ester (Japanese Patent Laid-Open No. 51-44706, JP-A-2003-253149) as an electron-accepting compound. Sex composition can also be applied (see FIG. 3).

The reversible thermochromic composition is a companion containing the above components (a), (b), and (c) as essential components, and the ratio of each component is the concentration, discoloration temperature, and discoloration morphology. Although it depends on the type of each component, the component ratio at which the desired characteristics are generally obtained is (a) component 1, (b) component 0.1 to 100, preferably 0.1 to 50. , More preferably 0.5 to 20, (c) component 5 to 200, preferably 5 to 100, and more preferably 10 to 100 (all of the above ratios are parts by mass).

As the photochromic material, a conventionally known spiroxazine derivative or spiropyran derivative that develops color when irradiated with sunlight, ultraviolet light, or blue light having a peak emission wavelength in the range of 400 to 495 nm and disappears when the irradiation is stopped. , And photochromic compounds such as naphthopyran derivatives.
Examples of the spiroxazine derivative include conventionally known indolinospirobenzoxazine-based compounds, indolinospironaftoxazine-based compounds, indolinospirofenantrooxazine-based compounds, and indolinospirinolinonoxazine-based compounds.
Further, conventionally known flugide derivatives, diarylethene derivatives and the like can be exemplified as photochromic compounds having photomemory properties (color memory properties and photochromic properties).

Further, as the photochromic material, a reversible photochromic composition in which the above-mentioned photochromic compound is dissolved in various oligomers can also be used.
Examples of the oligomer include styrene-based oligomers, acrylic-based oligomers, terpene-based oligomers, and terpene-based oligomers.
Examples of the styrene-based oligomer include low molecular weight polystyrene, styrene-α-methylstyrene copolymer, α-methylstyrene polymer, and a copolymer of α-methylstyrene and vinyltoluene.
Examples of the acrylic oligomer include an acrylic acid ester copolymer and the like.
Examples of the terpene-based oligomer include α-pinene polymer, β-pinene polymer, d-limonene polymer and the like.
Examples of the terpene phenol-based oligomer include α-pinene-phenol copolymer and the like.
By dissolving the photochromic compound in various oligomers, it is possible to improve the light resistance of the photochromic compound, improve the color development density, and adjust the discoloration sensitivity.

As the styrene-based oligomer, those having a mass average molecular weight of 200 to 6000, preferably 200 to 4000 are used. When the mass average molecular weight of the styrene-based oligomer exceeds 6000, color residue is likely to occur due to light irradiation, the color development density is likely to be low, and it is easy to adjust the color change sensitivity. On the other hand, when the mass average molecular weight is less than 200, the amount of the contained monomers increases and the stability is lacking, so that the light resistance is likely to be impaired.
As the acrylic oligomer, those having a mass average molecular weight of 12000 or less, preferably 1000 to 8000, and more preferably 1500 to 6000 are used. If the mass average molecular weight of the acrylic oligomer exceeds 12000, it tends to be difficult to adjust the discoloration sensitivity. On the other hand, when the mass average molecular weight is less than 1000, the amount of the contained monomers increases and the stability is lacking, so that the color density tends to be low and the light resistance tends to be impaired.
As the terpene-based oligomer, one having a mass average molecular weight of 250 to 4000, preferably 300 to 4000 is used. When the mass average molecular weight of the terpene-based oligomer exceeds 4000, color residue is likely to occur due to light irradiation, the color development density is likely to be low, and it is easy to adjust the color change sensitivity. On the other hand, when the mass average molecular weight is less than 250, the amount of the contained monomers increases and the stability is lacking, so that the light resistance is likely to be impaired.
As the terpene phenol-based oligomer, one having a mass average molecular weight of 200 to 2000, preferably 500 to 1200 is used. When the mass average molecular weight of the terpene phenol-based oligomer exceeds 2000, it tends to be difficult to adjust the discoloration sensitivity. On the other hand, when the mass average molecular weight is less than 200, the amount of the contained monomers increases and the stability is lacking, so that the color density tends to be low.
The mass average molecular weight of the above oligomer is a value measured by the GPC method (gel permeation chromatograph method).
In addition, the above-mentioned oligomers may be used alone or in admixture of two or more.

The mass ratio of the photochromic compound: styrene-based oligomer or the photochromic compound: acrylic-based oligomer is preferably 1: 1 to 1: 10000, and more preferably 1: 5 to 1: 500.
The mass ratio of the photochromic compound: the terpene-based oligomer is preferably 1: 1 to 1: 5000, more preferably 1: 5 to 1: 500.
The mass ratio of the photochromic compound: the terpene phenol-based oligomer is preferably 1: 1 to 1:50, more preferably 1: 2 to 1:30.
When the mass ratio of the photochromic compound and the oligomer is within the above range, the photochromic compound sufficiently exhibits the color-developing function and easily exhibits a sufficient color-developing density.

Microcapsule pigments are microencapsulated by conventionally known isocyanate-based interfacial polymerization methods, melamine-formalin-based in-situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, and phase separation methods from organic solvents. , Melting dispersion cooling method, air suspension coating method, spray drying method, etc., which are appropriately selected according to the intended use. Examples of the material of the capsule include epoxy resin, urea resin, urethane resin, isocyanate resin and the like.
Further, the surface of the microcapsules can be further provided with a secondary resin film depending on the purpose to impart durability, or the surface characteristics can be modified for practical use.

Further, as the colorant applied to the present invention, resin particles containing a pigment, a dye, or a functional material such as a thermochromic material or a photochromic material can be used.
Examples of the resin particles containing the pigment include resin particles in which the pigment is uniformly dispersed in the resin particles, resin particles in which the surface of the resin particles is coated with the pigment, and the like.
The pigment is not particularly limited as long as it can be dispersed or adsorbed on the resin constituting the resin particles, and the above-mentioned inorganic pigment, organic pigment, brilliant pigment, fluorescent pigment, phosphorescent pigment and the like can be used. The pigment may be surface-treated by various conventionally known methods for the purpose of improving the dispersibility or adsorptivity of the resin constituting the resin particles.
Examples of the resin constituting the resin particles include polystyrene, acrylic resin, epoxy resin, melamine resin, polyester, polyvinyl chloride, polybutadiene, benzoguanamine resin, polyamide, urethane resin, polymethyl methacrylate, and acrylic-urethane copolymer resin. Phenolic resin, polyethylene, polypropylene, polyacrylonitrile, polyacetal, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, styrene-butadiene copolymer resin, styrene-acrylonitrile copolymer resin, and acrylonitrile -The butadiene copolymer resin and the like can be exemplified.

Examples of the resin particles containing the dye include resin particles in which the dye is uniformly dissolved or dispersed in the resin particles, resin particles in which the dye is dyed on the resin particles, and the like.
The dye is not particularly limited as long as it can be dissolved, dispersed or dyed in the resin constituting the resin particles, and is not particularly limited as long as it is an acid dye, a basic dye, a direct dye, or the above-mentioned oil-soluble dye. Disperse dyes and the like can be used.

Examples of acid dyes include ponceau (CI 16255), tartrazine (CI 19140), acid blue black 10B (CI 20470), guinea green (CI 42085), and brilliant dyes. Blue FCF (CI 42090), Acid Violet 6B (CI 42640), Solble Blue (CI 42755), Naphthalene Green (CI 44025), Eosin (CI 45380) , Phloxine (CI 45410), erythrosine (CI 45430), ponceau (CI 50420), acid flavin (CI 56205) and the like.
Examples of basic dyes include chrysoydin (CI 11270), methyl violet FN (CI 42535), crystal violet (CI 42555), malachite green (CI 42000), and Victoria blue. Examples thereof include FB (CI 44045), Rhodamine B (CI 45170), acridine orange NS (CI 46005), methylene blue B (CI 52015) and the like.
Examples of the direct dye include Congo Red (CI 22120), Direct Sky Blue 5B (CI 24400), Violet BB (CI 27905), and Direct Deep Black EX (CI 30235). , Violet Black G Conc (CI 35225), Direct First Black G (CI 35255), Phthalocyanine Blue (CI 74180) and the like can be exemplified.

When the resin particles contain a dye, the resin constituting the resin particles is not particularly limited, and the same resin as the above-mentioned resin constituting the resin particles containing a pigment can be used. Of these resins, thermosetting resins are preferable. The thermosetting resin is suitable because it is superior in solvent resistance and heat resistance as compared with the thermoplastic resin, and also in the migration resistance of the contained dye, and can suppress the elution of the dye from the resin. Is.
Examples of the thermosetting resin include epoxy resin, epoxy acrylate resin, xylene resin, toluene resin, guanamine resin, benzoguanamine resin, melamine resin, urethane resin, phenol resin, alkyd resin, polyamide, polyimide, polyamide ester, urea resin, and the like. Examples thereof include silicone resin and unsaturated polyester. Among these resins, guanamine resin or melamine resin is preferable because the elution of dye can be further suppressed.

Examples of the resin particles containing the thermochromic material or the photochromic material include the resin particles in which the above-mentioned thermochromic material or the photochromic material is uniformly dispersed in the resin particles.

The resin constituting the resin particles is not particularly limited as long as it is a thermoplastic resin or a thermosetting resin, and for example, polystyrene, acrylic resin, polyester, polyvinyl chloride, polybutadiene, polymethyl methacrylate, acrylic-. Urethane copolymer resin, polyethylene, polypropylene, polyacrylonitrile, polyacetal, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, styrene-butadiene copolymer resin, styrene-acrylonitrile copolymer resin, And thermoplastic resins such as acrylonitrile-butadiene copolymer resin,
Epoxy resin, epoxy acrylate resin, xylene resin, toluene resin, guanamine resin, benzoguanamine resin, melamine resin, urethane resin, phenol resin, alkyd resin, polyamide, polyimide, polyamide ester, urea resin, silicone resin, unsaturated polyester, etc. The thermosetting resin can be exemplified respectively.

The resin particles described above can be produced by a pulverization method, a spray drying method, or a polymerization method in which the particles are polymerized in the presence of a pigment, a dye, a heat-discoloring material, or a photo-discoloring material in an aqueous or oil-based medium. Examples of the polymerization method include a suspension polymerization method, a suspension polycondensation method, a dispersion polymerization method, an emulsion polymerization method and the like.
The shape of the resin particles is not particularly limited, and spherical resin particles such as true spherical, elliptical spherical, and substantially spherical, polygonal, and flat resin particles can be used, but spherical resin particles are used. Is preferable.

The amount of the microcapsule pigment containing the pigment, the pigment or the dye, or the resin particles containing the pigment or the dye is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass in the total amount of the ink composition. It is blended in a range. When the blending ratio of the above pigment, microcapsule pigment, or resin particles exceeds 15% by mass, the viscosity of the ink composition tends to be high, the ink ejection property of the writing instrument containing the ink composition is lowered, and the writing performance is improved. It becomes easy to be hindered. On the other hand, if the blending ratio is less than 0.5% by mass, it becomes difficult to obtain a suitable handwriting concentration as a writing tool.
The microcapsule pigment containing the thermochromic material or the photochromic material, or the resin particles containing the thermochromic material or the photochromic material is preferably 5 to 40% by mass in the total amount of the ink composition. It is preferably blended in the range of 10 to 40% by mass, more preferably 15 to 35% by mass. When the blending ratio of the above-mentioned microcapsule pigment or resin particles exceeds 40% by mass, the viscosity of the ink composition tends to increase, the ink ejection property of the writing instrument containing the ink composition deteriorates, and the writing performance tends to be impaired. Become. On the other hand, if the blending ratio is less than 5% by mass, it is difficult to obtain suitable discoloration property and a suitable handwriting density as a writing tool, and it is difficult to sufficiently satisfy the discoloration function.

Further, as the colorant applied to the present invention, solid resin particles having no voids inside the particles, hollow resin particles having voids inside the particles, and the like can also be used.
The hollow resin particles have voids inside the particles, the voids are filled with air, and the outer shell of the particles is a crosslinked polymer layer. Light incident on the hollow resin particles is reflected at the interface between the polymer layer and the dispersion medium in which the hollow resin particles are dispersed and at the interface between the polymer layer and the voids, so that light is scattered as compared with the solid resin particles. Is likely to occur. Therefore, the hollow resin particles have a white color and can be used as a pigment having a hiding effect. Further, since it has a hollow structure having voids inside the resin, it has a characteristic that the specific gravity is smaller than that of a general pigment.
Examples of the resin constituting the polymer layer of the outer shell of the solid resin particles or the hollow resin particles include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, vinyl acetate, polystyrene, polymethyl methacrylate, and polyacrylonitrile. , Polyamide, Polycarbonate, Polyacetal, Polyethylene terephthalate, Polyurethane, Maleic acid resin, styrene-acrylonitrile copolymer resin, Acrylonitrile-butadiene-styrene copolymer, styrene-acrylic copolymer resin, styrene-butadiene copolymer, and modification thereof. The body and the like can be exemplified.

The solid resin particles or the hollow resin particles are blended in the total amount of the ink composition in the range of preferably 5 to 15% by mass, more preferably 5 to 10% by mass. When the blending ratio of the solid resin particles or the hollow resin particles exceeds 15% by mass, the viscosity of the ink composition tends to be high, the ink ejection property of the writing instrument containing the ink composition is lowered, and the writing performance is easily impaired. Become. On the other hand, if the blending ratio is less than 5% by mass, it becomes difficult to obtain a suitable handwriting concentration and concealing effect as a writing tool.

The above-mentioned reversible thermochromic composition or reversible photochromic composition is encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment or a reversible photochromic microcapsule pigment, or a thermoplastic resin or thermosetting. Reversible thermosetting resin particles or reversible photochromic resin particles can be formed by dispersing in the sex resin, and the above-mentioned reversible thermosetting composition or reversible photochromic composition is microcapsules. It is preferable to use it as a microcapsule pigment by encapsulating it in. By encapsulating it in microcapsules, it is possible to form a chemically and physically stable pigment, and further, under various conditions of use, the reversible thermodynamic composition or the reversible photochromic composition is the same. This is because the composition of the above can be maintained and the same action and effect can be obtained.

The reversible thermochromic microcapsule pigment or the reversible photochromic microcapsule pigment preferably has an inclusion: wall film mass ratio of 7: 1 to 1: 1, and the inclusion and wall film mass ratio is as described above. By being within the range, deterioration of color density and sharpness at the time of color development is prevented. More preferably, the mass ratio of inclusions: wall membrane is 6: 1 to 1: 1.
When the ratio of the inclusions to the wall film exceeds the above range, the thickness of the wall film of the microcapsule pigment becomes thin, and it is easily destroyed by heat or pressure. On the other hand, when the ratio of the wall film to the inclusions exceeds the above range, the color density and sharpness at the time of color development tend to decrease.

The average particle size of the colorant applied to the present invention is preferably 0.01 to 5 μm, more preferably 0.05 to 4 μm, still more preferably 0.1 to 3 μm, and 0. It is particularly preferably .5 to 3 μm. If the average particle size of the colorant exceeds 5 μm, it becomes difficult to obtain good ink ejection properties when used in a writing instrument. On the other hand, if the average particle size is less than 0.01 μm, it becomes difficult to exhibit high-concentration color development.
For the measurement of the average particle size, the particle area is determined by the image analysis type particle size distribution measurement software [Manufactured by Mountech Co., Ltd., product name: MacView], and the projected area circle equivalent diameter is determined from the area of the particle area. It is a value measured as the average particle diameter of particles corresponding to equal volume spheres by calculating (Heywood diameter).
If the particle size of all or most of the particles exceeds 0.2 μm, a particle size distribution measuring device [manufactured by Beckman Coulter Co., Ltd., product name: Multisizer 4e] is used by the Coulter method. It is also possible to measure as the average particle size of a considerable number of particles.
Furthermore, a laser diffraction / scattering type particle size distribution measuring device calibrated based on the numerical values measured using the above software or a measuring device by the Coulter method [manufactured by HORIBA, Ltd., product name: LA- 300], the particle size based on the volume and the average particle size may be measured.

The vehicle applied to the present invention is an aqueous vehicle containing water and, if necessary, an organic solvent.
The water is not particularly limited, and examples thereof include tap water, ion-exchanged water, ultra-filtered water, and distilled water.
Examples of the organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thioethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and the like. Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, etc. Can be exemplified.
Water, or water and the organic solvent, are blended in the total amount of the ink composition in the range of preferably 30 to 80% by mass, more preferably 40 to 70% by mass.

The vehicle applied to the present invention contains a cationic polymer selected from the above formulas (1) to (5). The above-mentioned cationic polymer is an amine-based polymer compound and is water-soluble. Here, the polymer (polymer compound) includes not only a polymer in which a plurality of one type of monomers (monomers) are polymerized, but also a copolymer in which a plurality of two or more types of monomers are polymerized.
The above-mentioned cationic polymer is adsorbed on the surface of the colorant in the ink composition to charge the colorant with a positive charge.

（式中、ｎは自然数を示す。）
また、式（１）において、ｎ１が１であるカチオン性高分子は下記式（１９）で示され、一級アミンのカチオンを有するアリルアミンの酸塩を繰り返し単位とする重合体である。

（式中、Ｘ_１は、塩酸、アミド硫酸、酢酸のいずれかを示し、ｎは自然数を示す。）
式（１）で示されるカチオン性高分子の質量平均分子量は５００～２００，０００の範囲にあり、ｎは、質量平均分子量が５００～２００，０００となるのに必要な重合度を示す。
式（１）で示されるカチオン性高分子として具体的には、ニットーボーメディカル（株）製、製品名：ＰＡＡ－０１，ＰＡＡ－０３、ＰＡＡ－０５、ＰＡＡ－０８、ＰＡＡ－１５、ＰＡＡ－１５Ｃ，ＰＡＡ－２５、ＰＡＡ－ＨＣｌ－０１、ＰＡＡ－ＨＣｌ－０３、ＰＡＡ－ＨＣｌ－０５、ＰＡＡ－ＨＣｌ－３Ｌ、ＰＡＡ－ＨＣｌ－１０Ｌ、ＰＡＡ－ＳＡ等を例示できる。 In the formula (1), the cationic polymer in which n1 is 0 is represented by the following formula (18), and is a polymer having an allylamine having a cation of a primary amine as a repeating unit.

(In the formula, n indicates a natural number.)
Further, in the formula (1), the cationic polymer in which n1 is 1 is represented by the following formula (19), and is a polymer having an allylamine acid salt having a primary amine cation as a repeating unit.

(In the formula, X ₁ indicates any of hydrochloric acid, amidosulfuric acid, and acetic acid, and n indicates a natural number.)
The mass average molecular weight of the cationic polymer represented by the formula (1) is in the range of 500 to 200,000, and n indicates the degree of polymerization required for the mass average molecular weight to be 500 to 200,000.
Specifically, the cationic polymer represented by the formula (1) is manufactured by Nittobo Medical Co., Ltd., and the product names are PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C. , PAA-25, PAA-HCl-01, PAA-HCl-03, PAA-HCl-05, PAA-HCl-3L, PAA-HCl-10L, PAA-SA and the like can be exemplified.

（式中、ｍ及びｎは、それぞれ独立に自然数を示す。）
また、式（２）において、ｎ２ａが１、且つ、ｎ２ｂが０であるカチオン性高分子は下記式（２１）で示され、一級アミンのカチオンを有するアリルアミンの酸塩と、二級アミンのカチオンを有するジアリルアミンとからなる共重合体である。

（式中、Ｘ_２ａは、塩酸、アミド硫酸、酢酸のいずれかを示し、ｍ及びｎは、それぞれ独立に自然数を示す。）
また、式（２）において、ｎ２ａが０、且つ、ｎ２ｂが１であるカチオン性高分子は下記式（２２）で示され、一級アミンのカチオンを有するアリルアミンと、二級アミンのカチオンを有するジアリルアミンの酸塩とからなる共重合体である。

（式中、Ｘ_２ｂは，塩酸、アミド硫酸、酢酸のいずれかを示し、ｍ及びｎは、それぞれ独立に自然数を示す。）
また、式（２）において、ｎ２ａ及びｎ２ｂが１であるカチオン性高分子は下記式（２３）で示され、一級アミンのカチオンを有するアリルアミンの酸塩と、二級アミンのカチオンを有するジアリルアミンの酸塩とからなる共重合体を示す。

（式中、Ｘ_２ａ及びＸ_２ｂは、それぞれ独立に、塩酸、アミド硫酸、酢酸のいずれかを示し、ｍ及びｎは、それぞれ独立に自然数を示す。）
式（２）で示されるカチオン性高分子の質量平均分子量は５００～２００，０００の範囲にあり、ｍ及びｎは、質量平均分子量が５００～２００，０００となるのに必要な重合度を示す。
式（２）で示されるカチオン性高分子として具体的には、ニットーボーメディカル（株）製、製品名：ＰＡＡ－Ｄ１１－ＨＣｌ、ＰＡＡ－Ｄ４１－ＨＣｌ、ＰＡＡ－Ｄ１９－ＨＣｌ、ＰＡＡ－Ｄ１９Ａ等を例示できる。 In the formula (2), the cationic polymer in which n2a and n2b are 0 is represented by the following formula (20), and is a copolymer composed of an allylamine having a primary amine cation and a diallylamine having a secondary amine cation. Is.

(In the formula, m and n each independently indicate a natural number.)
Further, in the formula (2), the cationic polymer in which n2a is 1 and n2b is 0 is represented by the following formula (21), and is an allylamine acid salt having a primary amine cation and a secondary amine cation. It is a copolymer composed of diallylamine having.

(In the formula, X _2a indicates any of hydrochloric acid, amidosulfuric acid, and acetic acid, and m and n independently indicate natural numbers.)
Further, in the formula (2), the cationic polymer in which n2a is 0 and n2b is 1 is represented by the following formula (22), and an allylamine having a primary amine cation and a diallylamine having a secondary amine cation are represented by the following formula (22). It is a copolymer composed of the acid salt of.

(In the formula, X _2b indicates any of hydrochloric acid, amidosulfuric acid, and acetic acid, and m and n independently indicate natural numbers.)
Further, in the formula (2), the cationic polymer in which n2a and n2b are 1 is represented by the following formula (23), and the acid salt of allylamine having a cation of a primary amine and the diallylamine having a cation of a secondary amine are used. Shows a copolymer composed of an acid salt.

(In the formula, X _2a and X _2b independently indicate any of hydrochloric acid, amidosulfuric acid, and acetic acid, and m and n independently indicate natural numbers.)
The mass average molecular weight of the cationic polymer represented by the formula (2) is in the range of 500 to 200,000, and m and n indicate the degree of polymerization required for the mass average molecular weight to be 500 to 200,000. ..
Specifically, as the cationic polymer represented by the formula (2), Nittobo Medical Co., Ltd., product names: PAA-D11-HCl, PAA-D41-HCl, PAA-D19-HCl, PAA-D19A and the like are used. It can be exemplified.

（式中、ｍ及びｎは、それぞれ独立に自然数を示す。）
また、式（３）において、ｎ３ａが１、且つ、ｎ３ｂが０であるカチオン性高分子は下記式（２５）で示され、一級アミンのカチオンを有するアリルアミンの酸塩と、三級アミンのカチオンを有するジメチルアリルアミンとからなる共重合体である。

（式中、Ｘ_３ａは、塩酸、アミド硫酸、酢酸のいずれかを示し、ｍ及びｎは、それぞれ独立に自然数を示す。）
また、式（３）において、ｎ３ａが０、且つ、ｎ３ｂが１であるカチオン性高分子は下記式（２６）で示され、一級アミンのカチオンを有するアリルアミンと、三級アミンのカチオンを有するジメチルアリルアミンの酸塩とからなる共重合体である。

（式中、Ｘ_３ｂは、塩酸、アミド硫酸、酢酸のいずれかを示し、ｍ及びｎは、それぞれ独立に自然数を示す。）
また、式（３）において、ｎ３ａ及びｎ３ｂが１であるカチオン性高分子は下記式（２７）で示され、一級アミンのカチオンを有するポリアリルアミンの酸塩と、三級アミンのカチオンを有するジメチルアリルアミンの酸塩とからなる共重合体である。

（式中、Ｘ_３ａ及びＸ_３ｂは、それぞれ独立に、塩酸、アミド硫酸、酢酸のいずれかを示し、ｍ及びｎは、それぞれ独立に自然数を示す。）
式（３）で示されるカチオン性高分子の質量平均分子量は５００～２００，０００の範囲にあり、ｍ及びｎは、質量平均分子量が５００～２００，０００となるのに必要な重合度を示す。
式（３）で示されるカチオン性高分子として具体的には、ニットーボーメディカル（株）製、製品名：ＰＡＡ－１１１２、ＰＡＡ－１１１２ＣＬ等を例示できる。 In the formula (3), the cationic polymer in which n3a and n3b are 0 is represented by the following formula (24), and has a copolymerization weight of allylamine having a cation of a primary amine and dimethylallylamine having a cation of a tertiary amine. It is a coalescence.

(In the formula, m and n independently indicate natural numbers.)
Further, in the formula (3), the cationic polymer in which n3a is 1 and n3b is 0 is represented by the following formula (25), and is an allylamine acid salt having a primary amine cation and a tertiary amine cation. It is a copolymer composed of dimethylallylamine having.

(In the formula, X _3a indicates any of hydrochloric acid, amidosulfuric acid, and acetic acid, and m and n independently indicate natural numbers.)
Further, in the formula (3), the cationic polymer in which n3a is 0 and n3b is 1 is represented by the following formula (26), and has an allylamine having a primary amine cation and a dimethyl having a tertiary amine cation. It is a copolymer composed of an allylamine acid salt.

(In the formula, X _3b indicates any of hydrochloric acid, amidosulfuric acid, and acetic acid, and m and n independently indicate natural numbers.)
Further, in the formula (3), the cationic polymer in which n3a and n3b are 1 is represented by the following formula (27), and a polyallylamine acid salt having a primary amine cation and a dimethyl having a tertiary amine cation are shown. It is a copolymer composed of an acid salt of allylamine.

(In the formula, X _3a and X _3b independently indicate any of hydrochloric acid, amidosulfuric acid, and acetic acid, and m and n independently indicate natural numbers.)
The mass average molecular weight of the cationic polymer represented by the formula (3) is in the range of 500 to 200,000, and m and n indicate the degree of polymerization required for the mass average molecular weight to be 500 to 200,000. ..
Specific examples of the cationic polymer represented by the formula (3) include those manufactured by Nittobo Medical Co., Ltd., product names: PAA-1112, PAA-1112CL and the like.

（式中、ｎは自然数を示す。）
また、式（４）において、ｎ４が１であり、且つ、Ｒ_１が水素原子であるカチオン性高分子は下記式（２９）で示され、二級アミンのカチオンを有するジアリルアミンの酸塩を繰り返し単位とする重合体である。

（式中、Ｘ_４は、塩酸、アミド硫酸、酢酸のいずれかを示し、ｎは自然数を示す。）
また、式（４）において、ｎ４が０であり、且つ、Ｒ_１が、炭素数１～３の直鎖又は分岐のアルキル基であるカチオン性高分子は下記式（３０）で示され、三級アミンのカチオンを有するアルキルジアリルアミンを繰り返し単位とする重合体である。

（式中、Ｒ_１′は、炭素数１～３の直鎖又は分岐のアルキル基を示し、ｎは自然数を示す。）
また、式（４）において、ｎ４が１であり、且つ、Ｒ_１が、炭素数１～３の直鎖又は分岐のアルキル基であるカチオン性高分子は下記式（３１）で示され、三級アミンのカチオンを有するアルキルジアリルアミンの酸塩を繰り返し単位とする重合体である。

（式中、Ｒ_１′は、炭素数１～３の直鎖又は分岐のアルキル基を示し、Ｘ_４は、塩酸、アミド硫酸、酢酸のいずれかを示し、ｎは自然数を示す。）
炭素数１～３の直鎖又は分岐のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基等を例示できる。
式（４）で示されるカチオン性高分子の質量平均分子量は５００～２００，０００の範囲にあり、ｎは、質量平均分子量が５００～２００，０００となるのに必要な重合度を示す。
式（４）で示されるカチオン性高分子として具体的には、ニットーボーメディカル（株）製、製品名：ＰＡＳ－２１、ＰＡＳ－２１ＣＬ、ＰＡＳ－Ｍ－１Ｌ、ＰＡＳ－Ｍ－１、ＰＡＳ－２２ＳＡ－４０、ＰＡＳ－Ｍ－１Ａ等を例示できる。 In the formula (4), the cationic polymer in which n4 is 0 and _R1 is a hydrogen atom is represented by the following formula (28), and is a polymer having diallylamine having a secondary amine cation as a repeating unit. Is.

(In the formula, n indicates a natural number.)
Further, in the formula (4), the cationic polymer in which n4 is 1 and _R1 is a hydrogen atom is represented by the following formula (29), and the acid salt of diallylamine having a secondary amine cation is repeated. It is a polymer as a unit.

( _In the formula, X4 indicates any of hydrochloric acid, amidosulfuric acid, and acetic acid, and n indicates a natural number.)
Further, in the formula (4), the cationic polymer in which n4 is 0 and _R1 is a linear or branched alkyl group having 1 to 3 carbon atoms is represented by the following formula (30). It is a polymer having an alkyl diallylamine having a cation of a secondary amine as a repeating unit.

(In the formula, R ₁ ′ indicates a linear or branched alkyl group having 1 to 3 carbon atoms, and n indicates a natural number.)
Further, in the formula (4), the cationic polymer in which n4 is 1 and _R1 is a linear or branched alkyl group having 1 to 3 carbon atoms is represented by the following formula (31). It is a polymer having an acid salt of alkyldiallylamine having a cation of a secondary amine as a repeating unit.

(In the formula, R ₁ ′ indicates a linear or branched alkyl group having 1 to 3 carbon atoms, X ₄ indicates any of hydrochloric acid, amidosulfuric acid, and acetic acid, and n indicates a natural number.)
Examples of the linear or branched alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
The mass average molecular weight of the cationic polymer represented by the formula (4) is in the range of 500 to 200,000, and n indicates the degree of polymerization required for the mass average molecular weight to be 500 to 200,000.
Specifically, the cationic polymer represented by the formula (4) is manufactured by Nittobo Medical Co., Ltd., and product names: PAS-21, PAS-21CL, PAS-M-1L, PAS-M-1, PAS-22SA. -40, PAS-M-1A and the like can be exemplified.

（式中、Ｒ_２及びＲ_３は、それぞれ独立に、炭素数１～３の直鎖又は分岐のアルキル基を示し、Ｘ_５は、塩素原子、ＣＨ_３ＳＯ_４、Ｃ_２Ｈ_５ＳＯ_４のいずれかを示し、ｎは自然数を示す。）
炭素数１～３の直鎖又は分岐のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基等を例示できる。
式（５）で示されるカチオン性高分子の質量平均分子量は１０，０００～３００，０００の範囲にあり、ｎは、質量平均分子量が１０，０００～３００，０００となるのに必要な重合度を示す。
式（５）で示されるカチオン性高分子として具体的には、ニットーボーメディカル（株）製、製品名：ＰＡＳ－Ｈ－５Ｌ、ＰＡＳ－Ｈ－１０Ｌ、ＰＡＳ－２４等を例示できる。 The cationic polymer represented by the formula (5) is a polymer having a diallyldialkylammonium salt having a cation of a quaternary amine as a repeating unit.

(In the formula, R ₂ and R ₃ each independently represent a linear or branched alkyl group having 1 to 3 carbon atoms, and X ₅ is a chlorine atom, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ . Either is indicated, and n indicates a natural number.)
Examples of the linear or branched alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
The mass average molecular weight of the cationic polymer represented by the formula (5) is in the range of 10,000 to 300,000, and n is the degree of polymerization required for the mass average molecular weight to be 10,000 to 300,000. Is shown.
Specific examples of the cationic polymer represented by the formula (5) include Nittobo Medical Co., Ltd., product names: PAS-H-5L, PAS-H-10L, PAS-24 and the like.

（式中、Ｒ_４は、炭素数１～３の直鎖又は分岐のアルキル基、炭素数１～３の直鎖又は分岐のアルコキシ基、アミノ基のいずれかを示し、ｍ及びｎは、それぞれ独立に自然数を示す。）
炭素数１～３の直鎖又は分岐のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基等を、
炭素数１～３の直鎖又は分岐のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基等を、それぞれ例示できる。
式（３２）で示されるカチオン性高分子の質量平均分子量は５００～２００，０００の範囲にあり、ｍ及びｎは、質量平均分子量が５００～２００，０００となるのに必要な重合度を示す。
式（３２）で示されるカチオン性高分子として具体的には、ニットーボーメディカル（株）製、製品名：ＰＡＡ－Ｕ５０００、ＰＡＡ－Ｕ７０３０、ＰＡＡ－ＡＣ５０５０Ａ、ＰＡＡ－Ｎ５０００、ＰＡＡ－Ｎ５０５０ＣＬ等を例示できる。 Further, as the cationic polymer, a polymer represented by the following formula (32) can also be used. The polymer represented by the formula (32) is a polymer in which the primary amine of a cationic polymer having n1 of 0 in the formula (1) is partially replaced with a group having a carbonyl group.

(In the formula, _R4 represents any of a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, or an amino group, and m and n are each. Independently shows natural numbers.)
Examples of the linear or branched alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
Examples of the linear or branched alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group and the like.
The mass average molecular weight of the cationic polymer represented by the formula (32) is in the range of 500 to 200,000, and m and n indicate the degree of polymerization required for the mass average molecular weight to be 500 to 200,000. ..
Specific examples of the cationic polymer represented by the formula (32) include Nittobo Medical Co., Ltd., product names: PAA-U5000, PAA-U7030, PAA-AC5050A, PAA-N5000, PAA-N5050CL and the like. ..

The cationic polymer applied to the present invention is the cationic polymer represented by the formula (1), in which n1 is 0, or n1 is ₁ , and X1 is hydrochloric acid or amide sulfate. Is preferable.
Further, in the cationic polymer represented by the formula (2), n2a and n2b are preferably 0 or 1, n2a and n2b are 0, or n2a and n2b are 1, and X _2a . And X _2b are more preferably the same, n2a and n2b are 0, or n2a and n2b are 1 and X _2a and X _2b are hydrochloric acid or acetic acid.
Further, in the cationic polymer represented by the formula (3), n3a and n3b are preferably 0 or 1, n3a and n3b are 0, or n3a and n3b are 1, and _X3a . And X _3b are more preferably the same, n3a and n3b are 0, or n3a and n3b are 1, and X _3a and X _3b are hydrochloric acid.
Further, in the cationic polymer represented by the formula (4), it is preferable that R ₁ is a hydrogen atom or a methyl group, and when R ₁ is a hydrogen atom, n4 is 0 or n4 is 1. And when X ₄ is hydrochloric acid or R ₁ is a methyl group, it is more preferable that n 4 is 1 and X ₄ is hydrochloric acid or amidosulfate.
Further, in the cationic polymer represented by the formula (5), it is preferable that R ₂ and R ₃ are methyl groups, or one of R ₂ and R ₃ is a methyl group and the other is an ethyl group. , R ₂ and R ₃ are methyl groups, and X ₅ is a chlorine atom, or when one of R ₂ and R ₃ is a methyl group and the other is an ethyl group, X ₅ is C. ₂ H ₅ SO ₄ is more preferable, R ₂ and R ₃ are methyl groups, and X ₅ is a chlorine atom.
Further, in the cationic polymer represented by the formula (32), it is preferable that _R4 is any one of a methyl group, a methoxy group and an amino group.
The above-mentioned cationic polymer is preferably used because it has excellent adsorptivity to the surface of the colorant and can charge the colorant to a positive charge more stably.

The mass average molecular weight of the cationic polymer represented by the formulas (1) to (4) applied to the present invention is not particularly limited as long as it is in the range of 500 to 200,000, but is 800 to 100. It is preferably in the range of 000, more preferably in the range of 1,000 to 50,000. The mass average molecular weight of the cationic polymer represented by the formula (5) is not particularly limited as long as it is in the range of 10,000 to 300,000, but is in the range of 25,000 to 250,000. It is preferably in the range of 50,000 to 250,000, and more preferably in the range of 50,000 to 250,000.

The vehicle applied to the present invention further contains an acrylic polymer dispersant in addition to the above-mentioned cationic polymer. By using a cationic polymer and an acrylic polymer dispersant in combination, an ionic interaction between a colorant charged with a positive charge by the cationic polymer and an acrylic polymer dispersant exhibiting anionic properties. The acrylic polymer dispersant causes a loose bridging action between the positively charged colorants, and the colorants form loose aggregates. Therefore, it is possible to suppress the adhesion of the colorants in close contact with each other, suppress the separation of the colorants, and easily redisperse the colorants even if they are separated. Then, when the ink composition is housed in a writing tool and put into practical use, the colorant is prevented from floating or settling to darken or lighten the handwriting, and in particular, an ink using a colorant having a large specific gravity is used. To prevent the colorant from settling and lightening the handwriting when the writing tool containing the composition is in an upright position and is subjected to external stimuli such as vibration or stored for a long period of time. Can be done.
The above-mentioned effect is effective for reversible thermochromic microcapsule pigments, which have a larger average particle size than general-purpose pigments and whose specific gravity tends to be particularly large due to the substances contained in the microcapsules, and are effective in ink compositions. It is preferably used because it suppresses the separation of microcapsule pigments and can be easily redispersed even if separated.

The acrylic polymer dispersant is preferably an acrylic polymer dispersant having a carboxy group, more preferably a comb-shaped acrylic polymer dispersant having a carboxy group in the side chain, and a side chain. It is more preferable to use an acrylic polymer dispersant having a comb-shaped structure having a plurality of carboxy groups.
Specific examples of the acrylic polymer dispersant having a comb-shaped structure having a plurality of carboxy groups in the side chain include Solsparse 43000 manufactured by Japan Lubrizol K.K.

Among the cationic polymers applied to the present invention, n1 is 0 or n1 is 0 in the cationic polymer represented by the formula (1) because it is excellent in ionic interaction with the acrylic polymer dispersant. , N1 is preferably ₁ , and X1 is hydrochloric acid or amide sulfate.
Further, in the cationic polymer represented by the formula (2), it is preferable that n2a and n2b are 1 and X _2a and X _2b are hydrochloric acid or acetic acid.
Further, in the cationic polymer represented by the formula (4), R ₁ is a hydrogen atom and n 4 is 0, or R ₁ is a hydrogen atom and n 4 is 1, and X ₄ is. It is preferably hydrochloric acid.
Further, in the cationic polymer represented by the formula (32), it is preferable that _R4 is an amino group.
The above-mentioned cationic polymer has an excellent ionic interaction with an acrylic polymer dispersant, suppresses the separation of the colorant, and has the effect of being easily redispersed even if separated. It can be further improved. Further, when the ink composition is housed in a writing tool and put into practical use, the colorant is further suppressed from floating or settling to darken or lighten the handwriting, and particularly when the specific gravity of the colorant is large. In addition, when the writing tool is in an upright position and is subjected to external stimuli such as vibration or stored for a long period of time, it is better to further suppress the colorant from settling and the handwriting from fading. It is preferably used because it can form handwriting.

In addition, the cationic polymers represented by the formulas (1) to (5) are not easily affected by excessive temperature changes, are strongly adsorbed on the surface of the colorant, and are ionically mutual with the acrylic polymer dispersant. Since the loose agglomerates formed by the action are not easily affected by excessive temperature changes, the colorant in the aqueous ink composition of the present invention is suppressed from agglomerating regardless of the temperature environment in which it is stored. .. Therefore, when the ink composition is frozen and thawed and the state of the ink composition changes from liquid to solid or from solid to liquid, it is suppressed that the colorant aggregates and separates, and the ink composition becomes a writing tool. When the ink is stored and put into practical use, the colorant aggregates and the ink is agglomerated even when the ink is left in a low temperature region below 0 ° C. where the ink freezes, or when the ink is left in a high temperature region, for example, in an environment of 50 ° C. It is possible to suppress the decrease in fluidity and make it difficult to impair the ink ejection property from the pen tip of the writing tool.
The above-mentioned effects are effective for reversible thermochromic microcapsule pigments or reversible thermochromic resin particles that easily aggregate over time to form a hard cake layer, and are reversible thermochromic microcapsule pigments or reversible thermochromic properties. It is preferably used because it suppresses aggregation of resin particles, can be easily redispersed, and is excellent in ink ejection property from a pen tip of a writing tool containing an ink composition.

In the water-based ink composition of the present invention, the mass ratio of the cationic polymer to the acrylic polymer dispersant is preferably 1: 2.5 to 1:16, preferably 1: 3 to 1:12. Is more preferable. When the mass ratio of the cationic polymer and the acrylic polymer dispersant is within the above range, the cohesive force of the loose aggregate of the colorant formed by the cationic polymer and the acrylic polymer dispersant is increased. It can be improved and stably dispersed in the ink composition, and the colorant can be prevented from floating or settling and being localized.

Further, in the aqueous ink composition of the present invention, the ionic interaction between the cationic polymer and the acrylic polymer dispersant tends to cause precipitation in the ink composition such as pigments or resin particles having a large specific gravity. It is also effective against colorants, and has the effect of suppressing the precipitation and localization of these colorants and the fading of the brush strokes.
Examples of the pigment having a large specific gravity include titanium oxide and a microcapsule pigment containing the same, a bright pigment and a microcapsule pigment containing the same, and a reversible heat containing a reversible thermochromic composition having a large hysteresis width (ΔH). Examples thereof include discolorable microcapsule pigments.
Examples of the resin particles having a large specific gravity include resin particles containing titanium oxide, resin particles containing a bright pigment, and reversible thermochromic resin particles containing a reversible thermochromic composition having a large hysteresis (ΔH). Etc. can be exemplified.
As the colorant applied to the present invention, the component (c) in the reversible thermochromic composition is in the range of 60 to 90% by mass with respect to the total amount of the reversible thermochromic composition, and the component (c) is used. Reversible thermal discoloration with a mass average molecular weight of 250 or more and a specific gravity of the reversible thermochromic microcapsule pigment in a completely color-developed state at 20 ° C. with respect to water of 1.05 to 1.20. Sexual microcapsule pigments are suitable. The above-mentioned reversible thermochromic microcapsule pigment has a large hysteresis width (ΔH), and such a reversible thermochromic microcapsule pigment is decolorized by heating and decolorized in a specific temperature range. It is widely used not only in the field of writing tools but also in a wide range of fields because it can maintain its state. However, the reversible thermochromic microcapsule pigment having a large hysteresis width (ΔH) has 2 benzene rings in the molecule as the component (c). Since the compounds having the above are often used, the specific gravity tends to be large, and they tend to settle and separate in the ink composition. When this is done, there is a problem that the colorant precipitates and separates, and further, it becomes difficult to redisperse. However, the water-based ink composition of the present invention can suppress the separation of the colorant even when a colorant having a large specific gravity such as the above-mentioned reversible thermochromic microcapsule pigment is used as the colorant, and further. Even when the ink composition is subjected to external stimuli such as vibration or stored for a long period of time, the separation of the colorant can be suppressed, and even if the colorant is separated, it can be easily redispersed. Therefore, it is preferably used.
Considering the dispersion stability of the above-mentioned reversible thermochromic microcapsule pigment in the water-based ink composition of the present invention, the component (c) in the reversible thermochromic composition is based on the total amount of the reversible thermochromic composition. A reversible thermochromic microcapsule pigment in a completely colored state when it is in the range of 65 to 85% by mass, the mass average molecular weight of the component (c) is 250 or more, and the temperature is 20 ° C. with respect to water. A reversible thermochromic microcapsule pigment having a specific gravity of 1.05 to 1.20 is more preferable, and in the above-mentioned reversible thermochromic microcapsule, the reversible thermochromic microcapsule pigment in a completely colored state has a specific gravity of 1. It is preferably 10 to 1.20, more preferably 1.12 to 1.15.
Further, the component (c) in the reversible thermochromic composition is in the range of 70 to 85% by mass with respect to the total amount of the reversible thermochromic composition, and the mass average molecular weight of the component (c) is 250 or more. Further, the reversible thermochromic microcapsule pigment having a specific gravity of 1.05 to 1.20 of the reversible thermochromic microcapsule pigment in a completely color-developed state at 20 ° C. with respect to water is more preferable. In the reversible thermochromic microcapsule, the specific gravity of the reversible thermochromic microcapsule pigment in the completely colored state is preferably 1.10 to 1.20, and more preferably 1.12 to 1.15. ..
Since the ratio of the component (c) in the reversible thermochromic composition to the total amount of the reversible thermochromic composition is within the above range, even if the temperature of the reversible thermochromic composition is repeatedly changed, the color changes on the high temperature side. It is difficult to impair the reversible thermal discoloration function, which is in the decolorization state in the temperature range above the point (complete decolorization temperature) and in the color development state in the temperature range below the low temperature side discoloration point (complete color development temperature), and the color density at the time of color development is high. It is vivid and has sufficient color density as a colorant.
The specific gravity of the reversible thermochromic microcapsule pigment can be measured by the following method.

(Method for measuring the specific gravity of reversible thermochromic microcapsule pigments)
1. 1. 30 ml of a glycerin aqueous solution and 1 g of a reversible thermochromic microcapsule pigment in a completely colored state are put into a screw tube bottle and mixed to prepare a reversible thermochromic microcapsule pigment dispersion.
2. 2. The temperature of 30 ml of the above microcapsule pigment dispersion is adjusted to 20 ° C., and the mixture is centrifuged under centrifugal conditions at a rotation speed of 1,000 rpm for 30 seconds. As the centrifuge, a cooling / desktop centrifuge [manufactured by Kokusan Co., Ltd., product name: H103N] can be used.
3. 3. Observe the microcapsule pigment dispersion.
When it is confirmed that most of the microcapsule pigment has settled on the bottom of the beaker, the state of the dispersion liquid is observed by performing the operations 1 and 2 again using the aqueous solution having a glycerin concentration higher than that of the glycerin aqueous solution at this time.
When it is confirmed that most of the microcapsule pigment has floated on the liquid surface, perform steps 1 and 2 again using an aqueous solution having a lower glycerin concentration than the glycerin aqueous solution at this time, and observe the state of the dispersion liquid. ..
In the above series of operations, most of the microcapsule pigment is not in a state of being settled or floating on the liquid surface, and the parts other than the liquid surface of the glycerin aqueous solution and the vicinity of the bottom of the screw tube bottle are uniformly colored. Repeat until the condition is visually confirmed. The specific gravity of the glycerin aqueous solution when this state is observed is measured and used as the specific gravity of the reversible thermochromic microcapsule pigment. The specific gravity of the glycerin aqueous solution can be measured by the floating method described in JIS K0061 7.1 for the aqueous solution whose temperature is adjusted to 20 ° C.

Further, by adding a specific gravity adjusting agent to the vehicle applied to the present invention, the colorant floats or precipitates and is localized in the ink composition even though the ink composition has a low viscosity. Can be further suppressed and the dispersion stability of the colorant can be improved.
The dispersion stability of the colorant is maximized when the difference in specific gravity between the vehicle and the colorant is extremely small, and the specific gravity adjusting agent brings the specific gravity of the vehicle closer to the specific gravity of the colorant. The specific density of the vehicle depends on the specific gravity of the water-soluble substance dissolved in the vehicle and the amount of the water-soluble substance added thereto. be able to.

Examples of the specific gravity adjusting agent include oxygen acids of Group 6 elements contained in the atomic weight range of 90 to 185 and salts thereof.
Such a specific gravity adjusting agent can adjust the specific gravity of the vehicle so as to be close to that of a colorant having a large specific gravity, and even though the ink composition has a low viscosity, external stimuli such as vibration may be applied or the ink composition may be long. It is preferably used because it is possible to prevent the colorant from settling and the handwriting from becoming lighter by storing it for a period of time.

The above oxygen acid and its salt are selected from the group consisting of the transition metal element oxygen acid and its salt, and the oxygen acid ion is a tetrahedron in which an oxygen atom is usually coordinated with a metal atom or the like by 4 or 6. Or it is said to form an octahedron.
The tetrahedral or octahedral unit may be a single unit, or may be a polyacid having a structure in which they are bonded via ridges and vertices and a polyate which is a salt thereof. Polyacids are multiple acids produced by condensation of the metal element oxygen acid, but polyacids that are composed of only one type of metal and have the same type of anions that condense are called isopolyacids, and are two or more types of anions. The polyacid condensed with is called a heteropolyacid. And each salt is called an isopolylate and a heteropolylate. The above-mentioned polyacids include isopolyacids, heteropolyacids and the like, and the above-mentioned polyacidates include isopolyrates, heteropolylates and the like.

Examples of the specific gravity adjusting agent include a single oxygen acid and a salt thereof, an isopolyacid and a salt thereof, a heteropolyacid and a salt thereof and the like.
Examples of the single oxygen acid include molybdenum acid and tungstate, and examples of the single oxygen acid salt include sodium molybdenate, potassium molybdenate, ammonium molybdenate, sodium tungstate, potassium tungstate, and tungsten. Examples thereof include ammonium acid, lithium tungstate, and magnesium tungstate.
Examples of the isopolyacid include metamolybdate, paramolybdate, metatungstate, paratungstate, and isotungstate, and examples of the isopolylate include sodium metamolybdate and metamolybdate. Potassium, ammonium metamolybdate, sodium paramolybdate, potassium paramolybdate, ammonium paramolybdate, sodium metatungstate, potassium metatungstate, ammonium metatungstate, barium metatungstate, sodium paratungstate, and isotungstate Examples thereof include sodium tungstate.
Examples of the heteropolyacid include molybdrine acid, molybdosilicic acid, tonguestophosphate, and tonguestosilicic acid, and examples of the heteropolyacidate include sodium molybdrine acid, sodium molybdosilicate, sodium tonguestrate, and tonguestokei. Examples thereof include sodium acid acid.
The above oxygen acid and its salt can be used alone or in admixture of two or more.

Among the above specific gravity adjusting agents, metatungstate, paratungstate, sodium metatungstate, potassium metatungstate, ammonium metatungstate, barium metatungstate, sodium paratungstate, sodium isotungstate, tangstric acid, Sodium tungstate, sodium tungstate, and sodium tungstate are preferred, and sodium isotungstate, sodium metatungstate, and sodium paratungstate are more preferred.
The above sodium isotungstate, sodium metatungstate, and sodium paratungstate are not only highly safe, but also have a high specific density in themselves, so it is easy to adjust the liquid with a high specific density according to the amount added. , Suitable for use.

The specific gravity adjusting agent is blended in the total amount of the ink composition in the range of preferably 2 to 20% by mass, more preferably 5 to 15% by mass. When the blending ratio of the specific gravity adjusting agent exceeds 20% by mass, the coloring agent tends to aggregate. On the other hand, if the blending ratio is less than 2% by mass, the effect of adjusting the specific gravity of the vehicle becomes poor.
The mass ratio of the colorant to the specific gravity adjusting agent is preferably 1: 0.05 to 1: 4, more preferably 1: 0.075 to 1: 2, and 1: 0.1 to 1: 2. It is more preferably 1: 1.5.

Vehicles containing the above-mentioned specific gravity adjusting agent are particularly effective for colorants such as pigments or resin particles having a large specific gravity, and when the ink composition has a low viscosity but is subjected to external stimuli such as vibration, When stored for a long period of time, it is possible to prevent the colorant from settling in the ink composition and improve the dispersion stability of the colorant.
Examples of the pigment having a large specific gravity include titanium oxide and a microcapsule pigment containing the same, a bright pigment and a microcapsule pigment containing the same, and a reversible thermochromic composition containing a large hysteresis (ΔH). Examples thereof include sex microcapsule pigments.
Examples of the resin particles having a large specific gravity include resin particles containing titanium oxide, resin particles containing a bright pigment, and reversible thermochromic resin particles containing a reversible thermochromic composition having a large hysteresis (ΔH). Etc. can be exemplified.
The specific gravity of the colorant such as the pigment or the resin particles is preferably 1.05 to 1.20, more preferably 1.10 to 1.20, when water is used as a reference substance at 20 ° C. It is preferably 1.12 to 1.15, and more preferably 1.12 to 1.15. When the specific gravity of the colorant is within the above range, the dispersion stability of the above pigment or resin particles in the ink composition containing the specific gravity adjusting agent is further improved, and the ink composition is vibrated from the outside. When the vehicle is stimulated or stored for a long period of time, it is possible to further suppress the precipitation and localization of the colorant even though the vehicle has a low viscosity.
The specific gravity of the colorant such as the pigment or the resin particles can be measured by the same procedure as the above-mentioned "method for measuring the specific gravity of the reversible thermochromic microcapsule pigment".
The color development and fluidity of handwriting by the ink composition of the present invention are easily affected by the particle size of the colorant, and a colorant having an average particle size outside the above numerical range has a low color development density or fluidity. However, the content of the colorant as a whole is small, and the effect on the performance of the ink composition is small. A colorant having an average particle size outside such a numerical range has a lighter or heavier specific gravity than a colorant having an average particle size within the above numerical range, and is used in the glycerin aqueous solution adjusted above. Settles on the bottom of the screw tube bottle or rises to the liquid surface. However, since the colorant having an average particle size within the above numerical range floats in the glycerin aqueous solution, by setting the specific gravity of the aqueous solution as the specific gravity of the vehicle, excellent dispersion stability and good color development of the brush stroke are used. It can be an ink composition having properties.

Further, the vehicle containing the above specific gravity adjusting agent has a specific density in the range of 1.00 to 1.30 when water is used as a reference substance at 20 ° C., and further, the specific gravity is 1.05 to 1. It is preferably .20, more preferably 1.08 to 1.18.
Further, the specific gravity of the vehicle is preferably 0.90 to 1.20 times, more preferably 0.95 to 1.10 times, the specific gravity of the colorant such as the pigment or the resin particles described above. preferable.
If the specific gravity of the vehicle is within the above range and the specific gravity of the vehicle with respect to the specific gravity of the colorant is within the above range, the ink composition may be stored for a long period of time or when external stimuli such as vibration are applied to the ink composition. In this case, while the vehicle has a low viscosity, it is possible to further suppress the precipitation and localization of the colorant in the ink composition, and further improve the dispersion stability of the colorant.

Further, by blending a water-soluble organic solvent into the vehicle applied to the present invention, the water evaporation of the ink composition is suppressed, the specific gravity fluctuation of the ink composition is prevented, and the good dispersion stability of the colorant is obtained. While maintaining it, it is possible to stabilize the structure of loose aggregates formed by the cationic polymer and the acrylic polymer dispersant.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thioethylene glycol, polyethylene glycol, propylene glycol, butylene glycol and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulforan, 2-pyrrolidone, and N-methyl-2- Pyrrolidone and the like can be exemplified.
When a reversible thermochromic microcapsule pigment or a reversible thermochromic resin particle having a large hysteresis width (ΔH) is used as the colorant, the specific gravity of the reversible thermochromic microcapsule pigment or the reversible thermochromic resin particle is larger than 1, and the ink. When adjusting the specific gravity of the composition, it is easy to adjust the specific gravity by using a water-soluble organic solvent having a specific gravity higher than that of water. Therefore, use glycerin or the like having a specific gravity of more than 1.1 as the water-soluble organic solvent. Is preferable.

The water-soluble organic solvent is blended in the total amount of the ink composition in the range of preferably 1 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 10 to 25% by mass. When the blending ratio of the water-soluble organic solvent exceeds 40% by mass, the ink viscosity tends to increase, the ink ejection property of the writing instrument containing the ink composition deteriorates, and the writing performance tends to be impaired. On the other hand, if the blending ratio is less than 1% by mass, the effect of suppressing water evaporation is poor, and it becomes difficult to prevent fluctuations in the specific gravity of the ink composition.

Further, by blending a water-soluble resin into the vehicle applied to the present invention, it is possible to impart adhesiveness and viscosity to the paper surface, and in the ink composition of the cationic polymer and the acrylic polymer dispersant. It is possible to improve the stability in.
Examples of the water-soluble resin include water-soluble alkyd resin, acrylic resin, styrene-maleic acid copolymer, cellulose derivative, polyvinylpyrrolidone, polyvinyl alcohol, dextrin and the like.
Further, since the acrylic polymer dispersant is excellent in stability, polyvinyl alcohol is preferable as the water-soluble resin, and partially saponified polyvinyl alcohol is more preferable, and partially saponified type having a saponification degree of 70 to 89 mol%. Polyvinyl alcohol is more preferred.
Specifically, as a water-soluble resin, manufactured by Japan Vam & Poval Co., Ltd., product name: J Poval JP series, JL series, JR series,
Made by Mitsubishi Chemical Corporation, Product name: G-type gosenol, K-type gosenol,
Made by Kuraray Co., Ltd., Product names: PVA203, 205, 210, 217, 217E, 217EE, 220, 220E, 224, 224E, 235, 403, 405, 420, Examples thereof include 420H, 424H, 505, L-8, L-9, L-9-78, and L-10.

The water-soluble resin is blended in the total amount of the ink composition in the range of preferably 0.1 to 1.5% by mass, more preferably 0.5 to 1% by mass. When the blending ratio of the water-soluble resin is within the above range, the stability of the acrylic polymer dispersant becomes good, and a reversible thermochromic microcapsule pigment or a reversible thermochromic resin particle is used as the colorant. If so, it becomes difficult to impair the color-developing property and discoloration property of these colorants.

In the water-based ink composition of the present invention, if necessary, other constitutional materials such as kaolin, talc, mica, clay, bentonite, calcium carbonate, aluminum hydroxide, sericite, and potassium titanate, and fluorosurfactants Wetting agents such as agents and nonionic surfactants, acrylic resin, urethane resin, styrene-butadiene resin, alkyd resin, sulfoamide resin, maleic acid resin, polyvinyl acetate, ethylene-vinyl acetate copolymer resin, vinyl chloride-acetic acid. Vinyl copolymer resin, styrene-maleic acid ester copolymer resin, styrene-acrylonitrile copolymer resin, cyanate-modified polyalkylene glycol, ester gum, xylene resin, urea resin, urea aldehyde resin, phenol resin, alkylphenol resin, terpene phenol resin, From resin having water solubility in resin used as a fixing agent such as rosin resin and its hydrogenated compound, rosin phenol resin, polyvinyl alkyl ether, polyamide, polyolefin, nylon resin, polyester, and cyclohexanone resin, and water-insoluble resin. Emulsion, polyolefin, acrylic resin, nylon resin, silicone resin, urethane resin, resin particles made of fluororesin, inorganic salts such as ammonia, sodium carbonate, sodium phosphate, sodium hydroxide, sodium acetate, and water-soluble PH adjusters such as organic basic compounds such as amine compounds, rust preventives such as benzotriazole, tolyltriazole, dicyclohexylammonitelite, diisopropylammonium nitrate, and saponin, urea, nonionic surfactants, reduced or non-reduced Wetting agents such as starch hydrolysates, disaccharides such as trehalose, oligosaccharides, sucrose, cyclodextrin, glucose, dextrin, sorbit, mannit, and sodium pyrophosphate, antifoaming agents, viscosity modifiers, preservatives, antiseptic Additives such as phenol can also be added.

The water-based ink composition of the present invention can be produced by any conventionally known method. Specifically, each of the above components can be blended in a required amount and mixed with various stirrers such as propeller stirring, homodisper, or homomixer, and various dispersers such as bead mills to produce the product.

When a reversible thermochromic microcapsule pigment or a reversible thermochromic resin particle, or a reversible photochromic microcapsule pigment or a reversible photochromic resin particle is used as the colorant applied to the present invention, the microcapsule pigment or the resin Pigments such as the above-mentioned inorganic pigments, organic pigments, brilliant pigments, fluorescent pigments, phosphorescent pigments, non-color-changing colorants such as dyes, and microcapsule pigments containing these in particles or ink compositions. Alternatively, by blending resin particles or the like containing the above-mentioned non-color-changing colorant, it is possible to exhibit a reciprocal color change from colored (1) to colored (2).

The viscosity of the aqueous ink composition of the present invention is preferably 1 to 20 mPa · s when measured under the condition of a rotation speed of 30 rpm in an environment of 20 ° C., and is preferably 1 to 10 mPa · s. Is more preferable, and 1 to 7 mPa · s is even more preferable. When the viscosity of the ink composition is within the above range, the localization of the colorant in the ink composition is suppressed, and the ink ejection property from the pen tip of the writing instrument containing the ink composition is improved. Therefore, it is possible to obtain an ink composition capable of forming a stroke with good color development by suppressing writing defects such as blurring and line skipping.
The viscosity was determined by using a BL type rotary viscometer [manufactured by Toki Sangyo Co., Ltd., product name: TVB-M type viscometer, L type rotor] and placing the ink composition in an environment of 20 ° C. It is a measured value.

The surface tension of the water-based ink composition of the present invention is preferably 25 to 50 mN / m, preferably 25 to 45 mN / m, and preferably 30 to 45 mN / m in an environment of 20 ° C. More preferred. Since the surface tension of the ink composition is within the above range, when writing with a writing instrument containing the ink composition, handwriting is less likely to cause blurring, and the ink is left in a temperature range of less than 0 ° C. where it freezes. Even when the ink is left in a high temperature range, for example, in an environment of 50 ° C., the ink ejection property is not impaired, and the handwriting density and the writing width are less likely to vary depending on the storage environment and the usage environment. In addition, it is easy to suppress bleeding of handwriting and strike-through on the paper surface, and it is possible to improve the wettability of the ink composition on the paper surface.
For the surface tension, a surface tension measuring instrument [manufactured by Kyowa Surface Chemistry Co., Ltd., product name: DY-300] was used, the ink composition was placed in an environment of 20 ° C., and a vertical flat plate using a glass plate was used. It is a value measured by the method.

Further, the pH of the aqueous ink composition of the present invention is preferably 3 to 8, more preferably 4 to 7, and even more preferably 5 to 7. When the pH of the ink composition is within the above range, the colorant contained in the ink composition, particularly the reversible thermochromic microcapsule pigment or the reversible thermochromic resin particles, aggregates or precipitates in a low temperature region. Can be suppressed. Further, when the pH exceeds 8, the ink ejection property when the writing instrument containing the ink composition is left in a low temperature range, that is, in a temperature range where the ink freezes, is liable to be impaired. On the other hand, when the pH is less than 3, when the reversible thermochromic microcapsule pigment or the reversible thermochromic resin particles are used as the colorant, the color developing property of the reversible thermochromic composition becomes strong, and the color residue remains at the time of decoloring. It is easy for problems to occur.
The pH is a value measured by placing the ink composition in an environment of 20 ° C. using a pH meter [manufactured by DKK-TOA CORPORATION, product name: IM-40S].

The water-based ink composition of the present invention is housed in a writing tool and used.
Examples of the writing tool include various writing tools such as a ballpoint pen, a marking pen, a fountain pen, a brush pen, and a calligraphy pen.

When the water-based ink composition of the present invention is used for a ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited. For example, the water-based ink composition is filled in a ballpoint pen refill or a ballpoint pen having an ink filling mechanism. Used.

The ball pen chip consists of a chip body and a ball provided at the front end of the chip body. For example, the ball is pressed and deformed inward from the outer surface near the tip of the chip body made of a metal pipe. A chip made by holding a chip, a chip made of a metal material, a chip formed by cutting with a drill or the like, and a chip made of a resin inside a metal or plastic chip. Examples thereof include a chip provided with a chip, or a ball held by the chip and urged forward by a spring body.
The material of the chip body and the ball is not particularly limited, and examples thereof include cemented carbide (cemented carbide), stainless steel, ruby, ceramic, resin, and rubber.
The diameter of the ball is preferably 0.1 to 3.0 mm, more preferably 0.2 to 2.0 mm, and even more preferably 0.3 to 1.0 mm. Further, the ball may be subjected to a surface treatment such as a DLC coat.

As the ink filling mechanism, for example, an ink container capable of directly filling an ink composition can be exemplified.
As the ink container, for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body is used.
A ballpoint pen refill (hereinafter, may be referred to as "refill") may be formed by directly connecting a ballpoint pen tip to an ink container or directly via a connecting member and directly filling the ink container with ink. can. A ballpoint pen can be formed by accommodating this refill in the barrel.

The rear end of the ink filled in the ink container is filled with an ink backflow preventive body. Examples of the ink backflow preventive body include a liquid stopper or a solid stopper.
The faucet consists of a non-volatile liquid and / or a refractory liquid, for example vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligoform, dimethyl. Examples thereof include silicone oil, methylphenyl silicone oil, amino-modified silicone oil, polyether-modified silicone oil, and fatty acid-modified silicone oil.
As the non-volatile liquid and / or the refractory volatile liquid, one kind or a mixture of two or more kinds can be used as appropriate.

It is preferable to add a thickener to the non-volatile liquid and / or the non-volatile liquid to increase the viscosity to a suitable viscosity.
Examples of the thickener include silica having a hydrophobic treatment on the surface, fine particle silica having a methylated surface, aluminum silicate, swelling mica, a clay-based thickener such as bentonite and montmorillonite having a hydrophobic treatment, and magnesium stearate. , Fatty acid metal soaps such as calcium stearate, aluminum stearate, and zinc stearate, trivendilidene sorbitol, fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, dextrine-based compounds such as fatty acid dextrin, and cellulose-based compounds can be exemplified. ..

Examples of the solid stopper include solid stoppers made of polyethylene, polypropylene, polymethylpentene and the like.
As the ink backflow preventive body, the above-mentioned liquid stopper and solid stopper can be used in combination.

In addition, the shaft cylinder itself is used as an ink filling mechanism, and ink is directly filled in the shaft cylinder, and a ballpoint pen tip is attached to the front end of the shaft cylinder to form a ballpoint pen equipped with a ballpoint pen tip and an ink filling mechanism. You can also do it.

When the ink filled in the ink filling mechanism has a low viscosity, the ballpoint pen provided with the ballpoint pen tip and the ink filling mechanism further supplies the ink to be filled in the ink filling mechanism to the pen tip. May be provided.
The ink supply mechanism is not particularly limited, and for example, (1) a mechanism in which an ink guide core made of a fiber bundle or the like is provided as an ink flow rate adjusting body and the ink is supplied to the pen tip by interposing the ink guide core. ) A mechanism that supplies ink to the pen tip by interposing a comb groove-shaped ink flow rate adjuster. A slit-shaped ink guide groove running through the pen and a ventilation groove wider than the groove are provided, and an ink guide core for guiding ink from the ink filling mechanism to the pen tip is arranged at the center of the pen via a pen core. Then, a mechanism for supplying ink to the pen tip and the like can be mentioned.
The material of the pen core is not particularly limited as long as it is a synthetic resin that can be injection-molded into a structure in which a large number of disks are formed into a comb groove shape. Examples of the synthetic resin include general-purpose polycarbonate, polypropylene, polyethylene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin) and the like. In particular, an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) is preferably used because it has high moldability and easy to obtain pen core performance.

When the ballpoint pen is provided with the above-mentioned ink supply mechanism, an ink storage body capable of filling ink can be used as the ink filling mechanism in addition to the above-mentioned ink container and shaft tube.
The ink occlusion body is a fiber focusing body in which crimped fibers are focused in the longitudinal direction, and is embedded in a covering body such as a plastic cylinder or a film so that the pore ratio is in the range of approximately 40 to 90%. It is configured by adjusting.

In addition, an ink supply mechanism is provided at the front end of the ink container so that the ink container is impregnated with ink and is connected to the ink storage body, and a ballpoint pen is provided so as to be connected to the ink supply mechanism. By connecting the tip directly or via a connecting member to the ink supply mechanism, it is also possible to form a ballpoint pen refill having a ballpoint pen tip, an ink filling mechanism, and an ink supply mechanism. Alternatively, an ink supply mechanism is provided inside the ink container so as to house the ink reservoir impregnated with ink in the ink container and connect to the ink reservoir, and a ballpoint pen to connect to the ink supply mechanism. A ballpoint pen refill can also be formed by connecting the tip directly or via a connecting member to the ink container.

Specifically, as a configuration of a ballpoint pen for accommodating an ink composition according to the present invention, (1) an ink accommodating body filled with ink is provided in a shaft cylinder, and the ink accommodating body is directly or via a connecting member. A ballpoint pen to which a ballpoint pen tip is connected and an ink backflow prevention body is filled in the end face of the ink, (2) Ink is directly filled in the shaft cylinder, and the ink consists of a comb groove-shaped ink flow rate adjusting body, a fiber bundle, etc. A ballpoint pen equipped with a mechanism that supplies ink to the pen tip by interposing an induction core as an ink flow control body, (3) Ink is directly filled in the shaft cylinder, and ink is supplied to the pen tip via the above pen core. A ballpoint pen equipped with a mechanism for ink, (4) an ink storage body made of a fiber bundle impregnated with ink is housed in a shaft cylinder, and an ink guide core made of a fiber bundle or the like is interposed as an ink flow rate adjusting body to make ink. An example is a ballpoint pen provided with a mechanism for supplying the ink to the pen tip.

Further, when the ink composition according to the present invention is used for a marking pen, the structure and shape of the marking pen itself are not particularly limited, and for example, a marking pen refill having a marking pen tip and an ink filling mechanism or It is used by filling a marking pen.

As the marking pen tip, for example, a resin processed body of a fiber, a fused processed body of a heat-meltable fiber, a felt body, etc. An example is a quality member or an extruded synthetic resin body having a plurality of axially extending ink outlet holes, and one end is processed into a shape suitable for the purpose such as a bullet shape, a rectangular shape, a chisel shape, etc. for practical use. Served.

As the ink filling mechanism, for example, an ink occlusion body capable of filling ink can be exemplified.
The ink occlusion body is a fiber focusing body in which crimped fibers are focused in the longitudinal direction, and is embedded in a covering body such as a plastic cylinder or a film to adjust the porosity to approximately 40 to 90%. It is composed.
An ink storage body impregnated with ink is housed in the shaft tube, and a marking pen tip is connected to the shaft cylinder directly or via a connecting member so as to be connected to the ink storage body to form a marking pen. be able to.
Further, by accommodating the ink storage body impregnated with ink in the ink storage body and connecting the marking pen tip to the ink storage body directly or via a connecting member so as to be connected to the ink storage body, the marking pen refill is performed. (Hereinafter, it may be referred to as "refill") can be formed. A marking pen can be formed by accommodating this refill in the barrel.
As the ink container, for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body is used.

The marking pen provided with the marking pen tip and the ink filling mechanism may further include an ink supply mechanism for supplying the ink composition to be filled in the ink filling mechanism to the pen tip.
The ink supply mechanism is not particularly limited, and for example, (1) a mechanism in which an ink guide core made of a fiber bundle or the like is provided as an ink flow rate adjusting body and the ink is supplied to the pen tip by interposing the ink guide core. ) A mechanism that supplies ink to the pen tip by interposing a comb groove-shaped ink flow rate adjuster. A slit-shaped ink guide groove running through the pen and a ventilation groove wider than the groove are provided, and an ink guide core for guiding ink from the ink filling mechanism to the pen tip is arranged at the center of the pen via a pen core. Examples thereof include a mechanism for supplying ink to the pen tip, and (4) a mechanism for supplying ink to the pen tip by opening a valve, which is provided with an ink flow rate adjusting body by a valve mechanism.
The material of the pen core is not particularly limited as long as it is a synthetic resin that can be injection-molded into a structure in which a large number of disks are formed into a comb groove shape. Examples of the synthetic resin include general-purpose polycarbonate, polypropylene, polyethylene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin) and the like. In particular, an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) is preferably used because it has high moldability and easy to obtain pen core performance.
As the valve mechanism, a conventional general-purpose pumping type that opens by pressing the tip can be used, and a valve mechanism set to a spring pressure that can be pressed and released by writing pressure is preferable.

When the marking pen is provided with an ink supply mechanism, as the ink filling mechanism, an ink container capable of directly filling ink can be used in addition to the ink storage body described above. Further, the ink may be directly filled by using the shaft cylinder itself as an ink filling mechanism.
In addition, an ink supply mechanism is provided at the front end of the ink container so that the ink container is impregnated with ink and is connected to the ink storage body, and marking is provided so as to be connected to the ink supply mechanism. By connecting the pen tip to the ink supply mechanism directly or via a connecting member, a marking pen refill including the marking pen tip, the ink filling mechanism, and the ink supply mechanism can be formed. Alternatively, an ink supply mechanism is provided inside the ink container so as to house the ink reservoir impregnated with ink in the ink container and connect to the ink reservoir, and marking so as to connect to the ink supply mechanism. The marking pen refill can also be formed by connecting the pen tip directly or via a connecting member to the ink container.

Specifically, as the configuration of the marking pen for accommodating the ink composition according to the present invention, (1) an ink reservoir made of a fiber bundle impregnated with ink was accommodated in the shaft cylinder, and a capillary gap was formed. , A marking pen made of a fiber-processed body or a resin molded body, which is directly connected to the shaft cylinder so that the ink storage body and the chip are connected to each other, or (2) directly in the shaft cylinder. A marking pen that is filled with ink and is equipped with a mechanism for supplying ink to the pen tip by interposing an ink guide core composed of a comb groove-shaped ink flow rate adjusting body or a fiber bundle as an ink flow rate adjusting body, (3) shaft tube. A marking pen that is directly filled with ink and has a mechanism to supply ink to the pen tip via the pen core described above. It has a marking pen in which the ink container is directly filled with ink, and (5) an ink container containing an ink storage body made of a fiber bundle body impregnated with ink in a shaft tube. Examples thereof include a marking pen in which a marking pen tip made of a fiber processed body or a resin molded body formed of the above is connected to an ink container directly or via a connecting member so that the ink storage body and the tip are connected to each other. ..

When the ballpoint pen or marking pen is directly filled with ink, a stirring ball or the like that stirs the ink in the ink container or the shaft cylinder filled with the ink in order to facilitate the redispersion of the colorant. The stirrer may be built in. Examples of the shape of the agitating body include a spherical body and a rod-shaped body. The material of the agitator is not particularly limited, and examples thereof include metal, ceramic, resin, and glass.

Further, the above-mentioned ballpoint pen or marking pen may be in the form of an ink cartridge as a removable structure. In this case, after the ink composition contained in the ink cartridge of the writing instrument is used up, it can be used by replacing it with a new cartridge.
As the ink cartridge, one that also serves as a shaft cylinder that constitutes a writing tool by being connected to the writing tool main body, or one that covers and protects the shaft cylinder (rear shaft) after being connected to the writing tool main body is used. In the latter case, in addition to using the ink cartridge alone, the writing instrument before use may be used by connecting the writing instrument body and the ink cartridge, or by connecting the ink cartridge in the barrel when the user of the writing instrument uses it. It may be any of those housed in the barrel in a disconnected state so as to start.

Further, the writing instrument having the above-described configuration may be provided with a cap attached so as to cover the writing tip (tip tip), or may be provided with a haunting mechanism that allows the writing tip to appear and disappear from the writing instrument body (shaft cylinder). It is preferable to do so, and it is possible to prevent the writing tip from becoming dry and unable to write, and preventing the writing tip from being contaminated or damaged.
Writing instruments provided with a haunting mechanism are stored in the barrel with the tip of the writing exposed to the outside air, and any writing instrument with a structure in which the tip of the writing protrudes from the opening of the barrel due to the actuation of the hoisting mechanism is used. For example, the above-mentioned ballpoint pen refill or marking pen refill can be produced, and the refill is housed in the barrel so that the writing tip protrudes from the opening of the barrel by the operation of the haunting mechanism. It is possible to manufacture a writing instrument (a haunting type writing instrument) provided with a mechanism.
Further, when a writing instrument in the form of a ballpoint pen is provided with a haunting mechanism, a plurality of ballpoint pen refills are housed in the barrel, and the writing tip of any of the ballpoint pen refills is haunted from the opening of the barrel by operating the haunting mechanism. It can also be a type of haunting writing instrument (hazardous ballpoint pen).

As the haunting mechanism, for example, (1) an operating portion (clip) that can move in the front-rear direction from the rear side wall of the axle cylinder is projected outward in the radial direction, and the operating portion is slid forward to operate the front end of the axle cylinder. Side-slide type infestation mechanism that allows the writing tip to appear and disappear from the opening, (2) Rear end knock that allows the writing tip to appear and disappear from the front end opening of the barrel by pressing the operation unit provided at the rear end of the barrel forward. Type infestation mechanism, (3) Side knock type infestation mechanism in which the writing tip is infested from the front end opening of the shaft cylinder by pressing the operation part protruding from the outer surface of the side wall of the shaft cylinder inward in the radial direction, (4) shaft. An example is a rotary infestation mechanism in which the writing tip is infested from the opening at the front end of the shaft by rotating the operation portion at the rear of the cylinder.

Furthermore, the form of the ballpoint pen or marking pen is not limited to the above-mentioned configuration, and a tip of a different form can be attached, a pen tip for drawing out ink of a different color tone can be attached, and a tip of a different form can be attached. It may be a compound writing instrument (double-headed type, pen tip feeding type, etc.) in which the color tone of the ink derived from each chip is different.

The writing tool containing the water-based ink composition of the present invention is preferably a writing tool provided with a marking pen tip made of a resin processed body or a resin molded body in which pore gaps are formed as a pen tip. In the water-based ink composition of the present invention, the colorant forms loose aggregates, which suppresses aggregation in the pores of the marking pen tip, and the ink is stably ejected from the pen tip of the writing tool. It is suitably used as a writing tool (marking pen) capable of forming a good writing stroke by suppressing writing defects such as blurring.
Further, more preferably as a writing tool containing the water-based ink composition of the present invention, the pen tip is provided with a marking pen tip made of a resin processed body or a resin molded body in which pore gaps are formed, and the marking pen tip is provided. It is attached to the shaft cylinder of the writing tool directly or via a relay member, and further, an ink storage body consisting of a fiber focusing body is built in the shaft cylinder as an ink filling mechanism, and the ink storage body and the marking pen tip are connected. It is a marking pen made by impregnating an ink storage body with an ink composition. In the writing instrument having the above configuration, in addition to the above-mentioned effect that the ink is stably ejected from the pen tip of the writing instrument, the ink occlusion body made of the fiber bundle makes the dispersibility of the loose aggregate of the colorant more stable. It is more preferably used because it can be retained in the ink, suppresses the darkening or lightening of the handwriting, and can form a better handwriting than the one having excellent color development.

Further, since the writing instrument accommodating the water-based ink composition tends to cause writing defects due to the drying of the writing tip, the writing instrument having the above configuration should cover the writing tip in order to prevent the writing tip from drying. It is preferable to provide a cap.

In the present invention, when a reversible thermochromic water-based ink composition using a reversible thermochromic microcapsule pigment or a reversible thermochromic resin particle as a colorant is housed in a writing instrument, writing is performed on the writing surface using this writing instrument. The resulting handwriting can be discolored by rubbing with a finger or by using a heating tool or a cooling tool.
Examples of the heating tool include an energizing heating discoloring tool equipped with a resistance heating element such as a PTC element, a heating discoloring tool filled with a medium such as hot water, a heating discoloring tool using steam or laser light, and application of a hair dryer. However, since the color can be changed by a simple method, a friction member and a friction body are preferable.
Examples of the cooling and heating tool include an energized cold and heat discoloring tool using a Pertier element and the like, a cold and heat discoloring tool filled with a refrigerant such as cold water and ice chips, a cold storage agent, and the application of a refrigerator or a freezer.

As the friction member and the friction body, elastic bodies such as elastomers and plastic foams, which are rich in elasticity and can generate appropriate friction at the time of rubbing to generate frictional heat, are preferable, but plastic molded bodies, stone materials, wood, etc. Metal, cloth and the like can also be used.
The handwriting may be scratched by using a general eraser used for erasing the handwriting with a pencil, but since the eraser is generated at the time of rubbing, the above-mentioned friction member and the above-mentioned friction member in which almost no eraser is generated. A friction body is preferably used.
Examples of the material of the friction member and the friction body include silicone resin and SEBS resin (styrene-ethylene-butadiene-styrene block copolymer). The SEBS resin is more preferably used because the silicone resin tends to adhere to the portion erased by rubbing and the handwriting tends to be repelled when writing repeatedly.

The above-mentioned friction member or friction body may be a member having an arbitrary shape separate from the writing instrument, but by providing the friction member or the friction body in the writing instrument, it can be made excellent in portability. Further, a writing instrument set can also be obtained by combining a writing instrument and a friction member or a friction body having an arbitrary shape separate from the writing instrument.

When the writing instrument is provided with a cap, the place where the friction member or the friction body is provided is not particularly limited. For example, the cap itself is formed of the friction member, the barrel itself is formed of the friction member, or a clip is provided. When provided, the clip itself can be formed of a friction member, or a friction member can be provided at the tip end portion (top) of the cap, the rear end portion of the barrel (the portion where the writing tip portion is not provided), or the like.
When the writing tool is a haunting type writing tool, the place where the friction member or the friction body is provided is not particularly limited. For example, when the barrel itself is formed of the friction member or when a clip is provided, the clip itself is rubbed. It can be formed of a member, or a friction member can be provided at the rear end portion of the barrel (the portion where the writing tip portion is not provided), the knock portion, or the like.

Examples are shown below, but the present invention is not limited thereto. In addition, the part in an Example shows a mass part.

Preparation of reversible thermochromic microcapsule pigment A (a) 3', 6'-bis [phenyl (3-methylphenyl) amino] spiro [isocyanbenzofuran-1 (3H), 9'-[9H] xanthene] as a component 3 parts of -3-on, 3 parts of 1,1-bis (4-hydroxyphenyl) -2-ethylhexane and 5 parts of 2,2-bis (4-hydroxyphenyl) hexafluoropropane as (b) components. (C) A reversible thermochromic composition composed of 50 parts of 4-benzyloxyphenylethyl capricate as a component is put into a mixed solution consisting of 35 parts of an aromatic isocyanate prepolymer and 40 parts of an auxiliary solvent as a wall film material. After that, the mixture was emulsified and dispersed in an 8% aqueous solution of polyvinyl alcohol, and stirring was continued while heating, then 2.5 parts of a water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule dispersion. A reversible thermochromic microcapsule pigment A having an average particle diameter of 1.9 μm was obtained from the above microcapsule dispersion by centrifugation.
The reversible thermochromic microcapsule pigment A had a complete color development temperature t ₁ of −20 ° C. and a complete decolorization temperature t ₄ of 60 ° C., and changed reversibly from blue to colorless due to temperature changes.
Further, the reversible thermochromic microcapsule pigment A in the completely colored state had a specific gravity of 1.08 to 1.09 at 20 ° C. with respect to water.

Preparation of reversible thermochromic microcapsule pigment B (a) 3', 6'-bis [phenyl (3-methylphenyl) amino] spiro [isocyanbenzofuran-1 (3H), 9'-[9H] xanthene] as a component 3 parts of -3-one, 3 parts of 1,1-bis (4-hydroxyphenyl) -2-ethylhexane and 5 parts of 2,2-bis (4-hydroxyphenyl) hexafluoropropane as (b) components. (C) After adding a reversible thermochromic composition consisting of 50 parts of 4-biphenylacetate cyclohexylmethyl as a component into a mixed solution consisting of 35 parts of an aromatic isocyanate prepolymer and 40 parts of an auxiliary solvent as a wall film material. After emulsifying and dispersing in an 8% aqueous solution of polyvinyl alcohol and continuing stirring while heating, 2.5 parts of a water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule dispersion. A reversible thermochromic microcapsule pigment B having an average particle size of 1.9 μm was obtained from the above microcapsule dispersion by centrifugation.
The reversible thermochromic microcapsule pigment B had a complete color development temperature t ₁ of −20 ° C. and a complete decolorization temperature t ₄ of 62 ° C., and changed reversibly from blue to colorless due to temperature changes.
Further, the reversible thermochromic microcapsule pigment B in the completely colored state had a specific gravity of 1.13 to 1.14 at 20 ° C. with respect to water.

Example 1
Preparation of Aqueous Ink Composition A 10% aqueous solution was prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-03 (concentration: 20%)] and water.
2.5 parts of the above 10% aqueous solution, 0.4 part of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsparse 43000], and preservative (2-pyridinethiol 1-oxide sodium) [Manufactured by Lonza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Lonza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 25 parts of glycerin, 0.01 part of antifoaming agent and 51.69 parts of water were mixed to prepare a vehicle.
Further, 20 parts of resin particles [manufactured by Nippon Shokubai Co., Ltd., product name: Epostal MA-1002] and the above vehicle were mixed to prepare an aqueous ink composition.
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 8.

Preparation of a filling type writing tool The above-mentioned water-based ink composition is impregnated in an ink occlusion body in which a polyester sliver is coated with a synthetic resin film, and the polyester sliver is housed in a barrel made of polypropylene resin. A resin-processed pen body (bullet type) made of polyester fiber was assembled in a connected state, a cap was attached, and three filling-type writing tools (marking pens) were manufactured.

Example 2
Preparation of Reversible Thermal Discoloration Aqueous Ink Composition A 10% aqueous solution was prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-03 (concentration: 20%)] with water.
2.5 parts of the above 10% aqueous solution, 0.4 part of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsparse 43000], and preservative (2-pyridinethiol 1-oxide sodium) [Manufactured by Lonza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Lonza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 25 parts of glycerin, 0.01 part of antifoaming agent and 48.69 parts of water were mixed to prepare a vehicle.
Further, 23 parts of the reversible thermochromic microcapsule pigment A (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 8.

Preparation of a filling type writing instrument (see Fig. 4)
The above ink composition is impregnated in an ink occlusion body 2 in which a polyester sliver is coated with a synthetic resin film, and the ink composition is housed in a shaft tube 4 made of polypropylene resin. The resin-processed pen body 3 (chisel type) was assembled in a connected state, and the cap 6 was attached to produce three filling type writing tools 1 (marking pens).
SEBS resin is attached to the top of the cap as a friction member 7.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 3
Preparation of Reversible Thermal Discoloration Aqueous Ink Composition A 10% aqueous solution was prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-03 (concentration: 20%)] with water.
2.5 parts of the above 10% aqueous solution, 0.4 parts of an acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsparse 43000], and an antiseptic (2-pyridinethiol 1-oxide sodium) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 10 parts of glycerin, 0.1 part of defoamer, 1 part of pH adjuster (10% phosphoric acid aqueous solution), 54.6 parts of water, and then specific gravity adjuster (polytungsten). (Sodium acid) [manufactured by SOMETU, product name: SPT] 10 parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment B (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific density of 1.155 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.01 to 1.02 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 8.

Preparation of a filling type writing instrument (see Fig. 5)
The above ink composition is impregnated in an ink occlusion body 2 in which a polyester sliver is coated with a synthetic resin film, and the ink composition is housed in a shaft tube 4 made of polypropylene resin. Assemble a resin-processed pen body 3 (bullet type) made of a polypropylene extruded body having a plurality of ink lead-out holes extending to the connected state, attach a cap 6, and attach three filling type writing tools 1 (marking pen). Made.
SEBS resin is attached to the top of the cap as a friction member 7.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 4
Preparation of reversible thermochromic water-based ink composition A 10% aqueous solution is prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-HCl-03 (concentration: 40%)] and water. did.
2.5 parts of the above 10% aqueous solution, 0.4 parts of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsperse 43000], and preservative (2-pyridinethiol-sodium oxide) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 24 parts of glycerin, 0.1 part of defoaming agent, and 45.6 parts of water are mixed, and then the specific gravity adjusting agent (sodium polytungstate) [manufactured by SOMETU, product name: SPT] 6 Parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment A (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific gravity of 1.150 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.06 to 1.07 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 4.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 5
Preparation of reversible thermochromic water-based ink composition A 10% aqueous solution is prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-HCl-3L (concentration: 50%)] and water. did.
2.5 parts of the above 10% aqueous solution, 0.4 parts of an acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsparse 43000], and an antiseptic (2-pyridinethiol 1-oxide sodium) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 10 parts of glycerin, 0.1 part of defoamer, 1 part of pH adjuster (10% phosphoric acid aqueous solution), 54.6 parts of water, and then specific gravity adjuster (polytungsten). (Sodium acid) [manufactured by SOMETU, product name: SPT] 10 parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment B (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific density of 1.155 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.01 to 1.02 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 3.2.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 6
Preparation of reversible thermochromic water-based ink composition A 10% aqueous solution is prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-D41-HCl (concentration: 40%)] and water. did.
2.5 parts of the above 10% aqueous solution, 0.4 part of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsparse 43000], and preservative (2-pyridinethiol 1-oxide sodium) [Manufactured by Lonza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Lonza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 25 parts of glycerin, 0.01 part of antifoaming agent, and 50.69 parts of water were mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment A (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 4.

Preparation of a filling type writing instrument (see Fig. 6)
The above-mentioned water-based ink composition is impregnated in an ink occlusion body 2 in which a polyester sliver is coated with a synthetic resin film, and is housed in a shaft cylinder 4 made of polypropylene resin. A resin-processed pen body 3 (bullet type) made of the above was assembled in a connected state, a cap 6 was attached, and three filling-type writing tools 1 (marking pens) were manufactured.
SEBS resin is attached to the top of the cap as a friction member 7.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 7
Preparation of reversible thermochromic water-based ink composition A 10% aqueous solution is prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-D19-HCl (concentration: 21%)] and water. did.
2.5 parts of the above 10% aqueous solution, 0.4 parts of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsperse 43000], and preservative (2-pyridinethiol-sodium oxide) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 24 parts of glycerin, 0.1 part of defoaming agent, and 45.6 parts of water are mixed, and then the specific gravity adjusting agent (sodium polytungstate) [manufactured by SOMETU, product name: SPT] 6 Parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment A (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific gravity of 1.150 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.06 to 1.07 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 7.6.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 8
Preparation of Reversible Thermal Discoloration Aqueous Ink Composition A 10% aqueous solution was prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-D19A (concentration: 20%)] and water.
2.5 parts of the above 10% aqueous solution, 0.4 parts of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsperse 43000], and preservative (2-pyridinethiol-sodium oxide) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 24 parts of glycerin, 0.1 part of defoaming agent, and 45.6 parts of water are mixed, and then the specific gravity adjusting agent (sodium polytungstate) [manufactured by SOMETU, product name: SPT] 6 Parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment A (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific gravity of 1.150 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.06 to 1.07 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 8.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 9
Preparation of Reversible Thermal Discoloration Aqueous Ink Composition A 10% aqueous solution was prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAS-21CL (concentration: 25%)] and water.
2.5 parts of the above 10% aqueous solution, 0.4 parts of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsperse 43000], and preservative (2-pyridinethiol-sodium oxide) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 24 parts of glycerin, 0.1 part of defoaming agent, and 45.6 parts of water are mixed, and then the specific gravity adjusting agent (sodium polytungstate) [manufactured by SOMETU, product name: SPT] 6 Parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment A (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific gravity of 1.150 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.06 to 1.07 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 6.4.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 10
Preparation of Reversible Thermal Discoloration Aqueous Ink Composition A 10% aqueous solution was prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-AC5050A (concentration: 15%)] and water.
2.5 parts of the above 10% aqueous solution, 0.4 parts of an acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsparse 43000], and an antiseptic (2-pyridinethiol 1-oxide sodium) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 10 parts of glycerin, 0.1 part of defoamer, 1 part of pH adjuster (10% phosphoric acid aqueous solution), 54.6 parts of water, and then specific gravity adjuster (polytungsten). (Sodium acid) [manufactured by SOMETU, product name: SPT] 10 parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment B (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific density of 1.155 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.01 to 1.02 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 10.7.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 11
Preparation of Reversible Thermal Discoloration Aqueous Ink Composition A 10% aqueous solution was prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAA-N5000 (concentration: 15%)] and water.
2.5 parts of the above 10% aqueous solution, 0.4 parts of an acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsparse 43000], and an antiseptic (2-pyridinethiol 1-oxide sodium) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 10 parts of glycerin, 0.1 part of defoamer, 1 part of pH adjuster (10% phosphoric acid aqueous solution), 54.6 parts of water, and then specific gravity adjuster (polytungsten). (Sodium acid) [manufactured by SOMETU, product name: SPT] 10 parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment B (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific density of 1.155 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.01 to 1.02 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 10.7.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Example 12
Preparation of reversible thermochromic water-based ink composition A 10% aqueous solution is prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAS-H-10L (concentration: 28%)] and water. did.
2.5 parts of the above 10% aqueous solution, 0.4 parts of an acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsparse 43000], and an antiseptic (2-pyridinethiol 1-oxide sodium) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 10 parts of glycerin, 0.1 part of defoamer, 1 part of pH adjuster (10% phosphoric acid aqueous solution), 54.6 parts of water, and then specific gravity adjuster (polytungsten). (Sodium acid) [manufactured by SOMETU, product name: SPT] 10 parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment B (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific density of 1.155 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.01 to 1.02 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 5.7.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Comparative Example 1
Preparation of water-based ink composition Acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsperse 43000] 0.4 part and preservative (2-pyridinethiol 1-oxide sodium) [Lonza Japan Co., Ltd. ), Product name: Sodium omadin] 0.2 parts, Preservative (3-iodo-2-propinyl N-butylcarbamate) [Lonza Japan Co., Ltd., Product name: Glycacil 2000] 0.2 parts, 25 parts of glycerin, 0.01 part of antifoaming agent and 54.19 parts of water were mixed to prepare a vehicle.
Further, 20 parts of resin particles [manufactured by Nippon Shokubai Co., Ltd., product name: Epostal MA-1002] and the above vehicle were mixed to prepare an aqueous ink composition.

Preparation of Filling-type Writing Instruments Three filling-type writing instruments (marking pens) were produced in the same procedure as in Example 1.

Comparative Example 2
Preparation of reversible thermochromic water-based ink composition 0.4 part of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsperse 43000] and preservative (2-pyridinethiol 1-oxide sodium) [ Lonza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [Lonza Japan Co., Ltd., product name: Glycacil 2000] 0. 2 parts, 25 parts of glycerin, 0.01 part of antifoaming agent and 51.19 parts of water were mixed to prepare a vehicle.
Further, 23 parts of the reversible thermochromic microcapsule pigment A (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..

Preparation of a filling type writing instrument (see Fig. 4)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 2.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Comparative Example 3
Preparation of reversible thermochromic water-based ink composition A 10% aqueous solution is prepared by mixing a cationic polymer [manufactured by Nittobo Medical Co., Ltd., product name: PAS-H-1L (concentration: 28%)] and water. did.
2.5 parts of the above 10% aqueous solution, 0.4 parts of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsperse 43000], and preservative (2-pyridinethiol-sodium oxide) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 24 parts of glycerin, 0.1 part of defoaming agent, and 45.6 parts of water are mixed, and then the specific gravity adjusting agent (sodium polytungstate) [manufactured by SOMETU, product name: SPT] 6 Parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment A (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific gravity of 1.150 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.06 to 1.07 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 5.7.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Comparative Example 4
Preparation of Reversible Thermal Discoloration Aqueous Ink Composition A 10% aqueous solution was prepared by mixing a cationic polymer [Nittobo Medical Co., Ltd., product name: PAA-1151 (concentration: 20%)] with water.
2.5 parts of the above 10% aqueous solution, 0.4 parts of acrylic polymer dispersant [manufactured by Japan Lubrizol Co., Ltd., product name: Solsperse 43000], and preservative (2-pyridinethiol-sodium oxide) [Manufactured by Ronza Japan Co., Ltd., product name: Sodium omadin] 0.2 parts and preservative (3-iodo-2-propinyl N-butylcarbamate) [manufactured by Ronza Japan Co., Ltd., product name: Glycacil 2000] 0 .2 parts, 24 parts of glycerin, 0.1 part of defoaming agent, and 45.6 parts of water are mixed, and then the specific gravity adjusting agent (sodium polytungstate) [manufactured by SOMETU, product name: SPT] 6 Parts were added and mixed to prepare a vehicle.
Further, 21 parts of the reversible thermochromic microcapsule pigment A (preliminarily cooled to −20 ° C. or lower to develop a blue color) and the above vehicle were mixed to prepare a reversible thermochromic water-based ink composition. ..
The above vehicle had a specific gravity of 1.150 measured at 20 ° C. using water as a reference substance, and the specific gravity of the vehicle was 1.06 to 1.07 times the specific density of the reversible thermochromic microcapsule pigment. ..
The mass ratio of the cationic polymer: the acrylic polymer dispersant is 1: 8.

Preparation of a filling type writing instrument (see Fig. 5)
Three filling-type writing tools 1 (marking pens) were produced in the same procedure as in Example 3.

Blue characters (handwriting) were formed by writing on the paper using the above marking pen.
The handwriting is blue in a room temperature (20 ° C.) environment, and when it is rubbed with a friction member attached to the cap, the handwriting is discolored and becomes colorless, and this state is maintained in a room temperature environment. When cooled to -20 ° C or lower, the original blue color was restored. The above-mentioned discoloration behavior could be reproduced repeatedly.

Viscosity measurement For each water-based ink composition prepared in Examples 1 to 12 and Comparative Examples 1 to 4, BL type rotational viscometer [manufactured by Toki Sangyo Co., Ltd., product name: TVB-M type viscometer L type Using a rotor], the viscosity was measured under the condition of a rotation speed of 30 rpm in an environment of room temperature (20 ° C.).

Surface Tension Measurement For each water-based ink composition prepared in Examples 1 to 12 and Comparative Examples 1 to 4, an automatic surface tension meter [manufactured by Kyowa Interface Science Co., Ltd., product name: DY-300] was used. The surface tension was measured by the vertical plate method using a glass plate in a room temperature (20 ° C.) environment.

pH measurement For each of the aqueous ink compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 4, a pH meter [manufactured by Toa DK Co., Ltd., product name: IM-40S] was used at room temperature (20 ° C.). ) The pH was measured in the environment.

Evaluation of Dispersibility of Colorant Each aqueous ink composition prepared in Examples 1 to 12 and Comparative Examples 1 to 4 was placed in a screw tube bottle and allowed to stand in a room temperature (20 ° C.) environment for 30 days. The dispersibility of the colorant after standing was evaluated according to the following criteria.
A: The colorant did not separate and could be easily redispersed.
B: The colorant separated to form a hard cake layer and could not be redispersed.

Evaluation of initial writing performance For each of the three writing tools produced in Example 1 and Comparative Example 1, A4 size black paper [manufactured by Nagatoya Shoten Co., Ltd., product name: color paper] under a room temperature (20 ° C) environment. A4 medium-thick mouth (thickness: 0.09 mm, density: 80 g / m ² )] (vertical) 15 elliptical circles with a major axis of 15 mm and a minor axis of about 8 mm per row in the direction parallel to the lateral direction. , I wrote continuously by hand in a spiral so that the circles touched each other, and I wrote this continuously for 10 lines.
For each of the three writing tools produced in Examples 2 to 12 and Comparative Examples 2 to 4, the marking pen provided with the bullet-shaped resin-processed pen body was a blank paper of A4 size under a room temperature (20 ° C.) environment. In the direction parallel to the lateral direction (vertical direction), 15 elliptical circles with a major axis of 15 mm and a minor axis of about 8 mm are continuously written by hand in a spiral so that the circles touch each other, and 10 lines are written. I wrote for a minute in a row. In addition, the marking pen equipped with a chisel-shaped resin-processed pen body adheres the wide surface of the pen body to the paper surface in a direction parallel to the short side of A4 size blank paper (vertical direction) in an environment of room temperature (20 ° C). Then, a 15 cm straight line was written, and this was done for 10 lines. As the blank paper, writing paper A conforming to the old JIS P3201 was used.
Next, the obtained handwriting was visually confirmed, and the initial writing performance was evaluated according to the following criteria.
A: There was no blurring in the handwriting, and a handwriting with good color development was obtained.
B: There was some blurring in the handwriting or the handwriting density was a little low, but there was no problem in practical use.
C: A large number of blurs were confirmed in the handwriting, the handwriting density was low, or the handwriting was impossible, and a handwriting with good color development could not be obtained.

Vibration test Put a cap on one of each of the three writing instruments used in the above-mentioned writing test, and put the writing tip upward (upright state) on the shaking machine [manufactured by Titec Co., Ltd., product name: Recipo Shaker]. ), And a vertical vibration was applied at 284 rpm for 12 hours in an environment of 40 ° C.

Storage over time Of the three writing instruments used in the above-mentioned writing test, put caps on the remaining two, and keep the writing tip facing up (upright) for 7 days in a room temperature (20 ° C) environment. And left to stand for 15 days.

Evaluation of writing performance after vibration test Each writing instrument after vibration test was subjected to a writing test by the same test method as the above-mentioned evaluation of initial writing performance.
Next, the obtained handwriting was visually confirmed, and the writing performance after the vibration test was evaluated according to the following criteria.
A: It was at the same level as the initial stage, and handwriting with good color development was obtained.
B: Compared with the initial stage, blurring was slightly confirmed in the handwriting or the handwriting density was slightly low, but it was at a level where there was no problem in practical use.
C: Compared with the initial stage, a large amount of blurring was confirmed in the handwriting, the handwriting density was low, or the handwriting was impossible, and a handwriting with good color development could not be obtained.

Evaluation of writing performance after storage over time Each writing instrument stored at room temperature for 7 days and 15 days was subjected to a writing test by the same test method as the above-mentioned evaluation of initial writing performance.
Next, the obtained handwriting was visually confirmed, and the writing performance after storage over time was evaluated according to the following criteria.
A: It was at the same level as the initial stage, and handwriting with good color development was obtained.
B: Compared with the initial stage, blurring was slightly confirmed in the handwriting or the handwriting density was slightly low, but it was at a level where there was no problem in practical use.
C: Compared with the initial stage, a large amount of blurring was confirmed in the handwriting, the handwriting density was low, or the handwriting was impossible, and a handwriting with good color development could not be obtained.

Tables 1 and 2 below show the values of viscosity, surface tension, and pH of each aqueous ink composition prepared in Examples 1 to 12 and Comparative Examples 1 to 4.
In addition, Tables 3 and 4 show the evaluation of the dispersibility of the colorant in each of the water-based ink compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 4, and the initial writing performance of each of the produced writing instruments. The results of the evaluation, the evaluation of the writing performance after the vibration test, and the evaluation of the writing performance after storage for 7 days and 15 days are shown.

t ₁ complete color development temperature t ₂ color development start temperature t ₃ complete decolorization start temperature t ₄ complete decolorization temperature T ₁ complete decolorization temperature T ₂ decolorization start temperature T ₃ color development start temperature T ₄ complete color development temperature ΔH hysteresis width 1 Writing tool 2 Ink storage body 3 Resin processed pen body (chip)
4 Shaft cylinder 5 Holder 6 Cap 7 Friction member

Claims (14)

A water-based ink for writing tools, which comprises a colorant selected from pigments or resin particles, at least water, a cationic polymer selected from the following formulas (1) to (5), and a vehicle containing an acrylic polymer dispersant. Composition.

(In the formula, n1 indicates 0 or an integer of 1, X ₁ indicates any of hydrochloric acid, amidosulfuric acid, and acetic acid, n indicates a natural number, and the mass average molecular weight is in the range of 500 to 200,000. be.)

(In the formula, n2a and n2b independently indicate an integer of 0 or 1, X _2a and X _2b independently indicate either hydrochloric acid, amidosulfate, or acetic acid, and m and n respectively. It independently shows a natural number, and its mass average molecular weight is in the range of 500 to 200,000.)

(In the formula, n3a and n3b independently indicate an integer of 0 or 1, X _3a and X _3b independently indicate either hydrochloric acid, amidosulfate, or acetic acid, and m and n respectively. It independently shows a natural number, and its mass average molecular weight is in the range of 500 to 200,000.)

(In the formula, R ₁ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, n4 represents an integer of 0 or 1, and X ₄ represents hydrochloric acid, amidosulfate, or acetic acid. Either is indicated, n indicates a natural number, and the mass average molecular weight is in the range of 500 to 200,000.)

(In the formula, R ₂ and R ₃ each independently represent a linear or branched alkyl group having 1 to 3 carbon atoms, and X ₅ is a chlorine atom, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ . In addition, the mass average molecular weight is in the range of 10,000 to 300,000.) The water-based ink composition for stationery according to claim 1, wherein n2a and n2b are integers of 0 or 1, or n3a and n3b are integers of 0 or 1. The water-based ink composition for stationery according to claim 2, wherein X _2a and X _2b are the same, or X _3a and X _3b are the same. The water-based ink composition for writing tools according to any one of claims 1 to 3, wherein the mass ratio of the cationic polymer to the acrylic polymer dispersant is 1: 2.5 to 1:16. The water-based ink composition for writing tools according to any one of claims 1 to 4, wherein the viscosity at a rotation speed of 30 rpm by a BL type rotational viscometer at 20 ° C. is 1 to 20 mPa · s. The water-based ink composition for stationery according to any one of claims 1 to 5, wherein the average particle size of the colorant is in the range of 0.01 to 5 μm. The pigment is at least from (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of the components (a) and (b). The water-based ink composition for writing instruments according to any one of claims 1 to 6, which is a reversible thermochromic microcapsule pigment containing a reversible thermochromic composition. When the component (c) is in the range of 60 to 90% by mass with respect to the total amount of the reversible thermochromic composition, the mass average molecular weight is 250 or more, and water is used as a reference substance at 20 ° C. The water-based ink composition for writing instruments according to claim 7, wherein the reversible thermochromic microcapsule pigment in a completely color-developed state has a specific gravity of 1.05 to 1.20. The water-based ink composition for writing tools according to any one of claims 1 to 8, wherein the acrylic polymer dispersant is a comb-shaped polymer dispersant having a carboxy group in the side chain. The water-based ink composition for writing tools according to any one of claims 1 to 9, wherein the vehicle contains a specific gravity adjusting agent consisting of an oxygen acid of a Group 6 element having an atomic weight of 90 to 185 or a salt thereof. A writing tool containing the water-based ink composition for writing tools according to any one of claims 1 to 10. The writing tool according to claim 11, wherein the writing tool includes a marking pen tip made of a resin processed body or a resin molded body having pores formed therein. A marking pen having an ink storage body made of a fiber focusing body built in the shaft cylinder of the writing tool, and the ink storage body and the marking pen tip connected to the ink storage body. The writing tool according to claim 12, which is a marking pen impregnated with the water-based ink composition for writing tools. The writing tool according to any one of claims 11 to 13, further comprising a friction member that discolors the handwriting by the writing tool by frictional heat.

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