阅读说明：本技术 可逆热变色性书写工具用水性墨液组合物、以及内置其的替换笔芯及水性圆珠笔 (Water-based ink composition for reversible thermal discoloration writing instrument, refill containing the same, and water-based ballpoint pen ) 是由 桝重直登 小椋麻美子 大野逸香 于 2020-03-30 设计创作，主要内容包括：本发明提供一种书写性优异,并且着色剂的凝集、组合物的粘度上升、笔迹浓度的下降等问题少的可逆热变色性水性墨液组合物、及内置其的替换笔芯及水性圆珠笔。本发明是可逆热变色性水性墨液组合物,其含有由有机树脂形成的微胶囊中内包可逆热变色性组合物而成的可逆热变色性微胶囊颜料、N-乙烯基-2-吡咯烷酮聚合物、甘油及水；并且将所述可逆热变色性微胶囊颜料、所述N-乙烯基-2-吡咯烷酮聚合物及所述甘油相对于所述墨液组合物的总质量的含有率(质量％)设为P-(MC)、P-(PVP)及P-(G)时,0.3≤P-(MC)/(P-(PVP)+P-(G))≤4并且0.2≤P-(PVP)/P-(G)≤5。并且提供内置所述组合物的替换笔芯及水性圆珠笔。(The invention provides a reversible thermal discoloration aqueous ink composition which is excellent in writing performance and has few problems such as aggregation of a colorant, increase in the viscosity of the composition, and decrease in the writing density, and a refill and an aqueous ball-point pen incorporating the same. The invention is a reversible thermal discoloration aqueous ink composition, which comprises a reversible thermal discoloration microcapsule pigment formed by encapsulating a reversible thermal discoloration composition in a microcapsule formed by an organic resin, an N-vinyl-2-pyrrolidone polymer, glycerol and water; and the content ratio (% by mass) of the reversible thermal discoloration microcapsule pigment, the N-vinyl-2-pyrrolidone polymer, and the glycerin with respect to the total mass of the ink composition is P MC 、P PVP And P G When P is not less than 0.3 MC /(P PVP +P G ) P is not less than 4 and not more than 0.2 PVP /P G Less than or equal to 5. And a refill for refill and a ballpoint pen containing the composition.)

1. A reversible thermal discoloration aqueous ink composition comprising a reversible thermal discoloration microcapsule pigment, an N-vinyl-2-pyrrolidone polymer having a polymerization degree of 2 to 20, glycerin and water,

the reversible thermal discoloration microcapsule pigment is a reversible thermal discoloration composition containing a component (a) which is an electron donating color developing organic compound, a component (b) which is an electron accepting compound, and a component (c) which is a reaction medium determining a temperature at which a color development reaction of the component (a) and the component (b) occurs, in a microcapsule made of an organic resin, and the reversible thermal discoloration microcapsule pigment is obtained by encapsulating the reversible thermal discoloration composition in a microcapsule

The contents of the reversible thermal discoloration microcapsule pigment, the N-vinyl-2-pyrrolidone polymer, and the glycerin in percentage by mass with respect to the total mass of the ink composition are respectively defined as P_MC、P_PVPAnd P_GAnd then, satisfy:

0.3≤P_MC/(P_PVP+P_G) 4 or less and

0.2≤P_PVP/P_G≤5。

2. the composition of claim 1, said P_MC5 to 40 mass%.

3. The ink composition of claim 1 or 2, wherein P is_MC5 to 40 mass% of the above P_PVP1 to 20 mass% of the above P_G1 to 20 mass%.

4. The ink composition of any one of claims 1 to 3, said P_MCThe P_PVPAnd said P_GThe total of (2) is 20 to 50 mass%.

5. The ink composition according to any one of claims 1 to 4, further comprising a polysaccharide.

6. The ink composition according to claim 5, wherein the polysaccharide is succinoglycan or xanthan gum.

7. A refill for replacement pen, which contains the reversible thermally discoloration aqueous ink composition according to any one of claims 1 to 6.

8. A water-based ball-point pen containing the reversible thermal discoloration water-based ink composition according to any one of claims 1 to 6.

9. The water-based ballpoint pen as described in claim 8, which comprises an in-out mechanism.

10. The water-based ballpoint pen as described in claim 8 or 9, wherein a friction member is fixed thereto.

Technical Field

The present invention relates to an aqueous ink composition for a reversible thermochromic writing instrument, and a refill and an aqueous ballpoint pen incorporating the same. More particularly, the present invention relates to an aqueous ink composition for a reversible thermal discoloration writing instrument, which exhibits a large hysteresis characteristic according to a change in temperature and exhibits color development and discoloration, and which can reversibly maintain either a colored state or a discolored state even after application of heat or cooling necessary for discoloration is removed, and a refill and an aqueous ballpoint pen incorporating the same.

Background

Conventionally, there have been proposed an aqueous ink composition for a reversible thermochromic writing instrument capable of forming a writing instrument or the like in which the state before and after discoloration can be stored in a certain temperature range such as a normal temperature range in a reversible manner, and a writing instrument incorporating the same. Such writing instruments are proposed in many fields, such as ball-point pens, marker pens, pens or solid writing forms. While the thermochromic property is an important property in a writing instrument containing the aqueous ink composition for a reversible thermochromic writing instrument, various properties such as high writing properties, high writing density, and high optical rotation resistance are desired as in a conventional writing instrument. However, since the colorant used in the thermochromic composition is specific, it is difficult to obtain excellent characteristics even when the same material or the same blending ratio as those of the usual ink composition is used. In particular, when a microcapsule pigment in which a reversible thermal discoloration composition is encapsulated in a microcapsule is used, it is necessary to increase the blending ratio of the pigment in order to achieve a high concentration, and it is difficult to directly apply the conventional ink composition ratio.

In particular, an aqueous ink composition for reversible thermal discoloration writing instruments contains an organic material as a reversible thermal discoloration colorant, but may interact with other organic materials contained in the composition. For example, aggregation of organic colorant particles, an increase in viscosity of the composition, a decrease in writing density, deterioration in writing property, and the like may occur.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2009-292878

Disclosure of Invention

Problems to be solved by the invention

The present invention aims to solve the problems of an aqueous ink composition for a writing instrument containing a reversible thermal discoloration colorant and to improve various properties.

Means for solving the problems

The reversible thermal discoloration aqueous ink composition of the present invention is characterized in that: contains reversible thermal discoloration microcapsule pigment, N-vinyl-2-pyrrolidone polymer with the polymerization degree of 2-20, glycerol and water,

the reversible thermal discoloration microcapsule pigment is a reversible thermal discoloration composition comprising a component (a) which is an electron donating color former organic compound, a component (b) which is an electron accepting compound, and a component (c) which is a reaction medium determining a temperature at which a color development reaction of the component (a) and the component (b) occurs, the reversible thermal discoloration microcapsule pigment being formed by encapsulating a microcapsule composed of an organic resin in the reversible thermal discoloration composition,

and is

The contents of the reversible thermal discoloration microcapsule pigment, the N-vinyl-2-pyrrolidone polymer, and the glycerin in percentage by mass with respect to the total mass of the ink composition are respectively defined as P_MC、P_PVPAnd P_GAnd then, satisfy:

0.3≤P_MC/(P_PVP+P_G) 4 or less and

0.2≤P_PVP/P_G≤5。

in addition, the refill for replacement of the present invention is characterized in that: the reversible thermal discoloration ink composition is incorporated.

Further, the water-based ballpoint pen of the present invention is characterized in that: the reversible thermal discoloration ink composition is incorporated.

Effects of the invention

The present invention provides a reversible thermal discoloration ink composition which is less susceptible to writing, particularly to blurring during writing when the pen point is dry. Further, the ink composition is excellent in effects of suppressing aggregation of organic colorant particles, an increase in viscosity of the composition, a decrease in writing density, and the like.

Drawings

Fig. 1 is a graph illustrating a hysteresis characteristic of a color density-temperature curve of a thermochromic color memory composition.

Fig. 2 is a graph of hysteresis characteristics of color density-temperature curves of other thermochromic color memory compositions.

FIG. 3 is a sectional view showing an example of a ballpoint pen according to embodiment 1 of the present invention.

FIG. 4 is a sectional view showing an example of a ballpoint pen according to embodiment 2 of the present invention.

FIG. 5 is a sectional view showing an example of a refill for a ballpoint pen of the present invention.

Fig. 6 is a sectional view showing an example of a ballpoint pen and a nib (ballpoint pen tip) provided in the refill for a ballpoint pen of the present invention.

Fig. 7 is an X-X sectional view of fig. 6.

FIG. 8 shows the ink composition of the example used for handwriting after evaluation of drying resistance.

FIG. 9 shows a handwriting after evaluation of drying resistance when the ink composition of comparative example was used.

Detailed Description

The embodiments of the present invention will be described in detail below.

Water-based ink composition for reversible thermal discoloration writing instrument

The aqueous ink composition for reversible thermal discoloration writing instruments (hereinafter, may be simply referred to as "ink composition") of the present invention contains a reversible thermal discoloration microcapsule pigment, a polymer of N-vinyl-2-pyrrolidone, glycerin, and water. These components are described in detail below.

< reversible thermal discoloration microcapsule pigment >

In the present invention, the reversible thermochromic microcapsule pigment (hereinafter, may be simply referred to as "microcapsule pigment") contains (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium which reversibly generates an electron transfer reaction between the component (a) and the component (b) in a specific temperature range.

As the microcapsule pigment, those described in Japanese patent publication (Kokoku) No. 51-44706, Japanese patent publication (Kokoku) No. 51-44707, and Japanese patent publication (Kokoku) No. 1-29398 can be used. These microcapsule pigments change color before and after a specific temperature (color change temperature) as a boundary, and show a discolored state in a temperature region of not lower than the high-temperature-side color change temperature and a developed state in a temperature region of not higher than the low-temperature-side color change temperature. And has the following features: in the normal temperature region, only one of the two states is present, and the other state is maintained during the application of heat or cooling necessary for expressing the state, but if there is no application of heat or cooling, the state returns to the state present in the normal temperature region. Here, the composition contained in these microcapsule pigments is a reversible thermal discoloration composition of a heat discoloration type (discolored by heating and developed by cooling) having a characteristic of a small temperature width (hereinafter referred to as retardation width Δ H) indicating the degree of retardation (Δ H is 1 to 7 ℃).

In addition, the microcapsule pigments described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936 and the like can also be used. These microcapsule pigments exhibit a large hysteresis property (. DELTA.H.8 to 50 ℃ C.). That is, the color change is performed along a path in which the temperature is increased from the low temperature side lower than the color change temperature region in the shape of a curve obtained by plotting the change in the coloring density due to the temperature change, and conversely, the temperature is decreased from the high temperature side higher than the color change temperature region (see fig. 2).

The hysteresis characteristic in the color density-temperature curve of the reversible thermal discoloration composition will be described in detail below with reference to the drawings.

In fig. 2, the vertical axis represents color density, and the horizontal axis represents temperature. The change in color density caused by the change in temperature proceeds along the arrow. Here, A represents the temperature t at which the completely discolored state is reached₄(hereinafter, referred to as a complete fading temperature), B represents a temperature t at which fading starts₃(hereinafter, referred to as a discoloration-starting temperature), and C represents a temperature t at which color development starts₂(hereinafter, referred to as a color development start temperature), and D represents a temperature t at which a completely developed state is reached₁(hereinafter, referred to as a complete color development temperature).

Color change temperature region t₁And t₄The temperature range therebetween can be either a colored state or a discolored state, and is defined as t in a region where the difference in color density is large₂And t₃Middle temperatureThe temperature zone is a substantially two-phase holding temperature zone.

The length of the line segment EF is a measure indicating the contrast of color change, the length of the line segment HG passing through the midpoint of the line segment EF is the hysteresis width Δ H, and if the Δ H value is small, only a specific one of the two states before and after color change in the normal temperature region can exist. Further, if the Δ H value is large, the respective states before and after the discoloration can be easily maintained.

As a reversible thermal discoloration composition having color memory, specifically, the complete color development temperature t₁Specifically, the temperature is-50 to 0 ℃, preferably-40 to-5 ℃, more preferably-30 to-10 ℃ and the complete fading temperature t is obtained only in a freezing chamber, a cold region and the like₄Specifically, the temperature obtained from a heating body around a hair dryer or the like, such as friction heat from an abrasive body, is 45 to 95 ℃, preferably 50 to 90 ℃, and more preferably 60 to 80 ℃, and the Δ H value is 40 to 100 ℃, whereby the color exhibited in a normal state (daily life temperature range) can be effectively maintained.

The following compounds are specifically exemplified for each component (a), (b) and (c).

The organic compound (a) of the present invention, which is an electron-donating color former, is a color-determining component, and is a compound that develops color by donating electrons to the component (b) serving as a developer.

The electron donating color former organic compound is preferably a phthalide compound, a fluoran compound, a styrylquinoline (styrynoquinoline) compound, a diaza rhodamine lactone compound, a pyridine compound, a quinazoline compound, a bisquinazoline compound, or the like, and among these, a phthalide compound and a fluoran compound are preferable.

Examples of the phthalide compound include: and a phenyl indole phthalide compound, an indole phthalide compound, a diphenyl methane azaphthalide compound, a phenyl indole azaphthalide compound, and derivatives thereof, and among these, a phenyl indole azaphthalide compound and derivatives thereof are preferable.

Further, examples of the fluoran compound include: aminofluoran compounds, alkoxyfluoran compounds and their derivatives.

The following are examples of compounds that can be used as component (a).

3, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,

3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide,

3, 3-bis (1-n-butyl-2-methylindol-3-yl) phthalide,

3, 3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,

3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,

3- (2-hexyloxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,

3- [ 2-ethoxy-4- (N-ethylphenylamino) phenyl ] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,

3- (2-acetamide-4-diethylaminophenyl) -3- (1-propylindol-3-yl) -4-azaphthalide,

3, 6-bis (diphenylamino) fluorane,

3, 6-dimethoxy fluorane,

3, 6-di-n-butoxy fluorane,

2-methyl-6- (N-ethyl-N-p-toluylamino) fluoran,

3-chloro-6-cyclohexylaminofluoran,

2-methyl-6-cyclohexylaminofluoran,

2- (2-chloroamino) -6-dibutylamino fluorane,

2- (2-chlorophenylamino) -6-di-n-butylaminofluorane,

2- (3-trifluoromethylphenylamino) -6-diethylaminofluorane,

2- (3-trifluoromethylphenylamino) -6-dipentylaminofluorane,

2- (dibenzylamino) -6-diethylaminofluorane,

2- (N-methylphenylamino) -6- (N-ethyl-N-p-toluylamino) fluoran,

1, 3-dimethyl-6-diethylaminofluorane,

2-chloro-3-methyl-6-diethylaminofluorane,

2-phenylamino-3-methyl-6-diethylaminofluorane,

2-phenylamino-3-methoxy-6-diethylaminofluorane,

2-phenylamino-3-methyl-6-di-n-butylaminofluoran,

2-phenylamino-3-methoxy-6-di-n-butylaminofluoran,

2-xylenylamino-3-methyl-6-diethylaminofluorane,

2-phenylamino-3-methyl-6- (N-ethyl-N-p-toluylamino) fluoran,

1, 2-benzo-6-diethylaminofluorane,

1, 2-benzo-6- (N-ethyl-N-isobutylamino) fluoran,

1, 2-benzo-6- (N-ethyl-N-isopentylamino) fluoran,

2- (3-methoxy-4-dodecyloxystyrene) quinoline,

Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (diethylamino) -8- (diethylamino) -4-methyl,

Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl,

Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (di-n-butylamino) -8- (diethylamino) -4-methyl,

Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (di-N-butylamino) -8- (N-ethyl-N-isopentylamino) -4-methyl,

Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (dibutylamino) -8- (dipentamino) -4-methyl,

4,5,6, 7-tetrachloro-3- [4- (dimethylamino) -2-methoxyphenyl ] -3- (1-butyl-2-methyl-1H-indol-3-yl) -1(3H) -isobenzofuranone,

4,5,6, 7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl ] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1(3H) -isobenzofuranone,

4,5,6, 7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl ] -3- (1-pentyl-2-methyl-1H-indol-3-yl) -1(3H) -isobenzofuranone,

4,5,6, 7-tetrachloro-3- [4- (diethylamino) -2-methylphenyl ] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1(3H) -isobenzofuranone,

3 ', 6 ' -bis [ phenyl (2-methylphenyl) amino ] -spiro [ isobenzofuran-1 (3H),9 ' - [9H ] xanthen ] -3-one,

3 ', 6 ' -bis [ phenyl (3-methylphenyl) amino ] -spiro [ isobenzofuran-1 (3H),9 ' - [9H ] xanthen ] -3-one,

3 ', 6 ' -bis [ phenyl (3-ethylphenyl) amino ] -spiro [ isobenzofuran-1 (3H),9 ' - [9H ] xanthen ] -3-one,

2, 6-bis (2 '-ethoxyphenyl) -4- (4' -dimethylaminophenyl) pyridine,

2, 6-bis (2 ', 4 ' -diethoxyphenyl) -4- (4 ' -dimethylaminophenyl) pyridine,

2- (4' -dimethylaminophenyl) -4-methoxy-quinazoline,

4, 4' - (ethylenedioxy) -bis [2- (4-diethylaminophenyl) quinazoline ]

In addition to the compounds in which the phenyl group forming the xanthene ring has a substituent, the fluorans may be compounds in which 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, or a halogen atom such as a chlorine group), which exhibit a blue color or a black color.

The electron accepting compound as the component (b) is a compound that accepts electrons from the component (a) and functions as a color developer of the component (a).

The electron-accepting compound is a compound selected from the group consisting of compounds having an active proton, pseudo-acidic compounds (compounds which do not act as an acid in the composition and which develop the color of the component (a)), compounds having an electron hole, and the like, and among these compounds, a compound selected from the group consisting of compounds having an active proton is preferable.

Examples of the group of compounds having an active proton include: the compound having a phenolic hydroxyl group and a derivative thereof, a carboxylic acid and a derivative thereof, preferably an aromatic carboxylic acid and a derivative thereof, an aliphatic carboxylic acid having 2 to 5 carbon atoms and a derivative thereof, a 2-hydroxycarboxylic acid derivative, an N-substituted amino acid derivative, an acidic phosphate ester and a derivative thereof, an azole compound and a derivative thereof, a 1,2, 3-triazole and a derivative thereof, a cyclic carbonyl sulfonyl imide, a halohydrin having 2 to 5 carbon atoms, a sulfonic acid and a derivative thereof, an inorganic acid, and the like.

Examples of the pseudo acidic compounds include: metal salts of the compounds having a phenolic hydroxyl group, metal salts of the carboxylic acids, metal salts of the acidic phosphoric acid esters, metal salts of the sulfonic acids, aromatic carboxylic anhydrides, aliphatic carboxylic anhydrides, mixed acid anhydrides of aromatic carboxylic acids and sulfonic acids, cyclic olefin dicarboxylic anhydrides, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, halogenated alcohols, and the like.

Examples of the group of compounds having an electron hole include: borates, inorganic salts, and the like.

Among these, compounds having a phenolic hydroxyl group are preferable because they can exhibit effective thermochromic properties.

The compound having a phenolic hydroxyl group broadly includes a mono-phenol compound to a poly-phenol compound, and further includes a di-type phenol, a tri-type phenol, and the like, and a phenol-aldehyde condensation resin, and the like. Among the compounds having a phenolic hydroxyl group, those having at least 2 benzene rings are preferable. Further, these compounds may have a substituent, and as the substituent, there may be mentioned: alkyl, aryl, acyl, alkoxycarbonyl, carboxyl, and esters or acylamino, halo, and the like.

Examples of the metal contained in the metal salt of the compound having a phenolic hydroxyl group include: sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, molybdenum, and the like.

As the compound having 1 phenolic hydroxyl group, there can be mentioned:

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-amylphenol; 4-n-octylphenol; 4-tert-octylphenol; 4-n-nonylphenol; 4-n-dodecylphenol; 3-n-pentadecylphenol; 4-n-stearylphenol; 1- (4-hydroxyphenyl) decan-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, 4' -dihydroxybenzophenone; 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; alpha-naphthol; beta-naphthol; 2, 3-dimethylphenol; 2, 4-dimethylphenol; 2, 6-dimethylphenol; 2, 6-di-tert-butylphenol; 2, 4-dichlorophenol; 2, 4-difluorophenol; daphniphenol; 3-methyl-4-methylphenylthiophenol; 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-benzoxathiepin-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-tetrachlorobenzotriazol; 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-hydroxybenzoic acid n-butyl ester; n-octyl 4-hydroxybenzoate; 2-heptadecafluorooctyl 4-hydroxybenzoate; benzyl 4-hydroxybenzoate; benzyl 4-hydroxybenzoate; 4-hydroxybenzoic acid-o-methylbenzyl ester; 4-hydroxybenzoic acid-m-methylbenzyl ester; 4-hydroxybenzoic acid-p-methylbenzyl ester; 4-hydroxybenzoic acid-p-ethylbenzyl ester; 4-hydroxybenzoic acid-p-propylbenzyl ester; 4-hydroxybenzoic acid-p-tert-butyl benzyl ester; phenyl ethyl 4-hydroxybenzoate; 4-hydroxybenzoic acid-o-methylphenyl ethyl ester; 4-hydroxybenzoic acid-m-methylphenyl ethyl ester; 4-hydroxybenzoic acid-p-methylphenyl ethyl ester; 4-hydroxybenzoic acid-p-ethylphenyl ethyl ester; 4-hydroxybenzoic acid-p-propylphenethyl ester; 4-hydroxybenzoic acid-p-tert-butylphenyl ethyl ester and the like.

As the compound having 2 phenolic hydroxyl groups, there can be mentioned:

resorcinol; 2-methylresorcinol; 4-n-hexylresorcinol; 4-n-octylresorcinol; 4-tert-octylresorcinol; 4-benzoylresorcinol; 4-nitroresorcinol; beta-clavulanic acid (i.e., 2, 4-dihydroxybenzoic acid) methyl ester; benzyl beta-clavulanate; 2-chloro-4-valerylresorcinol; 6-chloro-4-valerylresorcinol; 2-chloro-4-hexanoylresorcinol; 6-chloro-4-hexanoylresorcinol; 2-chloro-4-propionyl resorcinol; 6-chloro-4-propionyl resorcinol; 2, 6-dichloro-4-propionyl resorcinol; 6-fluoro-4-propionyl resorcinol; 2-chloro-4-phenylacetylresorcinol; 4-phenylacetyl-6-chlororesorcinol; 2-chloro-4- β -phenylpropionyl resorcinol; 6-chloro-4- β -phenylpropionyl resorcinol; 2-chloro-4-phenoxyacetyl resorcinol; 6-chloro-4-phenoxyacetyl resorcinol; 4-benzoyl-2-chlororesorcinol; 6-chloro-4-m-methylbenzoyl resorcinol; 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; 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' -isopropyl benzophenone; 2, 4-dihydroxy-4' -n-butylbenzophenone; 2, 4-dihydroxy-4' -isobutylbenzophenone; 2, 4-dihydroxy-4' -tert-butyl benzophenone; 2, 4-dihydroxy-4' -n-amyl benzophenone; 2, 4-dihydroxy-4' -n-hexylbenzophenone; 2, 4-dihydroxy-4' -n-heptyl benzophenone; 2, 4-dihydroxy-4' -n-octyl benzophenone; 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-butoxy benzophenone; 2, 4-dihydroxy-4' -isobutoxy benzophenone; 2, 4-dihydroxy-4' -n-pentyloxybenzophenone; 2, 4-dihydroxy-4' -n-hexyloxybenzophenone; 2, 4-dihydroxy-4' -n-heptyloxybenzophenone; 2, 4-dihydroxy-4' -n-octoxy benzophenone; 2, 4-dihydroxy-4' -n-nonanoyloxybenzophenone; 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; 2, 4-dihydroxy-3 ', 4 ', 5 ' -triethoxybenzophenone, and the like.

Further examples of the bisphenol-type phenol compound include:

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) 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-methylbutane; 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; a 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) 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) methyl propionate; 2, 2-bis (4-hydroxyphenyl) butyl propionate; 2, 2-bis (4-hydroxy-3-methylphenyl) methyl propionate; 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-ethyleneoxydiphenol; 1, 4-bis (4-hydroxybenzoate) -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-tetracene; 4, 4-dihydroxydiphenyl ether; bis (4-hydroxyphenylethyl) ether; bis (4-hydroxyphenyl) sulfone; 4-benzyloxy-4' -hydroxydiphenylsulfone; 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' -hydroxydiphenylsulfone; 4- (3-isopropylbenzyloxy) -4' -dihydroxyphenyl sulfone; 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' -hydroxydiphenylsulfone; 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-hydroxydiphenylsulfone; 4-methyl-4' -hydroxydiphenyl 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' -hydroxydiphenylsulfone; 4-isopropoxy-4' -hydroxydiphenylsulfone; 4-n-butoxy-4' -hydroxydiphenyl sulfone; 4-isobutoxy-4' -hydroxydiphenyl sulfone; 4-sec-butoxy-4' -hydroxydiphenyl sulfone; 4-tert-butoxy-4' -hydroxydiphenyl sulfone; 4-n-pentyloxy-4' -hydroxydiphenylsulfone; 4-isopentyloxy-4' -hydroxydiphenylsulfone; 4- (1-propenyloxy) -4' -hydroxydiphenylsulfone; 4- (2-propenyloxy) -4' -hydroxydiphenylsulfone; 4-benzyloxy-4' -hydroxydiphenylsulfone; 4- (β -phenoxyethoxy) -4' -hydroxydiphenyl sulfone; 4- (β -phenoxypropoxy) -4' -hydroxydiphenylsulfone; 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-methyldiphenylsulfone; 3,4, 4' -trihydroxydiphenylsulfone; bis (3, 4-dihydroxyphenyl) sulfone; 2,3, 4-trihydroxydiphenylsulfone; 4-isopropoxy-4' -hydroxydiphenylsulfone; 4-n-propoxy-4' -hydroxydiphenylsulfone; 4-allyloxy-4' -hydroxydiphenyl sulfone; 4-benzyloxy-4' -hydroxydiphenylsulfone; 4- (2-propenyloxy) -4' -hydroxydiphenylsulfone; 3-benzyl-4-benzyloxy-4' -hydroxydiphenylsulfone; 3-phenethyl-4-phenethyloxy-4' -hydroxydiphenyl sulfone; 3-methylbenzyl-4-methylbenzyloxy-4' -hydroxydiphenylsulfone; 4-benzyloxy-3 '-benzyl-4' -hydroxydiphenylsulfone; 4-phenethyloxy-3 '-phenethyl-4' -hydroxydiphenyl sulfone; 4-methylbenzyloxy-3 '-methylbenzyl-4' -hydroxydiphenylsulfone; α, α' -bis {4- (p-hydroxyphenylsulfone) phenoxy } -p-xylene; 4, 4' - { oxybis (ethylene oxide-p-phenylsulfonyl) } 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-octyl-phenyl) sulfide; bis (5-chloro-2-hydroxyphenyl) sulfide; bis (3-cyclohexyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenylethoxy) methane; 1,5- (4-hydroxyphenylthio) -3-oxapentane; 1, 8-bis (4-hydroxyphenylthio) -3, 6-dioxaoctane; and so on.

As the compound having 3 phenolic hydroxyl groups, there can be mentioned: pyrogallol, phloroglucinol carboxylic acid, gallic acid, octyl gallate, dodecyl gallate, and the like.

Further, as the compound of the trisype phenol, there can be mentioned:

4, 4' -methine trisphenol; 4, 4', 4 "-methlyltris (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' -ethenyl trisphenol; 4, 4', 4 "-ethylidenetris (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 } methylene ] bisphenol; 4, 4' - [1- {4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bisphenol; 4, 4' - [1- {4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl } propylene ] bisphenol; 4, 4' - [1- {4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl } butylene ] bisphenol; 4, 4' - [1- {4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl } pentylene ] bisphenol; 4, 4' - [1- {4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl } hexylene ] 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 } ethylene ] bisphenol; 3, 3' - [1- {4- [1- (3-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bisphenol; 4, 4' - [1- {4- [1- (3-fluoro-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2-fluorophenol); 4, 4' - [1- {4- [1- (3-chloro-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2-chlorophenol); 4, 4' - [1- {4- [1- (3-bromo-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2-bromophenol); 4, 4' - [1- {4- [1- (4-hydroxy-3-methylphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2-methylphenol); 4, 4' - [1- {4- [1- (3-ethyl-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2-ethylphenol); 4, 4' - [1- {4- [1- (3-tert-butyl-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2-tert-butylphenol); 4, 4' - [1- {4- [1- (4-hydroxy-3-trifluoromethylphenyl) -1-methylethyl ] phenyl } ethylene ] 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-hydroxyphenyl cyclohexane; 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' -methine 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 '- [ (4-hydroxy-3-methoxyphenyl) methylene ] bis (3,5, 6-trimethylphenol), 4' - [ (3-ethoxy-4-hydroxyphenyl) methylene ] bis (2-isopropylphenol), 2 '- [ (3-ethoxy-4-hydroxyphenyl) methylene ] bis (3,5, 6-trimethylphenol), 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-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2-tert-butylphenol); 4, 4' - [1- {4- [1- (3, 5-dimethyl-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2, 6-dimethylphenol); 4, 4' - [ (3-ethoxy-4-hydroxyphenyl) methylene ] bis (2-cyclohexyl-5-methylphenol); 4, 4' - [ (3-cyclohexyl-4-hydroxyphenyl) ethylene ] bis (2-cyclohexylphenol); 4, 4' - [ (5-cyclohexyl-4-hydroxy-2-methoxyphenyl) ethylene ] bis (2-cyclohexyl-5-methylphenol); 4, 4' - [1- {4- [1- (3-cyclohexyl-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2-cyclohexylphenol); 4, 4' - [1- {4- [1- (3-fluoro-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bisphenol; 4, 4' - [1- {4- [1- (3-fluoro-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] bis (2-methylphenol); 4, 4' - [1- {4- [1- (3-fluoro-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] 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 "-methlyltris (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-tris (4-hydroxy-3-phenylphenyl) adamantane; 1,3, 5-tris (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-biphenylpropylene ] bis (5-cyclohexyl-2-methylphenol); 4, 4' - [3- (2, 5-dimethyl-4-hydroxyphenyl) -3-phenylpropylene ] 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-methylbutane; 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-biphenyl) -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), and the like.

As the compound having 4 or more phenolic hydroxyl groups, there can be mentioned:

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; 1,1,2, 2-tetrakis (4-hydroxy-3-methylphenyl) ethane; 1,1,2, 2-tetrakis (3, 5-dimethyl-4-hydroxyphenyl) ethane; 1,1,4, 4-tetrakis (3, 5-dimethyl-4-hydroxyphenyl) benzene; 2, 2' -bis [4,4- (4-hydroxy-3-methylphenyl) cyclohexyl ] propane; 2, 2' - [ (3, 4-dihydroxyphenyl) methylene ] bis (3, 5-dimethylphenol); 3, 6-bis [ (3, 5-dimethyl-4-hydroxyphenyl) methyl) catechol; 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 [3- (2-hydroxybenzyl) -4-hydroxy-5-methylphenyl ] methane; bis [3- (3-hydroxybenzyl) -4-hydroxy-5-methylphenyl ] methane; bis [3- (4-hydroxybenzyl) -4-hydroxy-5-methylphenyl ] methane; bis [3- (2-hydroxybenzyl) -2-hydroxy-5-methylphenyl ] methane; bis [3- (2-hydroxybenzyl) -3-hydroxy-5-methylphenyl ] methane; bis [3- (2-hydroxybenzyl) -4-hydroxy-5-methylphenyl ] methane; bis [3- (3-hydroxy-2-methylbenzyl) -2-hydroxy-5-methylphenyl ] methane; bis [3- (4-hydroxy-3-methylbenzyl) -2-hydroxy-5-methylphenyl ] methane; bis [3- (3-hydroxy-4-methylbenzyl) -2-hydroxy-5-methylphenyl ] methane; bis [3- (2-hydroxy-3-methylbenzyl) -2-hydroxy-5-methylphenyl ] methane; α, α ', α ", α'" -tetrakis (4-hydroxyphenyl) benzene; bis [3- (3, 6-dimethyl-2-hydroxybenzyl) -2-hydroxy-5-methylphenyl ] methane; [3- (3, 6-dimethyl-2-hydroxybenzyl) -2-hydroxy-5-methylphenyl ] [3- (2, 5-dimethyl-4-hydroxybenzyl) -2-hydroxy-5-methylphenyl ] methane; bis [3- (2, 5-dimethyl-4-hydroxybenzyl) -2-hydroxy-5-methylphenyl ] methane; bis [3- (3, 5-dimethyl-4-hydroxybenzyl) -2-hydroxy-5-methylphenyl ] methane; bis [3- (2-hydroxy-3, 4, 6-trimethylbenzyl) -2-hydroxy-5-methylphenyl ] methane; bis [ 2-hydroxy-3- (4-hydroxy-2, 3, 5-trimethylbenzyl) -5-methylphenyl ] methane; 4,4 ', 4 ", 4" ' -tetrakis (4-hydroxyphenyl) -1,1 ' -bicyclohexane; 2, 2' -bis [4, 4-bis (4-hydroxyphenyl) cyclohexyl ] propane; 4,4 ', 4 ", 4" ' -tetrakis (4-hydroxy-3-methylphenyl) -1,1 ' -bicyclohexane; bis [3- (5-cyclohexyl-4-hydroxy-2-methylbenzyl) -4-hydroxy-5-methylphenyl ] methane; 4,4 ', 4 ", 4" ' -tetrakis (3, 5-dimethyl-4-hydroxyphenyl) -1,1 ' -bicyclohexane; 1, 1-bis [3- (2-hydroxy-5-methylbenzyl) -5-cyclohexyl-4-hydroxyphenyl ] cyclohexane; 1, 1-bis [3- (3, 5-dimethyl-4-hydroxybenzyl) -5-cyclohexyl-4-hydroxyphenyl ] cyclohexane; 1, 1-bis [3- (5-cyclohexyl-4-hydroxy-2-methylbenzyl) -5-cyclohexyl-4-hydroxyphenyl ] cyclohexane; 4, 6-bis [ α -methyl- (4-hydroxyphenyl) benzyl-1, 3-benzenediol; 2, 2-bis [3- (4-hydroxy-3-methylbenzyl) -4-hydroxy-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 (4-hydroxy-3-isopropylphenyl) -1,1 ' -bicyclohexane; 4, 4' -bis [ (3, 4-dihydroxyphenyl) methylene ] bis (2-isopropylphenol); 2,4, 6-tris (4-hydroxybenzyl) -1, 3-benzenediol; 4, 6-bis (3, 5-dimethyl-4-hydroxybenzyl) pyrogallol; 3, 3' - [ (2-hydroxyphenyl) methylene ] bis (5-methylcatechol); 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) resorcinol; 2,4, 6-tris (3, 5-dimethyl-2-hydroxybenzyl) resorcinol; 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) pyrogallol; 4, 4' - [1- {4- [1- (3, 5-bis (4-hydroxybenzyl) -4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylidene ] bis [2, 6-bis (4-hydroxybenzyl) phenol ]; 4, 4' - [1- {4- [1- (3, 5-bis (4-hydroxy-3-methylbenzyl) -4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylidene ] 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 } ethylidene ] 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 } ethylidene ] 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- (. alpha.,. alpha. -bis (4-hydroxy-3-methylphenyl) methyl-4-hydroxyphenyl ] methane, bis [3, 5-bis (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl ] methane, 4' -ethylidenetris { [2- (2-hydroxy-5-methyl) benzyl ] -6-methylphenol }, 2-bis [3, 5-bis (2-hydroxy-5-methylphenylmethyl) phenyl ] propane, bis [3- (. alpha.,. alpha. -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] -meta-cyclic aromatic hydrocarbon; 4, 4' - [1- {4- [1- (3, 5-bis (4-hydroxy-2-methylbenzyl) -4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylidene ] 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 } ethylidene ] 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 } ethylidene ] 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 } ethylene ] 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 } ethylidene ] bis [2, 6-bis (4-hydroxy-3-isopropylphenyl) phenol ]; bis [3- (. alpha.,. alpha. -bis (3, 5-dimethyl-4-hydroxyphenyl) methyl-4-hydroxyphenyl ] methane, bis [3- (. alpha.,. alpha. -bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) methyl-4-hydroxyphenyl ] methane, 4 ' - [ 4-hydroxy-3, 5-bis (2-hydroxybenzyl) methylene ] bis [2, 6-bis (2-hydroxybenzyl) ] phenol, 4 ' - [ 4-hydroxy-3, 5-bis (4-hydroxybenzyl) methylene ] bis [2, 6-bis (4-hydroxybenzyl) ] phenol, 4 ' -ethylidenetris [2, 6-bis (2-hydroxybenzyl) phenol ]; 4, 4', 4 "-ethylidenetris [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] -meta-cyclic arene (metacycloalkane); 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 } ethylidene ] 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 } ethylene ] bis [2, 6-bis (4-hydroxy-2, 3, 5-trimethylphenyl) phenol ]; 4, 4' - [1- {4- [1- (3, 5-bis (3-sec-butyl-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylidene ] bis [2, 6-bis (3-sec-butyl-4-hydroxyphenyl) phenol ]; 4, 4' - [1- {4- [1- (3, 5-bis (3-tert-butyl-4-hydroxyphenyl) -1-methylethyl ] phenyl } ethylene ] 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 so on.

Examples of the carboxylic acid and its derivative include:

3, 5-bis (α -methylbenzyl) salicylic acid; 4- (2-p-methoxyphenoxyethoxy) salicylic acid; 4-hydroxybenzylbenzoic acid; p-chlorobenzoic acid; 4- [2- (p-methoxyphenoxy) ethoxy ] salicylic acid; 4- [3- (p-tolylsulfonyl) propoxy ] salicylic acid; 5- [ p- (2-p-methoxyphenoxyethoxy) cumyl ] salicylic acid; 4-octyloxycarbonylaminosalicylic acid; 3, 5-distyrenated salicylic acid; n- (p-toluenesulfonyl) -glycine; n- (p-toluenesulfonyl) -alanine; n- (p-toluenesulfonyl) - β -alanine; n-phenylaminocarbonyl-glycine; n-phenylaminocarbonyl-valine; n- (m-toluidinocarbonyl) -phenylalanine; n- (m-toluidinocarbonyl) -cysteine-S-benzyl; n- (m-toluidinocarbonyl) -methionine; n- (m-toluidinocarbonyl) -tyrosine; n- (p-tolylaminocarbonyl) -phenylalanine; n- (p-toluidinocarbonyl) -cysteine-S-benzyl; n- (p-toluidinocarbonyl) -methionine; n- (p-toluidinocarbonyl) -methionine; n- (phenylaminocarbonyl) -methionine; n- (p-toluidinocarbonyl) -tyrosine; n- (m-toluidinocarbonyl) -methionine; n- (p-toluidinocarbonyl) -methionine; n- (phenylaminocarbonyl) -methionine; n- (m-toluidinocarbonyl) -valine; n- (m-toluidinocarbonyl) -phenylglycine; n- (m-toluidinocarbonyl) -tyrosine; 2-O- (phenylaminocarbonyl) -mandelic acid; 2-O- (p-toluidinocarbonyl) -mandelic acid; 2-O- (m-toluidinocarbonyl) -mandelic acid; 2-O- (O-tolylaminocarbonyl) -mandelic acid; 2-O- (1-naphthylaminocarbonyl) -mandelic acid; 2-O- (3-isopropenyl- α, α -dimethylbenzylcarbonyl) -mandelic acid; 2-O- (benzylaminocarbonyl) -mandelic acid; 2-O- (phenethylaminocarbonyl) -mandelic acid; 2-O- (phenylaminocarbonyl) -lactic acid; 2-O- (p-toluidinocarbonyl) -lactic acid; 2-O- (m-toluidinocarbonyl) -lactic acid; 2-O- (O-tolylaminocarbonyl) -lactic acid; 2-O- (1-naphthylaminocarbonyl) -lactic acid; 2-O- (3-isopropenyl- α, α -dimethylbenzylcarbonyl) -lactic acid; 2-O- (benzylaminocarbonyl) -lactic acid; 2-O- (phenethylaminocarbonyl) -lactic acid, and the like.

As the acidic phosphate ester compound, there may be mentioned:

methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, isotridecyl acid phosphate, oily acid phosphate, ditetradecyl acid phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate, bis (2-ethylhexyl) phosphate, and the like.

The compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, but may be a compound selected from the group consisting of aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms, metal salts of carboxylic acids, acidic phosphoric acid esters and metal salts thereof, 1,2, 3-triazole and derivatives thereof, and the like.

Component (c) is a reaction medium in which an electron transfer reaction between component (a) and component (b) reversibly occurs in a specific temperature range. Examples of the component (c) include: esters, ketones, ethers, alcohols, amides.

As the component (c), a carboxylate compound showing a Δ T value (melting point-cloud point) of 5 ℃ or more and less than 50 ℃ is used, which is capable of forming a reversible thermochromic composition showing a color memory property that changes in a color concentration-temperature curve (a curve obtained by plotting a change in color concentration due to a change in temperature is different between when the temperature is changed from a low temperature side to a high temperature side and when the temperature is changed from a high temperature side to a low temperature side) to thereby change the color, for example, a carboxylate containing a substituted aromatic ring in the molecule, an ester of a carboxylic acid containing an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylate containing a cyclohexyl group in the molecule, an ester of a fatty acid having 6 or more carbon atoms and an unsubstituted aromatic alcohol or phenol, an ester of a carboxylic acid having 6 or more carbon atoms and an unsubstituted aromatic alcohol or phenol, Esters of a fatty acid having 8 or more carbon atoms and a branched aliphatic alcohol, esters of a dicarboxylic acid and an aromatic alcohol or a branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, glycerol trilaurate, glycerol trimyristate, glycerol tristearate, glycerol dimyristate, and glycerol distearate.

Further, a fatty acid ester compound obtained from an aliphatic monohydric alcohol having an odd number of carbon atoms of 9 or more and an aliphatic carboxylic acid having an even number of carbon atoms, and a fatty acid ester compound having a total of 17 to 23 carbon atoms obtained from an aliphatic carboxylic acid having an even number of carbon atoms of 10 to 16 and n-pentanol or n-heptanol are also effective.

Specific examples thereof include: n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl hexanoate, n-tridecyl hexanoate, n-pentadecyl hexanoate, n-nonyl octanoate, n-undecyl octanoate, n-pentadecyl octanoate, n-heptyl decanoate, n-nonyl decanoate, n-undecyl decanoate, n-tridecyl decanoate, n-pentadecyl decanoate, n-pentyl laurate, n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-pentadecyl palmitate, n-decyl palmitate, n-decyl palmitate, n-decyl palmitate, n-decyl palmitate, n-decyl palmitate, n-, N-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosoate, n-undecyl eicosoate, n-tridecyl eicosoate, n-pentadecyl eicosoate, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate, and the like.

As ketones, aliphatic ketones having 10 or more total carbon atoms are effective, and include: 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone, 2-decadione, 3-decadione, 4-decadione, 5-decadione, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2-pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-icosanone, laurone, stearone and the like.

Examples of the aryl alkyl ketones having 12 to 24 carbon atoms in total include n-octadecanoylbenzene, n-heptadecanoylbenzene, n-hexadecanoylbenzene, n-pentadecanoylbenzene, n-tetradecanoylbenzene, 4-n-dodecylacetophenone, n-tridecanoylbenzene, 4-n-undecylacetophenone, n-dodecylacetophenone, 4-n-decylphenone, n-undecylacetophenone, 4-n-nonylacetophenone, n-decanoylbenzene, 4-n-octylacetophenone, n-nonanoylbenzene, 4-n-heptylacetophenone, n-octanoylbenzene, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylacetophenone, n-heptanoylbenzene, 4-n-pentylacetophenone, cyclohexylphenylketone, benzyl-n-butylketone, 4-n-butylacetophenone, n-hexanoylbenzene, 4-isobutylacetophenone, benzyl-n-butylacetophenone, 4-isobutylacetophenone, n-dodecylbenzene, n-butylacetophenone, n-dodecylbenzene, n-butylacetophenone, n-butylketone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone, etc.

As the ethers, aliphatic ethers having 10 or more total carbon atoms are effective, and there may be mentioned: dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediodimethyl ether, tridecanediodimethyl ether, decanediol diethyl ether, undecanediol diethyl ether and the like.

The alcohols are effective as monohydric aliphatic saturated alcohols having 10 or more carbon atoms, and include: decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, eicosanol, docosanol, etc.

Examples of amides include: caproamide, enanthamide, caprylamide, pelargonamide, capramide, undecanamide, lauramide, tridecanamide, myristamide, palmitamide, stearamide, behenamide and the like.

Further, as the component (c), a compound represented by the following general formula (1) may also be used.

(Here, R is¹Represents a hydrogen atom or a methyl group, q1 represents an integer of 0 to 2, X¹Any one of (A) to (B) represents- (CH)₂)_kOCOR' or- (CH)₂)_kCOOR 'and another represents a hydrogen atom, k represents an integer of 0 to 2, R' represents an alkyl or alkenyl group having 4 or more carbon atoms, Y₁Each independently represents an alkyl group having 1 to 4 carbon atoms, a methoxy group or a halogen, and each p1 independently represents an integer of 0 to 3)

In the compound represented by the formula (1), in R₁In the case of a hydrogen atom, it is preferable that R is further added because a reversible thermal discoloration composition having a wider retardation width can be obtained₁The case where m is 0 and is a hydrogen atom is more preferable.

Among the compounds represented by the formula (1), the compounds represented by the following general formula (1a) are more preferably used.

(where R is^1aAn alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms)

As the compound, specifically, there can be exemplified: octanoic acid-4-benzyloxy phenyl ethyl ester, nonanoic acid-4-benzyloxy phenyl ethyl ester, decanoic acid-4-benzyloxy phenyl ethyl ester, undecanoic acid-4-benzyloxy phenyl ethyl ester, dodecanoic acid-4-benzyloxy phenyl ethyl ester, tridecanoic acid-4-benzyloxy phenyl ethyl ester, tetradecanoic acid-4-benzyloxy phenyl ethyl ester, pentadecanoic acid-4-benzyloxy phenyl ethyl ester, hexadecanoic acid-4-benzyloxy phenyl ethyl ester, heptadecanoic acid-4-benzyloxy phenyl ethyl ester, octadecanoic acid-4-benzyloxy phenyl ethyl ester.

Further, as the component (c), a compound represented by the following general formula (2) may be used.

(Here, R is²Represents an alkyl group or alkenyl group having 8 or more carbon atoms, p2 each independently represents an integer of 0 to 3, and X²Each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen

As the compound, specifically, there can be exemplified: octanoic acid 1, 1-diphenylmethyl ester, nonanoic acid 1, 1-diphenylmethyl ester, decanoic acid 1, 1-diphenylmethyl ester, undecanoic acid 1, 1-diphenylmethyl ester, dodecanoic acid 1, 1-diphenylmethyl ester, tridecanoic acid 1, 1-diphenylmethyl ester, tetradecanoic acid 1, 1-diphenylmethyl ester, pentadecanoic acid 1, 1-diphenylmethyl ester, hexadecanoic acid 1, 1-diphenylmethyl ester, heptadecanoic acid 1, 1-diphenylmethyl ester, octadecanoic acid 1, 1-diphenylmethyl ester.

Further, as the component (c), a compound represented by the following general formula (3) may be used.

(Here, X³Each independently represents any one of alkyl with 1 to 4 carbon atoms, methoxyl or halogen atom, each p3 independently represents an integer of 0 to 3, q3 represents an integer of 1 to 20)

As the compound, there can be exemplified: malonic acid diester with 2- [4- (4-chlorobenzyloxy) phenyl) ] ethanol, succinic acid diester with 2- (4-benzyloxyphenyl) ethanol, succinic acid diester with 2- [4- (3-methylbenzyloxy) phenyl) ] ethanol, glutaric acid diester with 2- (4-benzyloxyphenyl) ethanol, glutaric acid diester with 2- [4- (4-chlorobenzyloxy) phenyl) ] ethanol, adipic acid diester with 2- (4-benzyloxyphenyl) ethanol, pimelic acid diester with 2- (4-benzyloxyphenyl) ethanol, suberic acid diester with 2- [4- (3-methylbenzyloxy) phenyl) ] ethanol, and mixtures thereof, The diester of suberic acid with 2- [4- (4-chlorobenzyloxy) phenyl) ] ethanol, the diester of suberic acid with 2- [4- (2, 4-dichlorobenzyloxy) phenyl) ] ethanol, the diester of azelaic acid with 2- (4-benzyloxyphenyl) ethanol, the diester of sebacic acid with 2- (4-benzyloxyphenyl) ethanol, the diester of 1, 10-decanedicarboxylic acid with 2- (4-benzyloxyphenyl) ethanol, the diester of 1, 18-octadecadicarboxylic acid with 2- (4-benzyloxyphenyl) ethanol, and the diester of 1, 18-octadecadicarboxylic acid with 2- [4- (2-methylbenzyloxy) phenyl) ] ethanol.

Further, as the component (c), a compound represented by the following general formula (4) may be used.

(Here, R is⁴Each independently represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and each p4 independently represents an integer of 1 to 3)

As the compound, there can be exemplified: diesters of 1, 3-bis (2-hydroxyethoxy) benzene with decanoic acid; diesters of 1, 3-bis (2-hydroxyethoxy) benzene with undecanoic acid; diesters of 1, 3-bis (2-hydroxyethoxy) benzene with lauric acid; diesters of 1, 3-bis (2-hydroxyethoxy) benzene with myristic acid; diesters of 1, 3-bis (2-hydroxyethoxy) benzene with palmitic acid; diesters of 1, 3-bis (2-hydroxyethoxy) benzene with cyclohexanecarboxylic acid; diesters of 1, 3-bis (2-hydroxyethoxy) benzene with cyclohexanoic acid propionic acid; diesters of 1, 4-bis (hydroxymethoxy) benzene with butyric acid; diesters of 1, 4-bis (hydroxymethoxy) benzene with isovaleric acid; diesters of 1, 4-bis (2-hydroxyethoxy) benzene with acetic acid; diesters of 1, 4-bis (2-hydroxyethoxy) benzene with propionic acid; diesters of 1, 4-bis (2-hydroxyethoxy) benzene with pentanoic acid; diesters of 1, 4-bis (2-hydroxyethoxy) benzene with hexanoic acid; diesters of 1, 4-bis (2-hydroxyethoxy) benzene with octanoic acid; diesters of 1, 4-bis (2-hydroxyethoxy) benzene with decanoic acid; diesters of 1, 4-bis (2-hydroxyethoxy) benzene with lauric acid; diesters of 1, 4-bis (2-hydroxyethoxy) benzene with myristic acid; diesters of 1, 4-bis (2-hydroxyethoxy) benzene with cyclohexanepropanoic acid.

Further, as the component (c), a compound represented by the following general formula (5) may be used.

(Here, X⁵Independently represents any one of alkyl with 1-4 carbon atoms, alkoxy with 1-4 carbon atoms or halogen atom, p5 independently represents an integer of 0-3, q5 represents an integer of 1-20)

As the compound, there can be exemplified: diesters of succinic acid with 2-phenoxyethanol, diesters of suberic acid with 2-phenoxyethanol, diesters of sebacic acid with 2-phenoxyethanol, diesters of 1, 10-decanedicarboxylic acid with 2-phenoxyethanol, and diesters of 1, 18-octadecanedioic acid with 2-phenoxyethanol.

Further, as the component (c), a compound represented by the following general formula (6) may be used.

(Here, R is⁶X represents any one of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkenyl group having 4 to 22 carbon atoms⁶Represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, q6 represents 0 or 1)

As the compound, there can be exemplified: decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, decyl 4-biphenylacetate, lauryl 4-biphenylacetate, myristyl 4-biphenylacetate, tridecyl 4-biphenylacetate, pentadecyl 4-biphenylacetate, cetyl 4-biphenylacetate, cyclopentyl 4-biphenylacetate, cyclohexylmethyl 4-biphenylacetate, hexyl 4-biphenylacetate, cyclohexylmethyl 4-biphenylacetate.

Further, as the component (c), a compound represented by the following general formula (7) may be used.

(Here, R is⁷X represents any one of an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms⁷Y represents any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, and a halogen atom⁷Z represents any of a hydrogen atom and a methyl group⁷Represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, and a halogen atom)

As the compound, there can be exemplified: 4-butoxy benzoic acid phenoxy ethyl ester, 4-pentoxy benzoic acid phenoxy ethyl ester, 4-tetradecyloxy benzoic acid phenoxy ethyl ester, 4-hydroxy benzoic acid phenoxy ethyl ester and ester of lauric acid, vanillic acid phenoxy ethyl ester dodecyl ether.

Further, as the component (c), a compound represented by the following general formula (8) may be used.

(Here, R is⁸X represents any one 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 group⁸Each independently represents an alkyl group, an alkoxy group or a halogen atom, p8 represents 0 or 1, q8 represents 0 to 5, r8 represents 0 to 4)

As the compound, there can be exemplified: the benzoic acid ester of octyl paraben, the benzoic acid ester of decyl paraben, the p-methoxybenzoic acid ester of heptyl paraben, the o-methoxybenzoic acid ester of dodecyl paraben, and the benzoic acid ester of cyclohexyl methyl paraben.

Further, as the component (c), a compound represented by the following general formula (9) may be used.

(Here, R is⁹Represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkylalkyl group having 5 to 8 carbon atoms, X⁹Represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, or a halogen atom, and p9 represents an integer of 1 to 3)

As the compound, there can be exemplified: diesters of 4-phenylphenol glycol ether with cyclohexanecarboxylic acid, diesters of 4-phenylphenol diglycol ether with lauric acid, diesters of 4-phenylphenol triethylene glycol ether with cyclohexanecarboxylic acid, diesters of 4-phenylphenol glycol ether with caprylic acid, diesters of 4-phenylphenol glycol ether with nonanoic acid, diesters of 4-phenylphenol glycol ether with capric acid, and diesters of 4-phenylphenol glycol ether with myristic acid.

Further, a microcapsule pigment containing a heat color development type (color development by heating and color fading by cooling) reversible thermal discoloration composition using a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms (Japanese patent application laid-open Nos. 11-129623 and 11-5973), a specific hydroxybenzoate (Japanese patent application laid-open No. 2001-105732), a gallic acid ester or the like (Japanese patent application laid-open No. 51-44706, Japanese patent application laid-open No. 2003-253149) as an electron accepting compound can also be used.

(a) The blending ratio of the components (b), (b) and (c) is affected by the concentration, the discoloration temperature, the discoloration form, or each component, and the ratio of the components to obtain a desired discoloration property is usually: the amount of the component (b) is 0.1 to 50 parts by mass, preferably 0.5 to 20 parts by mass, and the amount of the component (c) is 1 to 800 parts by mass, preferably 5 to 200 parts by mass, based on 1 part by mass of the component (a).

Here, a colorant such as a non-thermally discolorable dye or pigment may be added to the microcapsule pigment or the ink to change the color from the (1) to the (2) color.

The method for encapsulating the reversible thermal discoloration composition in the microcapsule is not particularly limited, and may be appropriately selected according to the application, for example, an interface polymerization method, an interface polycondensation method, an in-Situ (in Situ) polymerization method, a coating method by hardening in liquid, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a cooling method by melt dispersion, a coating method by suspension in gas, a spray drying method, and the like.

Examples of the material of the capsule include organic resins such as epoxy resin, urea resin, urethane resin, and isocyanate resin. In the present invention, the surface of the pigment particle is made of an organic material, and excellent characteristics can be exhibited by a three-way interaction with the following polymer of N-vinyl-2-pyrrolidone and glycerin. Therefore, the capsule must be made of an organic material.

Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

The average particle size of the microcapsule pigment is preferably 0.1 to 5.0. mu.m, more preferably 0.1 to 4.0. mu.m, and still more preferably 0.5 to 3.0. mu.m.

Furthermore, the mass ratio of the reversible thermal discoloration composition to the microcapsule wall film preferably satisfies the reversible thermal discoloration composition: wall film 7: 1-1: 1 (mass ratio), preferably 6: 1-1: 1, in the above range.

If the average particle diameter of the microcapsule pigment exceeds 5.0. mu.m, smooth writing feeling is difficult to obtain when used in a writing instrument, and if the average value of the maximum outer diameter is less than 0.1. mu.m, high-concentration color developability is difficult to exhibit.

The microcapsule pigment having an average particle diameter in the range, particularly in the range of 0.5 to 3.0 μm, exhibits high-concentration color developability and is easy to obtain good bleeding properties when used in a writing instrument.

If the ratio of the reversible thermal discoloration composition to the wall film is greater than the above range, the thickness of the wall film becomes too thin, and a decrease in resistance to pressure or heat tends to occur, and if the ratio of the wall film to the reversible thermal discoloration composition is greater than the above range, a decrease in color density and sharpness at the time of color development tends to occur.

The average particle diameter was measured by determining the region of the particles using image analysis type particle size distribution measurement software "mac view" manufactured by Mountech, calculating the projected area circle equivalent diameter (Heywood diameter) from the area of the region of the particles, and obtaining the average particle diameter of the particles corresponding to the same volume from the calculated projected area circle equivalent diameter.

When the particle size of all or most of the particles exceeds 0.2. mu.m, the average particle size of the particles corresponding to the volume spheres may be measured by the Coulter method using a particle size distribution measuring apparatus (product name: Multisizer 4e, manufactured by Beckman Coulter). Further, the volume-based particle diameter and the average particle diameter (median particle diameter) may be measured using a standard sample or a laser diffraction/scattering type particle diameter distribution measuring apparatus (apparatus name: LA-300, manufactured by horiba, Ltd.) calibrated based on a numerical value measured using a measuring apparatus using the Coulter method.

< polymers of N-vinyl-2-pyrrolidone >

The ink composition of the present invention further contains a polymer of N-vinyl-2-pyrrolidone (hereinafter, may be abbreviated as "PVP"). In the ink composition of the present invention, PVP has an effect of simultaneously achieving various properties. Specifically, the ink composition has an effect of adjusting the viscosity of the ink composition, an effect of suppressing aggregation of the microcapsule pigment, an effect of improving the fixing property or adhesion of the ink component to paper, and the like. Further, according to the study by the present inventors, it is found that the ink composition containing the microcapsule pigment has an effect of suppressing drying. For example, in the case where the ink composition is used for a ball-point pen or a marker pen, particularly a push-button ball-point pen, the pen tip is in a condition of being easily dried. As a result, these writing instruments sometimes become incapable of writing. While this state is referred to as drying, in accordance with the present invention, by using PVP for a specific ink composition, drying can be suppressed and excellent writing can be achieved.

PVP is obtained by polymerizing N-vinyl-2-pyrrolidone, but the polymerization degree of PVP is 2-20, preferably 2-10, more preferably 2-6. When the polymerization degree is within such a range, an increase in viscosity of the ink composition and aggregation of the microcapsule pigment can be suppressed when water in the ink composition evaporates. If PVP having an excessively high degree of polymerization is used, the viscosity of the ink composition becomes excessively high, and the writing performance may be adversely affected, and therefore care must be taken.

< Glycerol >

The ink composition of the present invention further contains glycerin. Glycerin is sometimes used as an organic solvent or a viscosity adjuster of a general ink composition. However, in the present invention, glycerol plays a previously unknown function. That is, when the microcapsule pigment having an organic resin on the surface and PVP coexist at a specific ratio, interaction between the three components occurs, and significant improvement in writing characteristics is achieved.

< water >)

The ink composition of the present invention is an aqueous ink composition, and contains water as a main solvent. The water used in the present invention is not particularly limited, and for example, ion-exchanged water, ultrafiltration water, distilled water, or the like can be used.

< composition of ink composition >

In the present invention, the content (P) of the microcapsule pigment with respect to the total mass of the ink composition_MC) The content of the organic solvent is necessarily 5 to 40% by mass, preferably 10 to 30% by mass, and more preferably 10 to 25% by mass. For example, when the ink composition is used for a ballpoint pen or the like, the amount of the pigment to be blended is usually less than 10% by mass based on the total amount of the ink composition, and when the microcapsule pigment is used as the colorant, it is preferable to increase the amount to be blended for achieving sufficient color development. In addition, since the solid content of an ink composition having a high content of a microcapsule pigment is generally higher than that of a normal ink, performance such as drying performance may be deteriorated. However, the ink composition of the present invention can solve such a problem by blending a specific material at a specific ratio.

In the present invention, the content (P) of PVP with respect to the total mass of the ink composition_PVP) Preferably 1 to 20 mass%, and preferably 2 to 10 mass%. When the content of PVP is in this range, the ink composition can be satisfactorily discharged from the pen tip, and a high writing density can be achieved.

In the present invention, the content (P) of glycerin with respect to the total mass of the ink composition_G) The amount of the ink composition is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, based on the total mass of the ink composition. When the content of glycerin is within this range, the ink composition can be satisfactorily discharged from the pen tip, and sharp handwriting can be formed.

The ink composition of the present invention contains a microcapsule pigment, PVP, glycerin and water as essential components, and the total content (P) of the microcapsule pigment, PVP and glycerin_MC+P_PVP+P_G) Preferably 20 to 50 mass%, more preferably 20 to 30 mass%. By making P_MC+P_PVP+P_GWithin this range, while maintaining a high handwriting density, blurring at the time of writing can be suppressed and high writing characteristics can be achieved.

In the present invention, microcapsules are blended at a specific ratioPigment, PVP and glycerol. Specifically, it is necessary to satisfy: p is more than or equal to 0.3_MC/(P_PVP+P_G) P is not less than 4 and not more than 0.2_PVP/P_G5, preferably: p is more than or equal to 0.5_MC/(P_PVP+P_G) P is not more than 2.5 or not more than 0.3_PVP/P_G≤2.5。

In the present invention, the desired effect can be exhibited only when the microcapsule pigment, PVP, and glycerin are blended so as to fall within the above range. In other words, it is considered that the effects of the present invention can be exhibited by interaction when the three are combined at a specific ratio. That is, the ink composition of the present invention can achieve writing density, drying resistance, stability over time, and the like at the same time. However, it does not merely exhibit the effects of each component. For example, PVP may be used as a material for improving the drying resistance of the ink composition. However, according to the study by the present inventors, it was found that when microcapsules and glycerin coexist, the drying resistance may be decreased by the increase of PVP (see the section of example). In addition, when a general inorganic pigment is used as the pigment, the effect of the present invention cannot be exhibited even when the pigment is blended at a ratio specified in the present invention. It is considered that the microcapsule pigment used in the invention of the present application has an organic resin on the surface, and therefore the organic resin interacts with PVP and glycerin, whereby the stability with time or the writing characteristics can be improved. That is, unexpectedly: in the ink composition in which the microcapsule pigment, PVP, and glycerin coexist, when the mutual ratio of these is a specific ratio, an ink composition having excellent characteristics can be obtained.

< other ingredients >

The ink composition of the present invention may be combined with any components in addition to the essential components as long as the effects of the present invention are not impaired.

Polysaccharides can be used as one of the optional components. The polysaccharides exert various effects, mainly including effects of adjusting the viscosity of ink (thickening agent), imparting shear thinning properties (shear thinning agent), and improving drying resistance.

Here, the shear thinning property means a property that the viscosity is high when the film is left to stand and the viscosity is reduced when a shear force is applied. Some ball-point pens have a pen with an ink composition, which is generally called gel ink, incorporated therein. The gel ink composition was as follows: the ink is kept stably in the writing instrument because of its high viscosity at the time of standing without applying a shear stress, and the ink in the vicinity of the ball is lowered in viscosity by the high shear force generated by the high-speed rotation of the ball at the time of writing, and as a result, the ink flows out from the gap between the ball and the ball containing portion and is transferred to the paper surface. The ink composition can be made into a gel ink by combining a shear thinning viscosity-imparting agent.

When polysaccharides are used, suitable polysaccharides include: a thickening polysaccharide or dextrin having a gelling ability extracted from seaweed, such as succinoglycan, xanthan gum, welan gum, guar gum, locust bean gum, carrageenan (carrageenan) and diutan gum (diutan gum), and derivatives thereof, cellulose derivatives, glucomannan, agar, and furcellaran (carrageenin). Among these, succinoglycan and xanthan gum are preferable because they have a large shear thinning effect, and succinoglycan is more preferable. The succinoglycan preferably has an average molecular weight of about 100 to 800 ten thousand. Examples of the cellulose derivative include hydroxymethyl cellulose.

When the ink composition of the present invention contains succinoglycan or xanthan gum, the content of succinoglycan or xanthan gum is preferably 0.01 to 1.0% by mass based on the total mass of the ink composition. When the content ratio of these is in this range, the ink flow-out property from the pen point can be maintained at a high level, and the aggregation of the microcapsule pigment can be suppressed.

Further, if dextrin or a cellulose derivative is used as the polysaccharide, high improvement effects such as adjustment of the ink viscosity, provision of shear thinning, improvement of drying resistance, and the like may be obtained at the same time. Among these, dextrin is preferable because the drying-resistant property improving effect is large.

The dextrin is preferably a sugar mixture containing a starch saccharide of 8 or more sugars and/or a reduced product thereof. The sugar mixture preferably contains not less than 30% by mass of not less than 8% by mass of a starch saccharide, more preferably not less than 50% by mass, and particularly preferably not less than 70% by mass. Such dextrin is preferable because it has a high effect of suppressing evaporation of water from the pen tip when the ink composition is applied to a writing instrument because of its excellent film-forming property.

When the ink composition of the present invention contains dextrin or a cellulose derivative, the content of these is preferably 0.1 to 5% by mass based on the total mass of the ink composition. When the content of the dextrin or the cellulose derivative is in this range, the ink flow-out property from the pen tip can be maintained at a high level, and the ink drop sagging and the evaporation of water from the pen tip can be suppressed.

These polysaccharides may be used alone or in combination of two or more.

Further, a substance other than polysaccharides may be used as the thickener. As other materials that can be used as a tackifier, there can be mentioned: alginic acid alkyl esters, polymers having a molecular weight of 10 to 15 ten thousand and containing alkyl methacrylate as a main component, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, cross-linkable acrylic acid polymers, inorganic fine particles, polyglycerol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene lanolin-beeswax derivatives, polyoxyethylene alkyl ether-polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, fatty acid amides, and other nonionic surfactants having an HLB value of 8 to 12, and salts of dialkyl or dialkenyl sulfosuccinic acid.

As another one of the optional components, a surfactant can be cited. The surfactant may preferably be any of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like. As the surfactant, there may be mentioned: phosphoric ester surfactants, silicone surfactants, surfactants having an acetylene bond in the structure, fluorine surfactants, and the like. These surfactants can be appropriately selected depending on the components, the use, and the like of the ink composition. For example, when the ink composition is used in a water-based ballpoint pen, a phosphate ester surfactant is preferable. The reason for this is that the phosphate ester surfactant exerts a good lubricating effect at the pen tip and allows smooth rotation of the ball. Specific examples of the phosphate ester surfactant include: phosphoric acid monoesters of polyoxyethylene alkyl ethers or polyoxyethylene alkylaryl ethers, phosphoric acid diesters of polyoxyethylene alkyl ethers or polyoxyethylene alkylaryl ethers, or metal salts, ammonium salts, amine salts, alkanolamine salts of these. When the ink composition of the present invention contains a surfactant, the content thereof is preferably 0.1 to 2.0% by mass, more preferably 0.3 to 1.5% by mass, based on the total mass of the ink composition.

As another optional component, a pH adjuster may be mentioned. In order to adjust the pH of the ink composition to an appropriate range, various acids or bases can be used as the pH adjuster. Examples of such pH regulators include: (a) inorganic basic compounds such as ammonia and sodium hydroxide, (b) inorganic acidic compounds such as phosphoric acid, hydrochloric acid, sulfuric acid and nitric acid, (c) inorganic salt compounds such as sodium carbonate and sodium phosphate, (d) water-soluble amine compounds such as triethanolamine and diethanolamine, urea derivatives such as urea, dimethylurea, diethylurea, hydroxymethylurea and hydroxyethylurea, organic basic compounds such as amide compounds such as acetamide and N-methylacetamide, (e) organic acidic compounds such as lactic acid, citric acid and tartaric acid, and (f) organic salt compounds such as sodium acetate, sodium bicarbonate and sodium tartrate. The content of the pH adjuster is preferably 0.1 to 5% by mass, more preferably 0.5 to 2% by mass, based on the ink composition.

The ink composition of the present invention may further comprise:

(i) rust inhibitors such as benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin and the like,

(ii) preservatives or mildewcides such as phenol, sodium salt of 1, 2-benzothiazolinone 3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl p-hydroxybenzoate, 2,3,5, 6-tetrachloro-4- (methylsulfonyl) pyridine and the like,

(iii) specific gravity adjusting agents such as sodium iso-tungstate, sodium meta-tungstate, sodium para-tungstate, etc.,

(iv) bubble absorbers such as ascorbic acids, isoascorbic acids, alpha-tocopherol, catechins, synthetic polyphenols, kojic acid, alkylhydroxylamine, oxime derivatives, alpha-glucosylrutin, alpha-lipoid acids, phosphonates, phosphinates, sulfites, disulfite sulfonate, thiosulfate, thiourea dioxide and the like,

(v) lubricants such as metal soaps, 2, 5-dimercapto-1, 3, 4-thiadiazole or salts or oligomers thereof, 3-amino-5-mercapto-1, 2, 4-triazole, thiocarbamate, dimethyldithiocarbamate, alpha-aliphatic acids, condensates of N-acyl-L-glutamic acid with L-lysine or salts thereof, ethylene oxide addition type cationic agents, N-acylamino acid surfactants, dicarboxylic acid type surfactants, beta-alanine type surfactants, and the like,

(vi) water-soluble organic solvents such as ethanol, propanol, butanol, sorbitol, glycol solvents, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, oligomers of N-vinyl-2-piperidone, N-vinyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, epsilon-caprolactam, N-vinyl-epsilon-caprolactam and the like,

(vii) glycol solvents, e.g. as glycol solvents

Ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, etc.,

(viii) water-soluble or water-insoluble resins such as polyamide resins, polyurethane resins, polyester resins, epoxy resins, melamine resins, phenol resins, silicone resins, polyvinyl alcohol, polyvinyl pyrrolidone having a polymerization degree of more than 20, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylic resins, maleic acid resins, gum arabic, cellulose and the like and derivatives thereof, copolymers of the resins and the like,

(ix) pigments other than the microcapsule pigment, for example, aluminum powder, metal pigments obtained by treating the surface of aluminum powder with a coloring resin, metallic luster pigments obtained by forming a metal vapor-deposited film on a transparent or colored transparent film, light-storing pigments, natural mica having a core material coated with a metal oxide such as titanium oxide, synthetic mica, glass flakes, aluminum oxide, and luster pigments such as pearl pigments obtained by coating the surface of a transparent film,

(x) Other components include, for example, a thiophosphoric triester such as casein, tris (alkoxycarbonylmethyl) thiophosphite, or tris (alkoxycarbonylethyl) thiophosphite, and the like.

< physical Properties of ink composition >

The ink composition of the present invention can be used for various writing instruments. In this case, the physical properties required for the ink composition vary depending on the type of writing instrument.

For example, when the ink composition of the present invention is used in a ball-point pen, the ink composition rotates at 20 ℃ for 3.84sec^-1When measured under the conditions (1) above, the viscosity is preferably 1 to 2000 mPas. The viscosity is more preferably 300 to 1500 mPas, particularly preferably 500 to 1000 mPas, considering the suppression of the precipitation and aggregation of the microcapsule pigment. Furthermore, at 20 ℃ the rotational speed is 384sec^-1The viscosity of the ink composition (1) is preferably 1 to 200 mPas, and more preferably 10 to 100 mPas, particularly preferably 20 to 50 mPas, from the viewpoint of improving the ink outflow from the tip. By having such a range, dispersion stability or easy flowability of the composition in the mechanism of the ball-point pen can be maintained at a high level.

Furthermore, the viscosity of the ink can be measured at a shear rate of 3.84sec in an environment of 20 ℃ using a DV-II viscometer (Cone Rotor CPE42) manufactured by Brookfield corporation^-1(1rpm) shear rate 384sec^-1The ink viscosity was measured under the condition of (100 rpm).

When the ink composition of the present invention is used in a ballpoint pen, the surface tension thereof is preferably 20 to 50mN/m, and more preferably 25 to 45mN/m, in an environment of 20 ℃. When the surface tension is within the above numerical range, the wettability of the ink composition to the coated surface can be improved and the ink composition tends to be prevented from penetrating into or penetrating into the coated surface when the ink composition is applied to a paper surface.

When the ink composition of the present invention is used in a ball point pen, the pH is preferably 3 to 10, more preferably 4 to 9, and particularly preferably 4 to 8 at room temperature (25 ℃ C.). By adjusting the pH value to such a range, aggregation and precipitation of the contained microcapsule pigment in a low temperature region can be suppressed.

When the ink composition of the present invention is used in a marker pen, the viscosity is preferably 1 to 30 mPas, more preferably 2 to 20 mPas, when the viscosity is measured at 20 ℃ and 30 rpm. In addition, the surface tension is preferably 25 to 45mN/m, more preferably 30 to 40mN/m in an environment of 20 ℃.

When the ink composition of the present invention is used in a pen, the viscosity is preferably 1 to 20 mPas, more preferably 1 to 10 mPas, when the viscosity is measured at 20 ℃ and 30 rpm. In addition, the surface tension is preferably 30 to 65mN/m, more preferably 35 to 55mN/m in an environment of 20 ℃.

The viscosity of the ink composition can be measured using a BL type rotational viscometer (product name: TVB-M type viscometer, B type spindle, manufactured by Toyobo industries Co., Ltd.). The surface tension was measured by a vertical plate method using a platinum plate using a surface tension meter manufactured by synechia interfacial science corporation.

Method for producing ink composition

The ink composition of the present invention can be produced by any method known in the art. Specifically, the above-mentioned components can be mixed in a necessary amount and mixed by various stirring machines such as a propeller stirrer, a homogeneous disperser and a homomixer, various dispersing machines such as a bead mill, and the like.

Writing tool

The ink composition of the present invention is used by being filled in a marker pen or a water-based ballpoint pen in which a marker pen tip or a ballpoint pen tip is attached to a writing tip portion, and writing instruments such as an ink pen, a fountain pen, and a writing pen.

When the ball-point pen is filled with the water-based ball-point pen, the structure and shape of the ball-point pen itself are not particularly limited, and examples thereof include: a ball-point pen having a structure in which ink is directly contained in a barrel and an ink flow rate adjusting member in a comb-groove shape or an ink flow rate adjusting member including a fiber bundle is interposed, the ink flow rate adjusting member being connected to a pen tip; the ball-point pen has an ink-containing tube filled with ink in the barrel, the ink-containing tube communicates with a pen tip having a ball attached to a tip end thereof, and a backflow prevention plug is closely attached to an end surface of the ink.

As described in more detail with respect to the ballpoint pen tip, the following can be applied: a pen tip (tubular ball point pen tip) in which a ball is held by a ball holding portion formed by pressing and deforming the vicinity of the tip of a metal tube from the outside to the inside, a pen tip in which a ball is held by a ball holding portion formed by cutting a metal material with a drill or the like, a pen tip in which a resin ball holder is provided inside a metal or plastic pen tip, a pen tip in which a ball held by the pen tip is energized forward by a spring body, or the like. The ballpoint pen tip is preferably a metal tube having a straight cylindrical body (straight tubular cylindrical body) at least at the tip end portion. Examples of the shape of the ballpoint pen tip include: the entire ballpoint pen tip includes a metal tube as a straight cylindrical body; or a metal pipe having a straight cylindrical shape at its tip end and having a shape with an enlarged outer diameter and inner diameter at its rear end. Among these, the latter is preferable because the ink flowing property is good.

Further, the ball is generally made of cemented carbide, stainless steel, ruby, ceramics, resin, rubber, or the like. In addition, the diameter of the beads is usually 0.2 to 3.0mm, preferably 0.25 to 1.5mm, more preferably 0.25 to 1.0mm, and particularly preferably 0.25 to 0.5 mm. Further, in the tubular ballpoint pen tip, by combining the ink composition of the present invention with a ballpoint pen having a ball diameter of, for example, 0.25 to 1.0mm, preferably 0.25 to 0.7mm, particularly preferably 0.25 to 0.5mm, a ballpoint pen excellent in ink flowing-out property and drying resistance can be obtained.

When the ink composition of the present invention is filled into a water-based ballpoint pen, the ball diameter and the amount of ink consumed preferably satisfy a specific relationship. Specifically, when the ink consumption per 100m of the water-based ballpoint pen is A (mg) and the ball diameter is B (mm), the relationship of 200. ltoreq. A/B.ltoreq.800 is preferable, and the relationship of 300. ltoreq. A/B.ltoreq.700 is more preferable. The reason for this is that: by setting the range, the ink consumption amount is appropriate for the bead diameter, whereby the ink fluidity is improved, and the blur of the handwriting or the like is suppressed, whereby the good handwriting can be easily obtained.

Further, regarding the ink consumption, a spiral writing test was performed using test sample 5 at a writing speed of 4 m/min under conditions of a writing angle of 70 ° and a writing load of 100g on writing paper JIS P3201 writing paper at 20 ℃, and the average of the ink consumption per 100m was defined as the ink consumption per 100 m.

The amount of movement (gap) of the ball in the longitudinal direction of the ball at the ballpoint pen tip is preferably 20 to 60 μm, and more preferably 30 to 45 μm, at the time of manufacturing or at the time of starting use of the ballpoint pen. The reason for this is that: if the gap is within the above range, the ink outflow amount can be appropriately adjusted, and line missing, blurring, or the like can be suppressed, whereby good handwriting can be easily obtained, and further, if the gap is within the above range, the above ratio a/B can be easily adjusted. In addition, the ink composition of the present invention contains a microcapsule pigment, and the gap may be adjusted according to the average particle diameter thereof to improve the running property of the ink. From this viewpoint, the ratio D/G of the average particle diameter D (μm) of the microcapsules based on the gap G (μm) is preferably 1/150. ltoreq. D/G. ltoreq. 1/3, more preferably 1/100. ltoreq. D/G. ltoreq. 1/5.

The amount of movement (gap) of the ball of the ballpoint pen tip in the longitudinal axis direction means the distance in which the ball can move in the longitudinal axis direction of the ballpoint pen tip body. Here, the movable amount is generally increased with use because the ball and the ball seat wear out with use. The movable amount is related to the amount of ink flowing out. Therefore, the amount of movement at the time of manufacturing or at the start of use of the ballpoint pen is usually set to the above range, and therefore, in order to achieve stable writing characteristics, it is preferable to keep the range until the end of use of the ballpoint pen.

As the ink containing tube for containing ink, for example, a molded body made of thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, and nylon is used. In order to prevent the ink composition contained therein from being modified by oxygen, a molded article containing a resin having low oxygen permeability and made of, for example, an ethylene-vinyl alcohol copolymer resin, a vinylidene chloride resin, an acrylonitrile resin, a polyester resin, or the like can be preferably used. The ink containing tube may have a single-layer structure or a multi-layer structure. In the case of the ink-receiving tube having a multilayer structure, at least 1 layer is preferably made of an ethylene-vinyl alcohol copolymer resin, a vinylidene chloride resin, an acrylonitrile resin, or a polyester resin. When the ink containing tube has a multilayer structure of 3 or more layers and is combined with layers containing ethylene-vinyl alcohol copolymer resin, vinylidene chloride resin, acrylonitrile resin, and polyester resin, the layers are preferably arranged except for the outermost layer and the innermost layer.

The pen tip may be directly connected to the ink containing tube, or the ink containing tube and the pen tip may be connected via a connecting member.

The ink storage tube may be in the form of a refill, and the refill may be stored in a shaft tube made of resin, metal, or the like, or the shaft tube itself having a pen tip attached to its tip may be used as an ink storage body, and the shaft tube may be directly filled with ink.

Preferably, the rear end of the ink contained in the ink containing tube is filled with an ink backflow preventer. The ink backflow preventer composition contains a nonvolatile liquid or a less volatile liquid.

Specifically, there may be mentioned: one or more kinds of vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α -olefin, oligomer or cooligomer of α -olefin, dimethylpolysiloxane oil, methylphenylpolysiloxane oil, amino-modified polysiloxane oil, polyether-modified polysiloxane oil, fatty acid-modified polysiloxane oil, and the like may be used.

The nonvolatile liquid and/or the nonvolatile liquid is preferably thickened to a preferred viscosity by adding a thickener, and examples of the thickener include: silica having a hydrophobic surface, fine-particle silica having a methylated surface, aluminum silicate, swellable mica, clay thickener such as bentonite or montmorillonite having a hydrophobic surface, fatty acid metal soap such as magnesium stearate, calcium stearate, aluminum stearate or zinc stearate, dextrin compound such as tribenzylsorbitol, fatty amide, amide-modified polyethylene wax, hydrogenated castor oil or fatty acid dextrin, cellulose compound, and the like. Further, a liquid ink backflow prevention member and a solid ink backflow prevention member may be used in combination.

In the case of filling into a marker pen, the structure and shape of the marker pen itself are not particularly limited, and examples thereof include: a marker pen in which an ink absorbing body made of a fiber aggregate is built in a barrel, a marker pen tip made of a fiber-processed body or a resin molded body having a capillary gap formed therein is attached to the barrel directly or via a relay member, and the ink absorbing body of the marker pen formed by connecting the ink absorbing body and the pen tip is impregnated with ink; or a marker pen having a structure in which ink is directly contained in the cylinder and the ink flow rate adjusting member is connected to the pen tip via a comb-shaped ink flow rate adjusting member or an ink flow rate adjusting member made of a fiber bundle; and a marker pen or the like in which a pen tip and an ink containing tube are arranged via a valve body openable by pressing the pen tip, and ink is directly contained in the ink containing tube.

The pen tip is a porous member having interconnected pores with a porosity selected from the range of approximately 30 to 70%, such as a resin processed body of fibers, a fused body of heat-fusible fibers, and a felt body, or an extrusion molded body of a synthetic resin having a plurality of ink outlet holes extending in the axial direction, and one end of the pen tip is processed into a shape for a purpose such as a shell shape, a rectangular shape, and a chisel shape, and is put into practical use.

The ink-absorbing body is formed by bundling the curled fibers in the longitudinal direction, is contained in a covering body such as a plastic cylinder or a film, and has a porosity adjusted to be in a range of approximately 40 to 90%.

The valve body may be of a suction type which has been conventionally used, but is preferably set to a spring pressure which can be pushed open by pen pressure.

The ink composition of the invention is suitable for the ink marker, in the barrel built-in by fiber bundles made of ink absorption body, formed with capillary gap by fiber processing body or resin molding made of marker nib directly or via the relay member is installed in the barrel, the ink absorption body in ink marker ink absorption body connected with the nib is impregnated with ink; the marker pen has a structure in which ink is directly contained in a barrel and the ink flow rate adjusting member is connected to a pen tip via a comb-shaped ink flow rate adjusting member or an ink flow rate adjusting member made of a fiber bundle, and more preferably, the marker pen has an ink storing body made of a fiber aggregate body and provided in the barrel, and a marker pen tip made of a fiber-processed body or a resin molded body having a capillary gap formed therein is attached to the barrel directly or via a relay member, and the ink storing body of the marker pen in which the ink storing body is connected to the pen tip is impregnated with ink. In the writing instrument having such a mechanism, an ink composition having low aggregation property of a microcapsule pigment and easy fluidity is required from the viewpoint of ink supply property to the pen tip, and therefore the ink composition of the present invention is particularly suitable for the writing instrument having the mechanism and can be suitably used as a reversible thermally color-changeable aqueous ink composition for a marker pen.

Further, the form of the ball-point pen or the marker is not limited to the above, and may be a composite writing instrument (a double-head type or a pen tip sequential discharge type) in which pen tips of different forms are attached or pen tips for discharging ink of different colors are attached.

The writing instrument of the above-described structure may be provided with a cap for protecting the pen tip or preventing drying.

Further, the writing instrument may be of a retractable type having a structure in which an ink storage body impregnated with ink is stored in an ink storage tube, a refill is prepared by attaching a pen body to a writing tip portion, the refill is stored in a barrel, and the writing tip portion is projected from an opening of the barrel by operation of a retractable mechanism. The ink composition of the present invention is preferably used for such an insertion/ejection type writing instrument because deterioration of writing characteristics due to drying of the pen tip is small.

Examples of the operation method of the access mechanism include: push-button, rotary, sliding, etc.

Handwriting formed by a writing instrument containing an ink composition may be discolored by friction generated by a finger or application of a heating or cooling instrument.

Examples of the heating tool include an electrically heating color-changing tool equipped with a resistance heating element, a heating color-changing tool filled with warm water or the like, and a hair dryer, and it is preferable to use a friction member or a friction body which can be changed in color by a simple method.

The friction member or the friction body is preferably an elastic body having a high elastic feeling and generating friction heat by appropriate friction at the time of friction, or an elastic body such as a plastic foam, and may be a plastic molded body, a stone material, a wood material, a metal, or a fabric.

Further, the handwriting may be rubbed using an eraser, but since eraser dust is generated during rubbing, it is preferable to use a rubbing member as described above.

As a material of the friction member or the friction body, silicone resin or SEBS resin (styrene-ethylene-butadiene-styrene block copolymer), SEPS resin (styrene-ethylene-propylene-styrene block copolymer), polyester resin, EPDM (ethylene-propylene-diene rubber) can be preferably used, and the silicone resin is more preferably used because the resin is easily attached to a portion to be erased by friction and the handwriting tends to be non-sticky during repeated writing.

The friction member may be a member (friction body) of any shape separate from the writing instrument, but is excellent in portability by being fixed to the writing instrument.

The site for fixing the friction member includes: a front end portion (top portion) of the cap or a rear end portion of the barrel (a portion where the writing front end portion is not provided).

Examples of the cooling tool include: the cooling color-changing tool using the Peltier component, the cooling color-changing tool filled with cold water, ice fragments and other refrigerants, and the refrigerator or the cold storage.

Further, a writing instrument kit may also be obtained by combining a writing instrument with an abrasive body.

Hereinafter, a preferred structure of the ballpoint pen and the refill for a ballpoint pen according to the present embodiment will be described with reference to the drawings.

< ball-point pen (embodiment 1) >)

FIG. 3 shows a ballpoint pen according to embodiment 1.

The ballpoint pen 1 includes a barrel 11, a ballpoint pen refill 2 housed in the barrel 11 so as to be movable in the front-rear direction, and an operation portion 12 provided on an outer surface of the barrel 11, and is configured as follows: by sliding the operation portion 12 (clip) forward, the ballpoint pen tip 3 (nib) of the ballpoint pen refill 2 can be inserted into and removed from the front end hole of the barrel 11.

The shaft tube 11 includes a front shaft 11a and a rear shaft 11b detachably screwed to the front shaft 11a, and the ball pen refill 2 in the shaft tube 11 can be exchanged by detaching the front shaft 11a from the rear shaft 11 b.

A friction body 13 made of an elastic material (e.g., rubber, elastomer, or other synthetic resin having elasticity) is attached to the rear end of the shaft tube 11. The ink for ink-jet recording is thermally discolored (or faded) by the frictional heat generated when the ink for ink-jet recording is rubbed by the rubbing body 13.

< ball-point pen (embodiment 2) >)

FIG. 4 shows a ballpoint pen according to embodiment 2.

The ballpoint pen 1 includes a barrel 11, a ballpoint pen refill 2 housed in the barrel 11, and a cap 14 detachably fitted to an outer surface of the barrel 11 on a ballpoint pen tip side (pen tip side), and a ballpoint pen tip 3 (pen tip) of the ballpoint pen refill 2 protrudes outward from a front end hole of the barrel 11.

The shaft tube 11 includes a front shaft 11a and a rear shaft 11b to which the front shaft 11a is detachably screwed, and the ballpoint pen refill 2 in the shaft tube 11 can be replaced by detaching the front shaft 11a from the rear shaft 11 b.

A friction body 13 made of an elastic material (e.g., rubber, elastomer, or synthetic resin having elasticity) is attached to the rear end of the shaft tube 11. The ink for ink-jet recording is thermally discolored (or faded) by the frictional heat generated when the ink for ink-jet recording is rubbed by the rubbing body 13.

Ball-point pen refill replacement

Fig. 5 to 7 show an embodiment of a ballpoint pen refill 2 used in the ballpoint pen 1.

The ballpoint pen refill 2 according to the present embodiment includes a ballpoint pen tip 3 that rotatably holds a ball 5 at a tip end portion, a spring 6 that is housed and arranged inside the ballpoint pen tip 3, a holder 7 that press-fixes the ballpoint pen tip 3 at a front portion, and an ink containing tube 8 that press-fixes a rear portion of the holder at a tip end opening portion.

In the present embodiment, the term "front" means the ball side of the tip, and the term "rear" means the opposite side.

Ballpoint pen nib

The ballpoint pen tip 3 is composed of a tip body 4 and a ball 5. The pen tip body 3 includes a metal cylinder including a small diameter cylinder 41 having a straight cylindrical shape and rotatably holding the ball 5 at a front end thereof, a tapered cylinder 42 integrally connected rearward from the small diameter cylinder 41 and having a diameter gradually increasing rearward, and a large diameter cylinder 43 having a straight cylindrical shape and integrally connected rearward from the tapered cylinder 42. The metal cylinder can be obtained, for example, from austenitic stainless steel such as SUS304, SUS305, and SUS 321.

A plurality of (for example, 4) inner protrusions 41b are formed on the inner surface of the pen tip body 3 near the tip end of the small-diameter cylinder 41 at equal intervals in the circumferential direction by inward pressing deformation. The bead seat is formed by the inner protrusion 41 b. Further, an inward front end edge portion 41a is formed at the front end of the pen tip body 3 by being pushed and deformed inward in a circumferential shape. A ball holding portion for rotatably holding the ball 5 is formed between the front surface of the inner protruding portion 41b (ball receiver) and the rear surface of the front end edge portion 41 a. Ink flow holes 41c extending radially outward from the center and penetrating in the axial direction are formed between the inner protrusions 41 b. That is, the ink flow hole 41c is formed in the ball holder. The ballpoint pen tip 3 may be of a type in which a ball holder is formed by cutting at the tip of a metallic tip body 3.

Straight cylindrical inner surface

A straight cylindrical inner surface is formed on the inner surface of the small-diameter cylinder portion 41 behind the inner protruding portion 41 b. A straight cylindrical inner surface is formed on the inner surface of the large diameter cylinder portion 43.

Conical inner surface

A tapered inner surface (or a conical inner surface) whose diameter gradually increases rearward is formed on the inner surface of the tapered tube portion 42.

Spring

The spring 6 is formed by integrally connecting a rod portion 61 provided at the front portion and a coil portion 62 provided at the rear portion with 1 metal wire (for example, a stainless steel wire having a wire diameter of 0.11 mm).

Rod part

The rod portion 61 extends linearly in the axial direction and is inserted into the ink flow hole 41c of the ball holder 41 b. The tip of the rod 61 abuts on a substantially central portion of the rear surface of the ball 5, and the ball 5 is directly energized forward by the rod 61. Thereby, the ball 5 is closely contacted with the inner peripheral surface of the tip edge portion 41a, and leakage of ink from the tip of the pen tip body 3 and evaporation of ink can be prevented.

Coil section

The coil portion 62 is formed by spirally winding a wire material. Close-wound portions in which the wire materials are closely adhered are formed at the front end portion and the rear end portion of the coil portion 62. The middle portion of the coil portion 62 excluding the front end portion and the rear end portion thereof forms an effective winding portion having a gap between the wires. The spring 6 sets the elastic force for biasing the ball 5 forward (specifically, the load when the ball 5 is pressed 0.01mm rearward) to be in the range of 14 g to 25 g (preferably 15 g to 22 g).

A holder

The holder 7 is a cylindrical body obtained by injection molding of a synthetic resin (e.g., polypropylene). The holder 7 includes a tapered front portion 71 to which the ballpoint pen tip 3 is attached, a flange portion 72 that abuts against the front end surface of the ink containing cylinder 8, and a rear portion 73 that is pressed into the front end opening of the ink containing cylinder 8. The rear portion of the pen tip body 3 is press-fitted into a mounting hole fixed to the front portion 71 of the holder 7. A step 74 is provided at the rear end of the inner surface of the mounting hole, the rear end of the pen tip body 3 is locked by the step 74, and the rear end of the spring 6 (the rear end of the coil portion 62) is locked by the step 74.

Ink cartridge

The ink cartridge 8 is a cylindrical body having openings at both ends, which is obtained by extrusion molding of a synthetic resin (e.g., polypropylene). The inside of the ink containing cylinder 8 is filled with an ink 81 and a follower 82 made of a high viscosity fluid that advances as the ink 81 is consumed. A tail plug 83 is press-fitted and fixed to a rear end opening of the ink cartridge 8. The tail plug 83 has a vent hole that allows the inside of the ink cartridge 8 to communicate with the outside air. The ink 81 is an aqueous ink composition for a ballpoint pen of the present invention. The follower 82 may be constituted by only a high-viscosity fluid or by containing a solid in a high-viscosity fluid, for example.

Round beads

The diameter A of the ball 5 is in the range of 0.25mm to 0.7mm (preferably 0.3mm to 0.5mm, more preferably 0.3mm to 0.45 mm). Specifically, the ball 5 is prepared in various sizes, for example, 0.25mm, 0.3mm, 0.4mm, 0.5mm, 0.7mm in diameter, according to the desired handwriting width.

The amount of axial movement of the ball 5 in the ball holding portion is preferably in the range of 0.02mm to 0.05mm in terms of obtaining smooth ink discharge. The amount of axial movement of the ball 5 in the ball holding portion varies depending on the diameter a of the ball 5, and is set to a range of 5% to 15% (preferably 8% to 12%) of the diameter a of the ball 5, whereby smooth ink flowing-out and sufficient ball exposure are obtained.

As the material of the ball 4, a metal generally used in ball-point pens, etc. can be used. Examples thereof include: titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or carbides or nitrides of the foregoing, and tungsten carbide (tungsten carbide) can be preferably used. Further, it is also preferable to use a cemented carbide containing cobalt as a binder and these materials as a base material.

When the ball is a cemented carbide containing cobalt, the binder may contain only cobalt, or may contain a metal such as iron or nickel in addition to cobalt. The content of cobalt is not particularly limited, and is preferably 5 to 20% by mass, more preferably 8 to 15% by mass, based on the total mass of the cemented carbide, in view of suppressing the deterioration of the surface of the bead and maintaining the good lubricity of the surface of the bead. Cobalt in the beads can be detected by analysis using an energy dispersive X-ray spectroscopy with a scanning electron microscope. For the measurement, an electron microscope (product name: Miniscope TM-1000, manufactured by Hitachi High-Technologies Co., Ltd.) and an EDX (Energy-dispersive X-ray) analyzer (product name: Swift ED-TM, manufactured by Oxford, UK) were used.

The amount of exposure E of the ball 5 to the axial forward direction is set to a range of 22% to 32% of the diameter A of the ball 5. The exposure amount E of the ball 5 in the axial forward direction is measured in a state where the ball 5 is in contact with each of the inner protrusions 41b (ball holders) by pushing the ball 5 in the backward direction against the forward bias of the spring. When a plurality of types of ball 5 having different diameters are used within the above range (particularly, the diameter A of the ball 5 is 0.3mm to 0.45mm) to obtain a plurality of types of ballpoint pen tips 3, a common spring 6 is used.

Minor diameter cylinder part

When the diameter a of the ball 5 is in the above range (particularly, the diameter a of the ball 5 is 0.3mm to 0.45mm), the inner diameter B of the straight cylindrical inner surface of the small-diameter cylinder portion 41 is set to be larger than the diameter a of the ball 5. Specifically, the inner diameter B of the small-diameter cylinder 41 is set to be 0.03mm to 0.06mm larger than the diameter a of the ball 5.

The axial length F of the straight cylindrical inner surface rearward of the inner projecting portion of the small-diameter cylinder portion 41 is set smaller than the diameter a of the ball 5. Thereby, the ink is supplied to the rear surface of the ball 5 in a lubricating manner, and a smooth ink flowing-out property is obtained.

Conical barrel portion

When the diameter a of the ball 5 is in the above range (particularly, when the diameter a of the ball 5 is 0.3mm to 0.45mm), the angle α of the tapered inner surface of the tapered cylindrical portion 42 (the angle α of the conical surface-shaped inner surface centered on the axis) is set to 30 degrees to 40 degrees. The length G in the axial direction of the tapered inner surface is set to be larger than the diameter A of the ball 5. Specifically, the axial length G of the tapered inner surface is set to 1.1 to 5.0 times (preferably 2 to 4.5 times) the diameter a of the ball 5. The tapered cylinder portion 42 can appropriately connect the small-diameter cylinder portion 41 and the large-diameter cylinder portion 43 so as to obtain smooth ink flow.

Large diameter barrel section

When the diameter a of the ball 5 is in the above range (particularly, the diameter a of the ball 5 is 0.3mm to 0.45mm), the inner diameter C of the straight cylindrical inner surface of the large-diameter tube 43 is set to 0.9mm or more (preferably 1mm or more), and the outer diameter D of the straight cylindrical inner surface of the large-diameter tube 43 is set to 1.2mm or more (preferably 1.3mm or more). The length H in the axial direction of the straight cylindrical inner surface of the large diameter cylinder 43 is set to be in the range of 4.0mm to 5.0 mm.

In the case where a plurality of types of ballpoint pens 3 are obtained using a plurality of types of balls 5 having different diameters within the above range (particularly, the diameter a of the ball 5 is 0.3mm to 0.45mm), the inner diameter C of each large-diameter cylindrical portion 43 is set to be the same, and the outer diameter D of each large-diameter cylindrical portion 43 is set to be the same, whereby the shape of the mounting portion of the ballpoint pen tip 3 to the holder 7 can be made common, and the manufacturing process can be simplified.

The ballpoint pen refill 2 of the present embodiment is required to have at least the following configuration.

The ballpoint pen refill 2 of the present embodiment includes: a ballpoint pen tip 3 having a tip end portion rotatably holding a ball 5, a spring 6 housed in the ballpoint pen tip 3, a holder 7 for fixing a rear portion 73 of the ballpoint pen tip 3, and an ink cartridge 8 having the rear portion 73 of the holder 7 fixed to a tip opening portion thereof,

the inside of the ink containing cylinder 8 is filled with a thermochromic ink 81 and a follower 82 composed of a high-viscosity fluid which advances as the ink 81 is consumed,

the ballpoint pen tip 3 includes a tip body 3 made of a metal cylinder including a small diameter cylinder 41 in a straight cylindrical shape rotatably holding a ball 5 at a front end, a tapered cylinder 42 integrally connected rearward from the small diameter cylinder 41 and gradually increasing rearward in diameter, and a large diameter cylinder 43 in a straight cylindrical shape integrally connected rearward from the tapered cylinder 42,

the elastic force of the spring 6 for energizing the ball 5 forward is set to be in the range of 14 g to 25 g,

the material of the ball 5 is a cemented carbide in which cobalt is contained in the bonding material,

the diameter A of the ball 5 is set to be in the range of 0.25mm to 0.7mm,

the movable amount of the ball 5 in the axial direction of the ball holding portion is set to be in the range of 0.02mm to 0.05mm,

the inner diameter B of the straight cylindrical inner surface of the small-diameter cylinder 41 behind the ball holder 41B is set to be 0.03 to 0.06mm larger than the diameter A of the ball 5,

the length F in the axial direction of the straight cylindrical inner surface of the small-diameter cylinder 41 behind the ball holder 41b is set to be smaller than the diameter A of the ball 5,

the inner diameter C of the straight cylindrical inner surface of the large diameter cylindrical portion 43 is set to 0.9mm or more.

Further, the structure of such a ballpoint pen or a refill for a ballpoint pen can provide excellent performance even when an ink composition other than the aqueous ink composition specified in the present invention is combined. In particular, in the case of a cemented carbide ball, if the ink composition is strongly acidic, the surface is sometimes deteriorated to reduce the lubricity of the ball surface. However, if the ink composition is strongly alkaline, the viscosity of the ink composition may increase due to interaction with a thickener usually contained in the ink composition. Therefore, the pH of the ink composition to be incorporated in the ballpoint pen or a ballpoint pen refill is preferably 4 or more and less than 7, and preferably 4.5 or more and less than 7. In particular, when the ink composition is an ink composition containing a microcapsule pigment, a ballpoint pen or a refill for a ballpoint pen having excellent characteristics can be obtained. That is, even in the case of using an ink composition in which the content of the reversible thermal discoloration microcapsule pigment, the N-vinyl-2-pyrrolidone polymer, and the glycerin is out of the range specified by the present invention, the reversible thermal discoloration aqueous ink composition containing the reversible thermal discoloration microcapsule pigment and the thickener and having a pH of 4 or more and less than 7 is incorporated, and the ballpoint pen or the refill for ballpoint pen having a ball containing a cemented carbide containing cobalt as a binder at the pen tip exhibits excellent characteristics.

[ examples ]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

The average particle diameter of the microcapsule pigment was measured using a volume-based average particle diameter (median particle diameter) measured by the above-mentioned laser diffraction/scattering type particle diameter distribution measuring apparatus (device name: LA-300, manufactured by horiba ltd., ltd.) calibrated with reference to a value measured by a measuring apparatus using the coulter method (electrical detection region method).

< preparation example 1: preparation of microcapsule pigment MC1

Preparation of reversible thermochromic compositions

A reversible thermal discoloration microcapsule pigment suspension encapsulating a reversible thermal discoloration composition composed of 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluoran as an electron donating color developing organic compound (component (a)), 4.5 parts of 1, 1-bis (4-hydroxyphenyl) n-decane and 7.5 parts of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane as an electron accepting compound (component (b)), and 50.0 parts of 4-benzyloxyphenylethyl decanoate as a reaction medium (component (c)) was obtained. The suspension is centrifuged to isolate the reversible thermochromic microcapsular pigment material. Further, the average particle diameter of the microcapsular pigment material was 2.5. mu.m, showing that t is₁：-20℃、t₂：-9℃、t₃：40℃、t₄: the behavior of the hysteresis characteristics at 57 ℃ and Δ H63 ℃ reversibly changes from black to colorless, and from colorless to black.

< preparation example 2: preparation of microcapsule pigment MC2

Obtaining a reversible thermochromic microcapsule pigment suspension encapsulating a thermochromic color memory composition composed of 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-nitrogen as an electron donating color developing organic compound (component (a))2.0 parts of heterophthalide, 8.0 parts of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane as an electron-accepting compound (component (b)), and 50.0 parts by mass of 4-benzyloxyphenylethyl decanoate as a reaction medium (component (c)). The suspension is centrifuged to isolate the reversible thermochromic microcapsular pigment material. The average particle diameter of the microcapsule pigment was 2.3 μm, showing that t is₁：-14℃、t₂：-6℃、t₃：48℃、t₄: the hysteresis characteristics at 60 ℃ and Δ H64 ℃ reversibly change from blue to colorless and from colorless to blue.

< example 1 >

The following components are mixed and mixed to obtain an ink composition.

18.0% by mass of reversible thermochromic microcapsules (MC1)

5.0% by mass of a polymer of N-vinyl-2-pyrrolidone (polymerization degree 2-20) (P1)

Glycerol (G) 5.0% by mass

Tackifier (V1) 0.2% by mass

(trade name: Rheozan, manufactured by Trilliac Kabushiki Kaisha)

Polysaccharide (D) 2.0% by mass

(trade name: Sundek 30, Sanhe starch industries Co., Ltd.)

0.5% by mass of the surfactant (S)

(trade name: Plyschf AL, manufactured by first Industrial pharmaceutical Co., Ltd.)

0.5% by mass of the pH adjustor (B)

(Triethanolamine)

0.2% by mass of preservative (AS)

(trade name: Proxel XL-2(S), manufactured by Lonza Japan K.K.)

Water (ion-exchanged water) residue

The obtained ink composition had a pH of 8.0 at 20 ℃ and a viscosity at a rotation speed of 3.84sec as measured at 20 DEG C^-1780 mPas at 384sec^-1At a temperature of 35.0 mPas, the surface tension at 20 ℃ was 37.0 mN/m.

< examples 2 to 12, comparative examples 1 to 8 >

Ink compositions of examples 2 to 12 and comparative examples 1 to 8 were obtained in the same manner as in example 1, except that the ink compositions were changed to the compositions shown in table 1.

< making of replacement refill for water-based ballpoint pen >

First, the ink compositions of the respective examples were filled into an ink-containing tube in which a ballpoint pen tip (trade name: vibration Ball 05, Ball diameter 0.5mm, gap 43 μm) manufactured by PILOT CORPORATION was fitted to one end of a polypropylene tube, and further, an ink backflow preventing member was brought into close contact with the rear end face of the ink to fill the ink-containing tube, thereby obtaining a ballpoint pen refill.

Regarding these replacement refills for ballpoint pens, the amount of ink consumed per 100m was studied. The ink consumption of the refill for a ballpoint pen containing the ink composition of example 1 (ball diameter: 0.5mm) was 280 mg. The same applies to examples 2 to 9, 11 to 12 and comparative examples 1 to 7 (all beads having a diameter of 0.5 mm). Further, in the refill for a water-based ballpoint pen of example 10 (ball diameter: 0.5mm), the amount of ink consumed was 230 mg. Further, the ink consumption per 100m of the ballpoint pen refill (ball diameter: 0.5mm) containing the ink composition of comparative example 8 was 160 mg.

Further, with respect to the ink compositions used in examples 11 and 12, the amount of ink consumed when the ink compositions were filled into refills of other ballpoint pens was also examined. Specifically, in embodiment 1, a ballpoint pen refill incorporating a ball having a ball diameter of 0.4mm or 0.5mm is prepared, and the refill is filled with an ink composition. The ink consumption amounts in the case of combining the ink compositions of examples 11 and 12 with ballpoint pen refill having a ball diameter of 0.4mm (examples 11A and 12A) were 220mg each, and the ink consumption amounts in the case of combining with ballpoint pen refill having a ball diameter of 0.5mm (examples 11B and 12B) were 300mg each.

< evaluation >

After each refill was allowed to stand at 50 ℃ for 30 days, the initial writing density and drying resistance were evaluated. Specifically, the pen tip is moved in a continuous circling manner while being brought into contact with the paper surface, thereby forming handwriting. At this time, the handwriting density at the writing start portion was visually confirmed, and the initial density was evaluated by the following criteria.

A: sufficient density can be confirmed at the writing start part

B: the concentration of the writing-starting part is slightly lower

C: the writing start part is hardly visually confirmed

The drying-resistant property was evaluated by counting the number of turns until the handwriting was formed, and by the following criteria.

A: blur within 1 circle

B: blur within 3 circles

C: blur within 6 circles

D: blur within 12 circles

E: can not write

Here, D and E are levels that are practically unusable.

In general, when the refill is left to stand for a long period of time, the pen tip may dry and solidify, and the ink composition may not flow out normally at the start of writing, resulting in blur in the handwriting. The less blurring at the start of writing, the more excellent drying-resistant property.

The results obtained are shown in table 1.

TABLE 1

In the table:

MC 1: microcapsule pigment MC1

MC 2: microcapsule pigment MC2

PIG 1: titanium oxide (trade name: CR-85, manufactured by Shinyuan Co., Ltd., average particle diameter: 0.25 μm)

P1: polymer of N-vinyl-2-pyrrolidone (degree of polymerization 2 to 20)

P2: epsilon-caprolactam

V1: succinoglycan (trade name: Rheozan, manufactured by Chili Kabushiki Kaisha)

V2: xanthan gum (trade name: Kelzan, manufactured by Trillium Kabushiki Kaisha)

D: dextrin (sugar mixture containing 94% of starch saccharide of 8 or more sugar, trade name: Sundek 30, manufactured by starch industries, Ltd.)

S: phosphate ester surfactant (trade name: Plysurf AL, first Industrial pharmaceutical Co., Ltd.)

B: triethanolamine

AS: trade name: proxel XL-2(S), manufactured by Lonza Japan K.K

The same evaluation was made on various performances when the ink compositions of examples 11 and 12 were filled in the refill for a ballpoint pen of the embodiment 1. The results of the evaluations were the same for examples 11A and 11B and examples 12A and 12B as in example 11.

Fig. 8 is a diagram showing an example of handwriting in the evaluation of drying performance. Fig. 8(a) is a photograph of a handwriting after evaluation of drying resistance when the ink composition of example 1 was used, and fig. 8(B) is an enlarged view of a drawn part thereof (upper left part of fig. 8 (a)). Fig. 9(a) is a photograph of a handwriting after evaluation of drying resistance when the ink composition of comparative example 1 was used, and fig. 9(B) is an enlarged view of a drawn part thereof (upper left part of fig. 9 (a)).

< example 13 >

The following components are mixed and mixed to obtain an ink composition.

10.0% by mass of reversible thermochromic microcapsules (MC2)

11.0% by mass of a bright pigment

(LG neo SILVER #325, manufactured by Oike Imaging Co., Ltd.)

24.0% by mass of a bright pigment

(Iriododin 103, manufactured by Merck Co., Ltd.)

5.0% by mass of a polymer of N-vinyl-2-pyrrolidone (polymerization degree 2-20) (P1)

Glycerol (G) 5.0% by mass

Urea 1.0% by mass

Tackifier (V1) 0.2% by mass

(trade name: Rheozan, manufactured by Trilliac Kabushiki Kaisha)

Polysaccharide (D) 2.0% by mass

(trade name: Sundek 30 III and manufactured by starch industries Co., Ltd.)

0.5% by mass of the surfactant (S)

(trade name: Plyschf AL, manufactured by first Industrial pharmaceutical Co., Ltd.)

0.2% by mass of the pH adjustor (B)

(Triethanolamine)

0.2% by mass of preservative (AS)

(trade name: Proxel XL-2(S), manufactured by Lonza Japan K.K.)

Water (ion-exchanged water) residue

< comparative example 9 >

Ink was prepared in the same manner as in example 13 except that the polymer of N-vinyl-2-pyrrolidone (polymerization degree 2 to 20) (P1) and glycerin (G) were removed and water (ion-exchanged water) was added.

In example 13 and comparative example 9, each of the prepared ink compositions was filled into an ink-containing tube in which a ballpoint pen tip (trade name: vibration Ball 07, Ball diameter 0.7mm, gap 46 μm) manufactured by PILOT CORPORATION was fitted to one end of a polypropylene tube, and further, an ink backflow preventer was brought into close contact with the ink rear end surface to fill the ink-containing tube, thereby obtaining a ballpoint pen refill.

The ink consumption per 100m of the ballpoint pen refill containing the ink composition of example 13 was 340 mg.

< evaluation >

The refill of each of example 13 and comparative example 9 was left to stand at 50 ℃ for 15 days, and then the initial writing density and drying resistance were evaluated in the same manner as in example 1. In example 13, the initial concentration and the drying resistance were evaluated as a, while the initial concentration of comparative example 9 was evaluated as a, but the drying resistance was evaluated as D, confirming that the ink composition of example 13 was excellent in drying resistance.

(reference example 1)

(preparation of reversible thermochromic microcapsular pigment microcapsule: microcapsular pigment MCA)

The inside of the capsule contains 4.5 parts of 2- (2-chlorophenylamino) -6-di-n-butylaminofluoran as the component (a),

4.5 parts of 1, 1-bis (4-hydroxyphenyl) n-decane, 7.5 parts of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane, and

50.0 parts of decanoic acid 4-benzyloxyphenylethyl ester as the component (c)

Microcapsule pigments of the compositionally reversible thermochromic composition (t)₁：-20℃，t₂：-9℃，t₃：40℃，t₄: 57 ℃, Δ H: 63 ℃, average particle size: 2.5 μm, from black to colorless, from colorless to black)

(preparation of aqueous ink composition)

The reversible thermal discoloration microcapsule pigment, the following raw materials and the amounts thereof were mixed at room temperature with stirring for 1 hour to obtain an aqueous ink composition. The pH of the aqueous ink composition thus obtained was measured using an IM-40S type pH meter (manufactured by DKK, east Asia), and it was found to be 5.7 at 20 ℃.

The viscosity of the aqueous ink composition was measured with an E-type rotational viscometer (trade name: DV-II viscometer, manufactured by Brookfield Co., Ltd., Rotor: Cone Rotor CPE42), and the rotational speed was 3.84sec at 20 ℃^-1The viscosity at room temperature was 780 mPas, and the rotation speed was 384sec^-1The viscosity at that time was 35.0 mPas.

Further, the surface tension of the aqueous ink composition was measured with a platinum plate using a surface tensiometer (vertical plate method, manufactured by Kyowa Kagaku K.K.) at 20 ℃ and was 37.0 mN/m.

16% by mass of reversible thermochromic microcapsule pigment (microcapsule pigment MCA)

Tackifier (succinoglycan, trade name: Rheozan, manufactured by Chili Kabushiki Kaisha) 0.3% by mass

Sugar (dextrin, trade name: Sundek 30, Sanyo starch industries Co., Ltd.) 1 mass%

0.5% by mass of a phosphate ester surfactant (polyoxyethylene aryl ether phosphoric acid, trade name: Plyschf AL, manufactured by first Industrial pharmaceutical Co., Ltd.)

0.2% by mass of triethanolamine

Phosphoric acid 0.2% by mass

0.2% by mass of a preservative (benzisothiazolin-3-one, trade name: Proxel XL-2(S), manufactured by Lonza Japan K.K.)

81.6% by mass of water

(reference examples 2 to 10, R1 to R6)

The ink compositions of reference examples 2 to 10 and R1 to R6 were obtained by changing the kind and amount of the components to be mixed with respect to reference example 1 as shown in table 2.

Details of the materials used in the examples are as follows.

Pigment (1) [ reversible thermochromic microcapsular pigment microcapsule (said microcapsular pigment MCA) ]

Pigment (2) [ titanium oxide (trade name: CR-85, manufactured by SHIYAKU-PRODUCTS CO., LTD., average particle diameter: 0.25 μm ]

Tackifier (succinoglycan, trade name: Rheozan, manufactured by Chili Kabushiki Kaisha)

Sugar (dextrin, trade name: Sundek 30, sugar mixture containing 94% of a starch saccharide of 8 or more sugars, manufactured by starch industries, Ltd.)

Phosphate ester surfactant (1) (polyoxyethylene aryl ether phosphoric acid, trade name: Plyschf AL, first Industrial pharmaceutical Co., Ltd.)

Phosphate ester surfactant (2) (polyoxyethylene aryl ether phosphoric acid, trade name: Dispersogen LFH, manufactured by Clariant Japan K.K.)

Phosphate ester surfactant (3) (polyoxyethylene tridecyl ether phosphoric acid, trade name: Plyschf A212C, manufactured by first Industrial pharmaceutical Co., Ltd.)

pH regulator (1) Triethanolamine

pH regulator (2) phosphoric acid

Preservative (benzisothiazolin-3-one, trade name: Proxel XL-2(S), manufactured by Lonza Japan K.K.)

Water-soluble organic solvent (Glycerol)

Water

The aqueous ink composition prepared was evaluated as follows. The results are shown in Table 2.

The ballpoint pen of embodiment 1 was produced and used in the evaluation test. The ball diameter of the ball-point pen was 0.4mm, and the amount of ink contained in the ball-point pen was 0.9 g.

In the table, cobalt contained in the beads was detected by EDX analysis (surface analysis at 1000-fold magnification) using an electron microscope (product name: Miniscope TM-1000, manufactured by Hitachi High-Technologies). The conditions for the analysis are as follows.

The device comprises the following steps: SEM: miniscope TM-1000 (manufactured by Hitachi High-Technologies Co., Ltd.)

EDX: SwiftED-TM (manufactured by Oxford, UK)

An electron gun: w hairpin filament type hot electron gun

Acceleration voltage: 15kV

A detector: silicon drift detector (EDX)

Measuring time: 100 seconds

(evaluation of blur and interruption of handwriting 1)

After the ball-point pen was left at 50 ℃ for 60 days, 10m circles of handwriting were continuously written on test paper under the writing conditions of 20 ℃ temperature, 100g writing load, 70 ° writing angle and 4 m/min writing speed, and the presence or absence of blurring or breaking of the handwriting was visually confirmed. The test paper used was JIS P3201 writing paper a.

A: no ambiguity, interruption, was confirmed.

C: blurring and interruption occur, and the handwriting has poor visibility. Has practical problems.

(evaluation of blur and interruption of handwriting 2)

The ballpoint pen used in evaluation 1 of blurring and breaking of handwriting was cooled in the following procedure 1 to 2, and then 10m continuous writing for forming a loop-like handwriting on test paper was performed. The blurring and the interruption of the handwriting at the moment are observed by eyes. The writing conditions, test paper, and the evaluation 1 of blurring and breaking of the handwriting were the same conditions.

1. The ballpoint pen was left at-20 ℃ for 24 hours in the lateral direction to freeze the ink.

2. After 24 hours at room temperature, the ink was thawed.

A: no ambiguity, interruption, was confirmed.

C: blurring and interruption occur, and the handwriting has poor visibility. Has practical problems.

(evaluation of lubricity of the bead surface)

The ballpoint pen used in the evaluation 2 for blurring and breaking of handwriting was checked to see whether or not writing was possible continuously until all the ink was consumed.

A; writing may continue continuously until all of the ink is consumed.

B: writing can continue until all of the ink is consumed, but there is little blurring, interruption in the writing immediately before all of the ink is consumed. Has no practical problem.

C: before the ink is completely consumed, the ball cannot be sufficiently rotated, and writing cannot be continued.

The test results are shown in Table 2 below.

[ Table 2]

Description of the reference numerals

t₁Complete color development temperature of microcapsule pigment of heat fading type

t₂The initial color development temperature of a pigment in a microcapsule of heat fading type

t₃The initial discoloration temperature of the pigment microcapsules of the heated discoloration type

t₄Complete fading temperature of heating fading type microcapsule pigment

Δ H is the hysteresis width.