WO2010035836A1 - Multi-color writing implement - Google Patents

Abstract

An attractive multi-color writing implement capable of producing a multi-colored written trace by using a single implement tip, having characteristics capable of producing a written trace of multiple colors formed at the same time in a single writing action, and capable of producing visually appealing written traces despite the use of a general-purpose structure. A multi-color writing implement (1) having a fiber tip, a felt tip, or a plastic tip (3) connected to one end or opposite ends of an ink occluding element (2) contained in a shaft tube (4).  Pigment-based ink (21, 22) of different colors is placed in the ink occluding element (2) in the longitudinal direction thereof.

Description

Multicolor writing instrument

The present invention relates to a multicolor writing instrument. Specifically, the present invention relates to a multicolor writing instrument that can form handwriting of a plurality of colors with a single nib.

Conventionally, a plurality of writing instruments having a structure in which inks having different color tones are supplied from two or more divided ink storage portions to the pen tip so that a plurality of colors of handwriting can be formed by a single pen tip (writing tip) are disclosed. (For example, see Patent Documents 1 to 3).

Japanese National Utility Model Publication No. 56-50687 Japanese National Utility Model Publication No. 61-53191 Japanese Unexamined Patent Publication No. 2004-27081

In the writing instrument, for example, in the configuration of Patent Document 3, two-color handwriting can be obtained with one pen tip, and two-color handwriting can be obtained at the same time with one writing, and each color tone overlaps (handwriting) (Substantially the central part of) can produce a gradation effect and form a special handwriting.

In order to obtain the handwriting stably over time, the writing instrument has a structure in which two or more ink storage portions are completely divided so that the stored ink does not mix during storage. Therefore, the structure of the entire writing instrument becomes complicated, and the manufacturing cost increases.

The present invention has the handwriting characteristics of the writing instrument, and is capable of stably obtaining a handwriting with a high visual effect for a long time even when a structure similar to that of a general-purpose marking pen is used. A color writing instrument is provided. Furthermore, the present invention provides a thermochromic multicolor writing instrument that has a color change due to heating of the handwriting and can exhibit a higher visual effect.

That is, the present invention has the following configuration.
(1) A writing instrument in which one of fiber tips, felt tips, and plastic tips is connected to one or both ends of an ink occlusion body accommodated in a shaft cylinder as a pen tip, and the color of the ink occlusion body has a color tone in the vertical direction. A plurality of different pigment-based inks are filled, and the non-color-changing pigment is suspended in a slowly aggregated state by a thermochromic ink using a thermochromic microcapsule pigment or a water-soluble polymer flocculant. A multicolor writing instrument characterized by being a turbid cohesive ink.
(2) A fiber tip, felt tip, or plastic tip provided with a plurality of connecting portions and a single writing tip for applying ink derived from each connecting portion is used as a pen tip, and each connecting portion is It is connected to the end of the same ink occlusion body, and is filled with pigment-based inks with different color tones extending in the vertical direction extending from each connection portion of the ink occlusion body. A multicolor writing instrument characterized by being a thermochromic ink using a microcapsule pigment or a cohesive ink in which a non-color-changing pigment is suspended in a gentle coagulated state with a water-soluble polymer coagulant.

(3) The multicolor writing instrument as described in (1) or (2) above, wherein the pigment-based ink is a thermochromic ink using a thermochromic microcapsule pigment.
(4) The thermochromic ink is decolored by heating, and the color tone of the colored state is different from the color tone of the other inks, as described in any one of (1) to (3) above Color writing instrument.
(5) Either of the above (1) or (2), wherein the pigment-based ink is a pigment-based aggregating ink in which a pigment is suspended in a loosely aggregated state with a water-soluble polymer flocculant. The multicolor writing instrument described.

(6) The multicolor writing instrument according to any one of (1) to (5), wherein the polymer flocculant is a water-soluble cellulose derivative.
(7) The multicolor writing instrument as described in any one of (1) to (6) above, wherein each ink contains a comb-type polymer dispersant having a carboxyl group.
(8) The multicolor writing instrument as described in any one of (1) to (7) above, wherein each ink contains an organic nitrogen sulfur compound.

(9) The multicolor writing instrument as described in any one of (1) to (8) above, wherein a difference in viscosity of each ink filled in the ink occlusion body is within 8 mPa · s.
(10) The multicolor writing instrument according to any one of (1) to (9) above, wherein a writing tip shape of the nib is a chisel shape.

According to the present invention, a multi-color writing instrument capable of forming a multicolored handwriting with a single nib and forming a multicolored handwriting with a gradation effect in a portion where each tone overlaps can be formed with a single writing. In addition, it is possible to stably form the handwriting over a long period of time without mixing ink in the ink occlusion body. Furthermore, when the handwriting is composed of thermochromic ink, the visual effect is higher than that when the handwriting is discolored by heating. Moreover, since a general-purpose marking pen structure can be applied, it is highly manufacturable and convenient.

4 is a graph illustrating hysteresis characteristics in a color density-temperature curve of a reversible thermochromic composition used in the present invention. It is a longitudinal cross-sectional explanatory drawing which shows an example of the thermochromic multicolor writing instrument used for this invention. It is longitudinal cross-sectional explanatory drawing which shows another example of the thermochromic multicolor writing instrument used for this invention. FIG. 4 is a cross-sectional view of the thermochromic multicolor writing instrument of FIG. 3 along AA. It is a longitudinal cross-sectional explanatory drawing which shows another example of the multicolor writing instrument used for this invention. It is a longitudinal cross-sectional explanatory drawing which shows another example of the multicolor writing instrument used for this invention. It is a longitudinal cross-sectional explanatory drawing which shows another example of the multicolor writing instrument used for this invention. It is AA sectional drawing of the multicolor writing instrument of FIG.

The multicolor writing instrument of the present invention accommodates a single ink occlusion body filled with pigment-based inks of a plurality of colors in a shaft cylinder (an exterior member made of a resin molded product or a metal processed body). This is a general-purpose marking pen with a pen tip connected to the end (so-called “filled type marking pen”). Can be formed automatically.

The pen nib is a fiber resin processed body, a fiber chip that is a fusion processed body of a heat-meltable fiber, a felt chip made of a felt body, and a plastic in which a plurality of filamentous resins are fused to form an ink flow path inside. A chip or the like utilizing a capillary force is applied, and one end is processed into a shape corresponding to the purpose such as a bullet shape, a rectangular shape, a chisel shape, etc.
In particular, the chisel-shaped nib can be used for fine writing and thick writing by changing the position of contact with the writing surface, and each ink color can be written individually. Since it has versatility that can form a mark with a width (handwriting formed with a plurality of colors at the same time), it is possible to construct a writing instrument with excellent convenience for forming various handwriting.

The rear end of the nib (that is, the portion connected to the ink occluding member) is composed of one or a plurality of connecting portions. When a plurality of connection portions are used, the same number as the kind (number) of inks accommodated in the ink occlusion body is applied.
In addition to being formed integrally with the writing tip portion, the connecting portion can be applied by connecting a separate body (so-called relay member).

The ink occlusion body is a general-purpose one in which crimped fibers are converged in the longitudinal direction (longitudinal direction). The ink occlusion body is contained in a covering such as a plastic cylinder or a film and has a porosity of approximately 40 to 90%. Configured to adjust to the range. Therefore, when a plurality of dye-based inks are filled in the vertical direction, the colors of the inks are mixed over time.
In addition, the said ink occlusion body can also be comprised by accommodating a plurality (each ink occlusion body filled with two or more colors of ink) in the shaft cylinder.

The writing instrument (pen nib and ink occlusion body) is composed of a single ink occlusion body arranged in a shaft cylinder filled with a plurality of colors of ink in the vertical direction, and the ink occlusion body is filled with the ink evenly. The one provided with a single nib (one or a plurality of connecting portions) at a position to be supplied is directly or via a relay member.
The pen tip is not only connected to one end of the ink occlusion body, but can also be applied to both ends and used in the form of a double-headed writing instrument.

As the ink filled in the multicolor writing instrument (ink occlusion body) of the above-mentioned form, a plurality of colors of pigment-based ink are applied. At least one of them can be applied with a thermochromic ink by adding a thermochromic microcapsule pigment.

The thermochromic microcapsule pigment is blended in the ink as a colorant, alone or in combination with a general pigment, and any conventionally known composition can be used as long as it exhibits heat decoloring characteristics. In particular, (b) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible heat containing at least three essential components of a reaction medium that determines the temperature at which the color reaction of both occurs. A pigment in which a color-changing composition is encapsulated in microcapsules is effective.
Among the reversible thermochromic compositions, examples of compositions that can be erased by heating include Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-229398, and the like. The color changes before and after the predetermined temperature (discoloration point) described in the above, exhibits a decolored state in the temperature range above the high temperature side discoloration point, and develops a color development state in the temperature range below the low temperature side discoloration point. Of the states, only one specific state exists in the normal temperature range, and the other state is maintained while the heat or cold necessary to develop the state is applied, but the heat or cold A composition having a characteristic (ΔH = 1 to 7 ° C.) having a relatively small hysteresis width that returns to a state exhibited in a normal temperature range when the application of is eliminated can be exemplified.
Also, Japanese Patent Publication No. 4-17154, Japanese Unexamined Patent Publication No. 7-179777, Japanese Unexamined Patent Publication No. 7-33997, Japanese Unexamined Patent Publication No. 8-39936, Japanese Unexamined Patent Publication No. 2005-1369. When the temperature rises from the lower temperature side than the discoloration temperature range when the shape of the curve that shows the large hysteresis characteristics (ΔH = 8 to 70 ° C) described in the official gazette, etc. On the contrary, the color changes by following a very different route from when the temperature is lowered from the color change temperature range, and the color development state in the low temperature range or the color disappearance state in the high temperature range is stored and retained in the specific temperature range. A reversible thermochromic composition that can be used can also be used.

The hysteresis characteristic in the color density-temperature curve of the composition will be described in detail.
In FIG. 1, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating the density at the lowest temperature T ₄ (hereinafter referred to as the complete color erasing temperature) reaching the complete color erasing state, and B is the maximum temperature T ₃ (hereinafter referred to as the color erasing) capable of maintaining the complete color development state. C is a point indicating the density at the lowest temperature T ₂ (hereinafter referred to as a color development start temperature) at which a completely decolored state can be maintained, and D reaches a complete color development state. This is a point indicating the density at the maximum temperature T ₁ (hereinafter referred to as a complete color development temperature).
Discoloration temperature region is a temperature region between the T ₁ and T _4, the colored state and the decolored state can coexist, temperature range substantially discoloration temperature between T ₂ and T ₃ is a large area of the difference in color density (Two-phase holding temperature range).
The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). If this ΔH value is small, only one specific state can exist in the normal temperature range among both states before and after the color change. Further, when the ΔH value is large, it is easy to maintain each state before and after the color change.

By using a reversible thermochromic composition having a color memory property among the above-described compositions, the color can be easily changed from the first state (colored) to the second state (colorless). And different colors can be seen interchangeably.
Specifically, the complete color development temperature T ₁ is a temperature that can be obtained only in a freezing room, a cold district, etc., that is, −30 to 10 ° C., preferably −30 to 0 ° C., more preferably −30 to −10 ° C. The complete decoloring temperature T ₄ is specified to be a temperature obtained from a familiar heating body such as frictional heat from a friction body, a hair dryer, that is, a range of 50 to 100 ° C., preferably 55 to 95 ° C., and a ΔH value of 40 to 80 By specifying the temperature in ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily life temperature range).

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

(B) Component electron-accepting compounds include active proton-containing compounds, pseudo-acidic compounds (a group of compounds that are not acids but act as acids in the composition to cause (a) components to develop color), electrons There is a group of compounds having pores.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Alternatively, those having an amide group, a halogen group, and the like, and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

Specific examples are given below.
Phenol, o-cresol, tertiary butyl catechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -3-methylbu 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxyphenyl) n-heptane, , 1-bis (4-hydroxyphenyl) n-octane, 1,1-bis (4-hydroxyphenyl) n-nonane, 1,1-bis (4-hydroxyphenyl) n-decane, 1,1-bis ( 4-hydroxyphenyl) n-dodecane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ethylpropionate, 2,2-bis (4-hydroxyphenyl)- 4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) n-heptane, 2,2-bis It is 4-hydroxyphenyl) n- nonane.

The compound having a phenolic hydroxyl group is a compound having a phenolic hydroxyl group having at least 3 or more benzene rings and having a molecular weight of 250 or more, preferably a molecular weight of 250 to 500, or a compound represented by the general formula (C ₆ H ₂ R ₁ R ₂ OH) ₂ S (wherein R ₁ represents an alkyl group having 1 to 8 carbon atoms, and R ₂ represents hydrogen or an alkyl group having 1 to 8 carbon atoms). When a compound having a hydroxyl group is used, the color change sensitivity at the time of transition from the decolored state to the colored state can be made more sensitive. Specifically, discoloration behavior when reaching the temperature (T ₁₎ indicating the complete coloring temperature via the temperature (T ₂₎ to start the coloring from the temperature (T ₄₎ showing complete decolored state as shown in FIG. 1 in the temperature to start the color development (T ₂₎ showed no behavior that develops color gradually shifted to the high temperature side, the temperature indicating the complete coloring temperature and the temperature (T ₂₎ to start the color development as in FIG. 1 (T ₁ ) The temperature difference is small, and it becomes easy to show a behavior that shifts sharply from the decolored state to the colored state.

As the compound having at least 3 or more benzene rings and having a phenolic hydroxyl group having a molecular weight of 250 or more,
4,4 ', 4 "-methylidenetrisphenol,
2,6-bis [(2-hydroxy-5-methylphenol) methyl] -4-methylphenol,
4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol,
4,4 ′, 4 ″ -ethylidene tris [2-methylphenol],
4,4 '-[(2-hydroxyphenyl) methylene] bis [2,3,6-triphenylphenol],
2,2-methylenebis [6-[(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol],
2,4,6-tris (4-hydroxyphenylmethyl) 1,3-benzenediol,
4,4 ', 4 "-ethylidene trisphenol,
4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylphenol],
4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol],
4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylphenol],
4,4 '-[(4-hydroxyphenyl] methylene] bis [2,6-dimethylphenol],
4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol],
2,4-bis [(5-methyl-2-hydroxyphenyl) methyl] -6-cyclohexylphenol,
4,4 '-[1- [4- [1- (4-hydroxy-3-methylphenol) -1-methylethyl] phenyl] ethylidene] bis [2-methylphenol],
4,4 '-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol],
4,6-bis [(4-hydroxyphenyl) methyl] 1,3-benzenediol,
4,4 '-[(3,4-di-hydroxyphenyl) methylene] bis [2,6-dimethylphenol],
4,4 '-(1-phenylethylidene) bisphenol,
5,5 '-(1-methylethylidene) bis [1-phenyl-2-ol],
4,4 ', 4 "-methylidenetrisphenol,
4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol,
4,4 '-(phenylmethylene) bisphenol,
4,4 '-[1,4-phenylenebis (1-methylethylidene)] bis [2-methylphenol],
5,5 '-(1,1-cyclohexylidene) bis- [1-biphenyl-2-ol] and the like.

As the compound having a phenolic hydroxyl group represented by the general formula (C ₆ H ₂ R ¹ R ² OH) ₂ S,
Bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl), bis (3-ethyl-4-hydroxyphenyl) sulfide, bis (3,5-diethyl-4-) Hydroxyphenyl) sulfide, bis (3-propyl-4-hydroxyphenyl) sulfide, bis (3,5-dipropyl-4-hydroxyphenyl) sulfide, bis (3-tert-butyl-4-hydroxyphenyl) sulfide, bis ( 3,5-t-butyl-4-hydroxyphenyl) sulfide, bis (3-pentyl-4-hydroxyphenyl) sulfide, bis (3-hexyl-4-hydroxyphenyl) sulfide, bis (3-heptyl-4-hydride) Xylphenyl) sulfide, bis (5-octyl-2-hydroxyphenyl) Rufido, and the like.
The compound having a phenolic hydroxyl group can exhibit the most effective thermochromic property, but it is an aromatic carboxylic acid, an aliphatic carboxylic acid having 2 to 5 carbon atoms, a carboxylic acid metal salt, an acidic phosphate, and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

The component (c) of the reaction medium that causes the electron transfer reaction by the components (a) and (b) to occur reversibly in a specific temperature range will be described. Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
The component (c) is preferably a color density-temperature curve with a large hysteresis characteristic (a curve plotting a change in color density due to a temperature change is a case where the temperature is changed from the low temperature side to the high temperature side, and the temperature is changed from the high temperature side to the low temperature side). A carboxylic acid ester compound having a ΔT value (melting point-cloud point) of 5 ° C. or more and less than 50 ° C., which can form a reversible thermochromic composition exhibiting color memory properties, which changes color when changing to the side) For example, a carboxylic acid ester having a substituted aromatic ring in the molecule, an ester of a carboxylic acid having an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester having a cyclohexyl group in the molecule, 6 carbon atoms Fatty acid and unsubstituted aromatic alcohol or phenol ester, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid And esters of aromatic alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, Dimyristin, distearin and the like are used.

Also, fatty acid ester compounds obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even carbon number, n-pentyl alcohol or n-heptyl alcohol and an even fat having 10 to 16 carbon atoms. A fatty acid ester compound having a total carbon number of 17 to 23 obtained from a group carboxylic acid is also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, lauric acid n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate Undecyl, n-tridecyl myristate, N-pentadecyl ristinate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, stearic acid n-undecyl, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-behenate Examples include undecyl, n-tridecyl behenate, and n-pentadecyl behenate.

Further, as ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, and 5-undecanone. 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2 -Pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadacanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.
Also, arylalkyl ketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano Phenone, 4-n-dodecanacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n -Decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone, n-heptaphenone, 4-n-pentylacetopheno , Phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone.

As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and 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, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, undecane diol diethyl ether Etc.

Furthermore, compounds described in Japanese Patent Application Laid-Open No. 2006-137886 and Japanese Patent Application Laid-Open No. 2006-188660 are more preferably used as the component (c).

Although the form of the microcapsule pigment applied to the present invention does not refuse application of a circular cross-sectional form, a non-circular cross-sectional form is effective.
The reversible thermochromic handwriting formed by writing has the above-mentioned microcapsule pigment closely oriented and fixed in close contact with the writing surface on the long diameter side (maximum outer diameter side). In addition, the microcapsule pigment is slightly elastically deformed into a shape that relaxes the external force against the external force caused by rubbing with a friction body such as rubber, and the destruction of the wall film of the microcapsule is suppressed. It can be expressed effectively without impairing the function.
Here, the non-circular cross-sectional shape microcapsule pigment has an average maximum outer diameter in the range of 0.5 to 5.0 μm, and a reversible thermochromic composition / wall film = 7/1 to 1 / 1 (weight ratio) is preferably satisfied.
The microcapsule pigments (including those having a circular cross-sectional shape) exhibit a decrease in the ability to flow out from the capillary gap when the average maximum outer diameter exceeds 5.0 μm, while the average maximum outer diameter When the value is 0.5 μm or less, it is difficult to show high density color development. Preferably, the average value of the maximum outer diameter is in the range of 1 to 4 μm, the average particle diameter of the microcapsule [(maximum outer diameter + center The minimum outer diameter of the part) / 2] is preferably in the range of 1 to 3 μm.
If the ratio of the reversible thermochromic composition to the wall film is larger than the above range, the wall film becomes too thin, causing a decrease in pressure and heat resistance, and conversely, the reversible thermochromic composition of the wall film. When the ratio to the above is larger than the above range, the color density and sharpness at the time of color development are inevitably lowered, and preferably the reversible thermochromic composition / wall film = 6/1 to 1/1 (weight ratio). .

For the microencapsulation of the reversible thermochromic composition, known means such as an interfacial polymerization method, an interfacial polycondensation method, an in situ polymerization method, and a coacervate method can be applied, but the particle size range satisfying the above-described requirements of the present invention In order to obtain a microcapsule pigment having a non-circular cross-sectional shape, it is effective to apply an interfacial polymerization method or an interfacial polycondensation method that hardly causes aggregation and coalescence.

The thermochromic microcapsule pigment can be blended in an amount of 5 to 40% by mass, preferably 10 to 40% by mass, more preferably 10 to 30% by mass, based on the total amount of the ink composition.
If it is less than 5% by mass, the color density is insufficient, and if it exceeds 40% by mass, the ink outflow is reduced and writing performance is impaired.

As a general pigment (also referred to as a non-color-changing pigment) used for adding to the thermochromic ink to change the color from colored 1 to colored 2 or for general ink (non-color-changing ink), an aqueous system is used. All general-purpose materials that can be dispersed in the medium can be used, and inorganic pigments such as carbon black and ultramarine blue, organic pigments such as copper phthalocyanine blue and benzidine yellow, and surfactants and resins in advance can be used in a fine and stable manner. A water-dispersed pigment product dispersed in a medium is used.
Further, a synthetic resin fine particle-shaped fluorescent pigment in which various fluorescent dyes are formed into a solid solution in a resin matrix, a white pigment such as titanium dioxide, a metal powder such as aluminum, a natural mica, a synthetic mica, alumina, and a glass piece. A pearl pigment whose surface is coated with a metal oxide such as titanium dioxide, a cholesteric liquid crystal type glitter pigment, a photochromic composition or a microcapsule pigment containing a fragrance can also be used.
Moreover, the microcapsule pigment formed by encapsulating the general pigment or general-purpose dye can also be applied. In that case, the particle size of the microcapsule particles is preferably in the range of 0.5 to 5.0 μm. By setting the above range, it is difficult to mix the inks of each color tone in the ink occlusion body, which is useful in the writing instrument of the present application configuration. In addition, the effect by the said particle size is acquired also about the above-mentioned non-color-change pigment in general.

As a medium used for the thermochromic ink and general ink (non-color-changing ink), water and, if necessary, a water-soluble organic solvent are used.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2- Pyrrolidone, or the like is used.
Incidentally, the microcapsule pigment encapsulating the reversible thermochromic composition having a large hysteresis width has a specific gravity of more than 1, so that the water-soluble organic solvent to be applied is preferably more than 1.1.

Further, a water-soluble polymer flocculant can be added to the pigment-based ink (thermochromic ink or non-thermochromic ink), and the flocculant is loose between the particles of the microcapsule pigment or the general pigment. It causes a bridging action and shows a loose aggregation state. Since the ink showing such a loose aggregation state can suppress separation of each pigment, it is possible to suppress mixing (color mixing) of ink in the pen tip or the ink occlusion body for a long period of time. Therefore, it becomes more useful in the multicolor writing instrument of this application structure.

A water-soluble polymer is used as the polymer flocculant, and examples thereof include polyvinyl pyrrolidone, polyethylene oxide, and water-soluble polysaccharides.
Examples of the water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, water-soluble cellulose derivatives and the like. Specific examples of water-soluble cellulose derivatives include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose. Among them, the water-soluble cellulose derivative functions more effectively.
Two or more kinds of the polymer flocculants can be used in combination, and 0.05 to 20% by weight can be blended with respect to the total amount of the ink composition.

Combining the polymer flocculant with a comb-type polymer dispersant having a carboxyl group in the side chain or an organic nitrogen-sulfur compound together improves the dispersibility of loose aggregates of each pigment by the polymer flocculant. In particular, the microcapsule pigment exhibits a high effect.
The comb polymer dispersant is not particularly limited as long as it is a comb polymer compound having a plurality of carboxyl groups in the side chain, but an acrylic polymer compound having a plurality of carboxyl groups in the side chain may be used. Preferred examples of the compound include trade name: Solsperse 43000 manufactured by Nippon Lubrizol Corporation.

The organic nitrogen-sulfur compound further suppresses the precipitation of microcapsule pigments and general pigments due to vibration when the ink composition is filled into a writing instrument for practical use.
This further improves dispersibility in which loose aggregates of microcapsule pigments are dispersed by a comb-type polymer dispersant having a carboxyl group in the side chain.
As the organic nitrogen sulfur compound, a compound selected from thiazole compounds, isothiazole compounds, benzothiazole compounds, and benzoisothiazole compounds is used.
Specific examples of the organic nitrogen sulfur compound include 2- (4-thiazoyl) -benzimidazole (TBZ), 2- (thiocyanatomethylthio) -1,3-benzothiazole (TCMTB), 2-methyl-4-isothiazoline- One or more compounds selected from 3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are used, preferably 2- (4-thiazoyl) -benzimidazole (TBZ), 2 One or more compounds selected from -methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are used.
As the organic nitrogen sulfur compound, manufactured by Permachem Asia Co., Ltd., trade names: Topside 88, 133, 170, 220, 288, 300, 400, 500, 600, 700Z, 800, 950, manufactured by Hokuko Sangyo Co., Ltd., trade names: Hokuster HP, E50A, Hokuside P200, 6500, 7400, MC, 369, R-150.
The mass ratio of the comb-type polymer dispersant having a carboxyl group in the side chain to the organic nitrogen sulfur compound is 1: 1 to 1:10, preferably 1: 1 to 1: 5, and satisfies the above range. Thus, the dispersibility of loose aggregates of the microcapsule pigment and the suppression of sedimentation of the microcapsule pigment due to vibration can be sufficiently expressed.

In addition, resins such as alkyd resins, acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin can be added as necessary to impart adhesion and viscosity to the paper surface. As the polyvinyl alcohol, a partially saponification type polyvinyl alcohol having a saponification degree of 70 to 89 mol% is more preferably used because the ink is highly soluble even in an acidic region.
The water-soluble resin is added in an amount of 0.3 to 3.0% by mass, preferably 0.5 to 1.5% by mass in the ink.
Furthermore, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin, etc. Rust inhibitor, coal acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (Methylsulfonyl) pyridine and other preservatives or antifungal agents, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin, sorbit, man Knit, Pi Wetting agents such as phosphoric acid sodium, defoamers, dispersing agents, a surfactant may be added a fluorine-based surfactant or a nonionic improve the ink permeability.

Plural types of pigment-based inks (thermochromic ink and non-color-changing ink) accommodated in the writing instrument have a viscosity difference of 0 to 8 mPa · s (measured value at a BL type viscometer 30 rpm at 20 ° C.) It is preferable to prepare and use so that.
By setting it as the said range, since accommodation ink moves uniformly within a nib and an ink occlusion body with consumption of ink, the stable handwriting can always be formed. In particular, it is most preferable to eliminate the viscosity difference between the inks (that is, 0).
In addition, the viscosity of each ink with which an ink occlusion body is filled will not be limited if it is a range which can be applied to a general purpose filling-type marking pen.

Further, the surface tension of each pigment-based ink can be adjusted to 25 to 45 mN / m, preferably 30 to 45 mN / m.
By adjusting the surface tension within the above range, it is difficult to cause blurring when writing, and the ink can be left in a temperature range below 0 ° C. where the ink freezes, or left in a high temperature range, for example, 50 ° C. It is difficult to cause variations in handwriting density and writing width depending on the storage environment and use environment without impairing the flowability.
In particular, in a thermochromic ink, if the surface tension is less than 25 mN / m, the outflow property of the ink tends to be unstable, and the handwriting density becomes non-uniform. Further, when the surface tension exceeds 45 mN / m, line breakage is likely to occur, and the ink outflow amount decreases due to the storage environment and use environment described above, and the handwriting density decreases, and the writing width tends to vary. .

In addition, the handwriting using the above-mentioned thermochromic ink can change the color tone from the colored state to the colorless state or the colored two state by applying a heating means such as a finger rubbing or a heating tool.
As the heating means, a thermosensitive device such as a copying machine suitable for erasing a large area at once, a lighting device such as a light bulb, a hair dryer, etc. are used, and further, an energizing heating color changing tool equipped with a resistance heating element, Application of heating discoloration tools filled with warm water or the like can be mentioned. Moreover, since it is a means which can be discolored by a simple method, a scraping member (friction body) is preferably used.
As the rubbing member, an elastic body such as an elastomer or plastic foam which is rich in elasticity and can generate frictional heat by rubbing at the time of rubbing is preferable, but a plastic molded body, stone material, wood, Metals and fabrics may be used.
Although it is possible to scrape the handwriting by using an eraser, it is preferable to use a rubbing member as described above because erase scraps are generated at the time of rubbing.
As the material of the rubbing member, silicone resin, SBS resin, SEBS resin and the like are preferably used. Further, as the scraping member, a member having a Shore hardness A of 55 degrees or more in JIS K6253A is more preferable.
Although the rubbing member may be a member having an arbitrary shape that is separate from the writing instrument, it is excellent in portability by being fixed to the writing instrument.
Examples of the location where the rubbing member is fixed include the tip of the cap (top) or the tip of the shaft tube (the portion where the writing tip is not provided).
Furthermore, it is also possible to provide a small protrusion of any shape on a part of the cap or a part of the shaft tube to make a scraping member.

Examples and Comparative Examples are shown below, but the present invention is not limited to these Examples. In addition, the part in an Example and a comparative example is a weight part.
The viscosity of each ink was measured at 30 rpm at 20 ° C. using a BL type rotational viscometer [manufactured by Tokyo Keiki Co., Ltd.].
Originally, the ink occlusion body is one member. For convenience, in FIGS. 2 to 8, the places where inks of different colors are filled are drawn with different hatchings.

Preparation of thermochromic ink Preparation of reversible thermochromic microcapsule pigment A (a) 3.0 parts of 1,3-dimethyl-6-diethylaminofluorane as component (1,) 1,1-bis (4- Hydroxyphenyl) -2-ethylhexane (3.0 parts), 2,2-bis (4′-hydroxyphenyl) -hexafluoropropane (5.0 parts), (c) 4-benzyloxyphenylethyl caprate as component (c) A microcapsule pigment suspension containing a reversible thermochromic composition having color memory properties consisting of parts was obtained.
The suspension was centrifuged to isolate reversible thermochromic microcapsule pigment A.
The microcapsule pigment A has an average particle size of 2.5 μm, a complete color erasing temperature of 60 ° C., and a complete color development temperature of −20 ° C., which changes from orange to colorless according to temperature change.

Preparation of reversible thermochromic water-based ink A 20.0 parts of the microcapsule pigment A (previously cooled to −20 ° C. or less to develop an orange color), 0.5 part of hydroxyethyl cellulose, a comb polymer dispersant [ Nippon Lubrizol Co., Ltd., trade name: Solsperse 43000], 0.2 parts, organic nitrogen sulfur compound [manufactured by Hokuko Chemical Co., Ltd., trade name: Hokuside R-150, 2-methyl-4-isothiazoline-3- Mixture of ON and 5-chloro-2-methyl-4-isothiazolin-3-one] 1.0 part, 0.5 part of polyvinyl alcohol, 25.0 parts of glycerin, 0.02 part of antifoaming agent, 52.78 water Parts were mixed to obtain a reversible thermochromic aqueous ink composition A.
The ink composition A had a viscosity of 16.1 mPa · s.

Preparation of reversible thermochromic microcapsule pigment B (a) 4,5,6,7-tetrachloro-3- [4- (dimethylamino) -2-methylphenyl] -3- (1-ethyl-2) as component -Methyl-1H-indol-3-yl) -1 (3H) -isobenzofuranone 2.0 parts, (ro) component 1,1-bis (4-hydroxyphenyl) n-heptane 3.0 parts, , 2-bis (4'-hydroxyphenyl) -hexafluoropropane, and (c) a reversible thermochromic composition having color memory, comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) To obtain a microcapsule pigment suspension encapsulating.
The suspension was centrifuged to isolate reversible thermochromic microcapsule pigment B.
The microcapsule pigment B has an average particle size of 2.5 μm, a complete color erasing temperature of 55 ° C., a complete color development temperature of −20 ° C., and changes color from blue to colorless with temperature change.

Preparation of reversible thermochromic water-based ink B 20.0 parts of the reversible thermochromic microcapsule pigment B (previously cooled to −20 ° C. or less to develop a blue color), 0.5 parts of hydroxyethyl cellulose, comb type high 0.2 parts of a molecular dispersant [manufactured by Nippon Lubrizol Co., Ltd., trade name: Solsperse 43000], organic nitrogen sulfur compound [manufactured by Hokuko Chemical Co., Ltd., trade name: Hokuside R-150, 2-methyl-4- Mixture of isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one] 1.0 part, 0.5 part of polyvinyl alcohol, 25.0 parts of glycerin, 0.02 part of antifoaming agent, 52.78 parts of water was mixed to obtain a reversible thermochromic water-based ink composition B.
The ink composition B had a viscosity of 18.2 mPa · s.

Preparation of reversible thermochromic microcapsule pigment C (a) 3.0 parts of 4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine as component (b) Reversible heat having color memory composed of 10.0 parts of 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane as component and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) A microcapsule pigment suspension containing the color-changing composition was obtained.
The suspension was centrifuged to isolate reversible thermochromic microcapsule pigment C.
The microcapsule pigment C has an average particle size of 2.5 μm, a complete color erasing temperature of 59 ° C., and a complete color development temperature of −20 ° C., which changes from yellow to colorless according to temperature change.

Preparation of reversible thermochromic water-based ink C 25.0 parts of the reversible thermochromic microcapsule pigment C (previously cooled to −20 ° C. or less to develop yellow color), 0.5 part of hydroxyethyl cellulose, comb-shaped high 0.2 parts of a molecular dispersant [manufactured by Nippon Lubrizol Co., Ltd., trade name: Solsperse 43000], organic nitrogen sulfur compound [manufactured by Hokuko Chemical Co., Ltd., trade name: Hokuside R-150, 2-methyl-4- Mixture of isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one] 1.0 part, 0.5 part of polyvinyl alcohol, 25.0 parts of glycerin, 0.02 part of antifoaming agent, Reversible thermochromic water-based ink C was obtained by mixing 47.78 parts of water.
The viscosity of the ink composition C was 16.5 mPa · s.

Preparation of reversible thermochromic microcapsule pigment D (I) 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine- 1.0 part of 5,1 ′ (3′H) -isobenzofuran] -3-one, 3.0 parts of 1,1-bis (4-hydroxyphenyl) n-decane as component (b), 2,2- A reversible thermochromic composition having color memory composed of 5.0 parts of bis (4'-hydroxyphenyl) -hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) was included. A microcapsule pigment suspension was obtained.
The suspension was centrifuged to isolate reversible thermochromic microcapsule pigment D.
The microcapsule pigment D has an average particle size of 2.3 μm, a complete color erasing temperature of 58 ° C., a complete color development temperature of −20 ° C., and changes from pink to colorless according to temperature change.

Preparation of reversible thermochromic water-based ink D 20.0 parts of the reversible thermochromic microcapsule pigment D (previously cooled to -20 ° C. or less to develop a pink color), 0.5 parts of hydroxyethyl cellulose, comb-shaped 0.2 part of a polymer dispersant [manufactured by Nippon Lubrizol Co., Ltd., trade name: Solsperse 43000], 1.0 part of an organic nitrogen sulfur compound [manufactured by Hokuko Chemical Co., Ltd., trade name: Hokuside 369], polyvinyl alcohol 0.5 part, 25.0 parts of glycerin, 0.02 part of antifoaming agent and 52.78 parts of water were mixed to obtain a reversible thermochromic water-based ink D.
The ink composition D had a viscosity of 20.3 mPa · s.

Preparation of reversible thermochromic water-based ink E Reversible thermochromic water-based ink E was obtained by adding and mixing 0.5 parts of a blue fluorescent pigment (manufactured by Sinloihi) into the reversible thermochromic ink D. The ink composition E had a viscosity of 18.0 mPa · s.
The ink E gives a purple handwriting at the time of writing, changes to blue when heated to 58 ° C. or higher, and returns to the original purple when further cooled to −20 ° C. or lower.

Preparation of reversible thermochromic water-based ink F Reversible thermochromic water-based ink F was obtained by adding 1.0 part of yellow fluorescent pigment (manufactured by Sinloihi) to the reversible thermochromic ink B and mixing them. The ink composition F had a viscosity of 17.1 mPa · s.
The ink F gives a green handwriting at the time of writing, changes to yellow when heated to 55 ° C. or higher, and returns to the original green when further cooled to −20 ° C. or lower.

Example 1
Production of thermochromic multicolor writing instruments (see Fig. 2)
Into the cylindrical ink occlusion body 2 in which a polyester sliver is coated with a synthetic resin film, the previously prepared thermochromic inks A and B are uniformly impregnated in the vertical direction by needle injection, and the shaft cylinder 4 made of polypropylene resin is impregnated. After assembling the polyester fiber resin processing pen tip 3 (chisel type) and connecting state (the pen tip connecting portion is located at the approximate center of the circumference of the ink occlusion body) accommodated and attached to the tip of the shaft cylinder, A multicolor writing instrument 1 (marking pen) was obtained by attaching the cap 5. A friction body 6 made of SEBS resin is mounted on the rear end portion of the shaft cylinder. The difference in viscosity between the two types of ink is 2.1 mPa · s.
In the ink occlusion body 2, reference numerals 21 and 22 indicate a location where the ink A is filled and a location where the ink B is filled, respectively.

When writing on the paper surface using the marking pen, when drawing a thick line, a multicolored handwriting of orange and blue with a boundary at the gradation is obtained, and when drawing a thin line at each top, an orange or blue color is obtained. Monochromatic handwriting was obtained.
The handwriting was multicolored or monochromatic at room temperature (25 ° C.). When the handwriting was rubbed with the friction body 6 at the rear end of the shaft cylinder, the handwriting was discolored and became colorless. This state was maintained at room temperature, and the original color tone was restored by cooling to −20 ° C. or lower. The discoloration behavior was reproduced repeatedly.

Example 2
Production of thermochromic multicolor writing instrument (see Fig. 3 and Fig. 4)
A cylindrical ink occlusion body 2 coated with a polyester sliver with a synthetic resin film is impregnated with the three types of previously prepared thermochromic inks B, C and D evenly in the vertical direction by needle injection, and is made of polypropylene resin. A polyester fiber resin processing pen tip 3 (cannonball type) housed in the shaft tube 4 and attached to the tip of the shaft tube and a connected state (the pen tip connection portion is located at substantially the center of the circumference of the ink occlusion body) After assembling, the multi-color writing instrument 1 (marking pen) was obtained by attaching the cap 5. A friction body 6 made of SEBS resin is mounted on the rear end portion of the shaft cylinder. Regarding the difference in viscosity between the three types of ink, the difference in viscosity between ink B and ink C is 1.7 mPa · s, the difference in viscosity between ink B and ink D is 2.1 mPa · s, and ink C and ink D. And the viscosity difference was 3.8 mPa · s.
In the ink occlusion body 2, reference numerals 21, 22, and 23 indicate a location where the ink B is filled, a location where the ink C is filled, and a location where the ink D is filled.

When writing on the paper surface using the marking pen, blue, yellow, and pink multicolored handwriting with gradation at each boundary portion was obtained.
The handwriting exhibited a multicolor state at room temperature (25 ° C.). When the handwriting was rubbed with the friction body 6 at the rear end of the shaft cylinder, the handwriting was decolored and became colorless. This state was maintained at room temperature, and the original color tone was restored by cooling to −20 ° C. or lower. The discoloration behavior was reproduced repeatedly.

Example 3
Production of thermochromic multicolor writing instruments (see Fig. 2)
In the cylindrical ink occlusion body 2 in which a polyester sliver is coated with a synthetic resin film, the previously prepared thermochromic inks E and F are uniformly impregnated in the longitudinal direction by needle injection, and the shaft cylinder 4 made of polypropylene resin is filled in. After assembling the polyester fiber resin processing pen tip 3 (chisel type) and connecting state (the pen tip connecting portion is located at the approximate center of the circumference of the ink occlusion body) accommodated and attached to the tip of the shaft cylinder, A multicolor writing instrument 1 (marking pen) was obtained by attaching the cap 5. A friction body 6 made of SEBS resin is mounted on the rear end portion of the shaft cylinder. The difference in viscosity between the two types of ink is 0.9 mPa · s.
In the ink occlusion body 2, reference numerals 21 and 22 indicate a location where the ink E is filled and a location where the ink F is filled, respectively.

When writing on the paper surface using the marking pen, a purple and green multicolored handwriting is obtained when the thick line is drawn, and a purple or green color is drawn when a thin line is drawn at each top. Monochromatic handwriting was obtained.
The handwriting exhibits the color tone at room temperature (25 ° C.), and when it is rubbed using the friction body 6 at the rear end of the shaft cylinder, the handwriting (the thick line) is a blue and yellow multicolored handwriting (the boundary portion is gradation). Changed). The fine lines changed to blue and yellow monochromatic handwriting, respectively. This state was maintained at room temperature, and the original color tone was restored by cooling to −20 ° C. or lower. The discoloration behavior was reproduced repeatedly.

Preparation of non-thermochromic ink The composition of each ink is shown in the table below. In addition, each ink mixed the raw material described in the table | surface, it stirred with the disper at room temperature, and then prepared the non-color-changeable ink by filtering.

The contents of the raw materials in the table will be described along the note numbers.
(1) Product name: SW-17 Pink (active ingredient 42%)
(2) Product name: SW-15 Lemon Yellow (active ingredient 42%)
(3) Sanyo Dye Co., Ltd., trade name: Sundai Super Blue GLL (active ingredient 24%)
(4) Sanyo Dye Co., Ltd., trade name: Sundai Super Pink FBL (active ingredient 21.5%)
(5) Nippon Lubrizol Co., Ltd., trade name: Solsperse 43000
(6) A mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, manufactured by Hokuko Chemical Co., Ltd., trade name: Hokuside R-150
(7) Product name: FS Antiform 013A, manufactured by Toray Dow Corning Co., Ltd.

Example 4
Production of multicolor writing instruments (see Fig. 5)
The cylindrical ink occlusion body 2 in which a polyester sliver is coated with a synthetic resin film is uniformly impregnated with the previously prepared inks G and H in the longitudinal direction by needle injection, and is accommodated in a shaft cylinder 4 made of a transparent polypropylene resin. After assembling the polyester fiber resin processing nib 3 (chisel type) attached to the tip of the shaft tube and the connected state (the nib connecting part 31 is located at the approximate center of the circumference of the ink occlusion body) The multicolor writing instrument 1 (marking pen) was obtained by attaching the cap 5. Although the writing instrument 1 has a general-purpose structure, the writing instrument 1 is rich in decorativeness so that two colors of ink can be visually recognized on the nib 3 and the ink occlusion body 2. The difference in viscosity between the two types of ink is 1.8 mPa · s.
In the ink occlusion body 2, reference numerals 21 and 22 indicate a location where the ink G is filled and a location where the ink H is filled.

When writing on the paper surface using the marking pen, when drawing a thick line, a pink and yellow multicolored handwriting is obtained with a gradation at the boundary, and when drawing a thin line at each top, pink or A yellow monochromatic handwriting was obtained.
Further, after the writing instrument 1 was allowed to stand at 50 ° C. for 30 days, the appearance (mixed color of ink in the pen tip 3 and the ink occlusion body 2) and handwriting were confirmed, and the same state as the initial state was maintained.

Example 5
Production of multicolor writing instruments (see Fig. 6)
The cylindrical ink occlusion body 2 in which a polyester sliver is coated with a synthetic resin film is uniformly impregnated with the previously prepared inks I and J by needle injection into the cylindrical tube 4 made of transparent polypropylene resin. did. Further, a polyester fiber resin processing nib 3 (chisel type) having a lower portion (connecting portion 31) formed in a bifurcated portion is attached to the tip of the shaft cylinder, and the connecting portion 31 is connected to each of the inks I and J in the ink occlusion body 2. After assembling in a connected state at the contact position, a multicolor writing instrument 1 (marking pen) was obtained by attaching the cap 5. Although the writing instrument 1 has a general-purpose structure, the writing instrument 1 is rich in decorativeness so that two colors of ink can be visually recognized on the nib 3 and the ink occlusion body 2. The difference in viscosity between the two types of ink is 2.4 mPa · s.
In the ink occlusion body 2, reference numerals 21 and 22 indicate a location where the ink I is filled and a location where the ink J is filled.

When writing on the paper surface using the marking pen, when drawing a thick line, a blue and red multicolored handwriting is obtained with gradation at the boundary, and when drawing a thin line at each top, blue or red Monochromatic handwriting was obtained.
Further, after the writing instrument 1 was allowed to stand at 50 ° C. for 30 days, the appearance (mixed color of ink in the pen tip 3 and the ink occlusion body 2) and handwriting were confirmed, and the same state as the initial state was maintained.

Example 6
Production of multi-color writing instruments (see Figs. 7 and 8)
A cylindrical ink occlusion body 2 in which a polyester sliver is coated with a synthetic resin film is uniformly impregnated with the three types of inks G, H and I prepared previously by needle injection in a shaft made of a transparent polypropylene resin. The polyester fiber resin processing pen tip 3 (cannonball type) accommodated in the tube 4 and attached to the tip of the shaft tube and the connected state (the connection portion 31 of the pen tip 3 is positioned at the approximate center of the circumference of the ink occlusion body) After assembling, a multicolor writing instrument 1 (marking pen) was obtained by attaching the cap 5.
Although the writing instrument 1 has a general-purpose structure, it is rich in decorativeness so that three colors of ink can be visually recognized on the nib 3 and the ink occlusion body 2. Regarding the difference in viscosity between the three types of ink, the difference in viscosity between ink G and ink H is 1.8 mPa · s, the difference in viscosity between ink G and ink I is 4.6 mPa · s, and ink H and ink I. And the viscosity difference was 6.4 mPa · s.
In the ink occlusion body 2, reference numerals 21, 22, and 23 indicate a location where the ink G is filled, a location where the ink H is filled, and a location where the ink I is filled.

When writing on the paper surface using the marking pen, pink, yellow, and blue multicolored handwriting with gradations at each boundary portion were obtained.
Further, after the writing instrument 1 was allowed to stand at 50 ° C. for 30 days, the appearance (mixed color of ink in the pen tip 3 and the ink occlusion body 2) and handwriting were confirmed, and the same state as the initial state was maintained.

Comparative Example 1
Production of multicolor writing instruments (see Fig. 5)
The multicolor writing instrument 1 was obtained by injecting (filling) the inks K and L to the marking pen having the shape used in Example 4 instead of the inks G and H.
The difference in viscosity between the two types of ink is 0.9 mPa · s, and initially the ink is not mixed, and the state where the two colors of ink are visually recognized by the nib 3 or the ink occlusion body 2 is maintained. The handwriting similar to Example 1 could be formed. However, after the writing instrument 1 was allowed to stand at 50 ° C. for 30 days, ink color mixing occurred in the pen tip 3 and the ink occlusion body 2, and the same handwriting as in the initial stage could not be obtained.

Comparative Example 2
Production of multicolor writing instruments (see Fig. 6)
The multicolor writing instrument 1 was obtained by injecting (filling) the inks M and N in place of the inks I and J to the marking pen having the shape used in Example 5.
The viscosity difference between the two types of ink is 0.8 mPa · s, and the ink is not mixed in the initial stage, and the state where the two colors of ink are visually recognized by the pen tip 3 or the ink occlusion body 2 is maintained. The same handwriting as in Example 2 could be formed. However, after the writing instrument 1 was allowed to stand at 50 ° C. for 30 days, ink color mixing occurred in the pen tip 3 and the ink occlusion body 2, and the same handwriting as in the initial stage could not be obtained.

According to the present invention, it is possible to obtain handwriting of a plurality of colors with a single nib, and further has handwriting characteristics such that a handwriting of a plurality of colors can be obtained at the same time with one writing, and a general-purpose structure can be used. It is possible to provide an entertaining multicolor writing instrument that can obtain a handwriting with a high visual effect that is stable in the long term.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on September 29, 2008 (Japanese Patent Application No. 2008-250885) and a Japanese patent application filed on October 27, 2008 (Japanese Patent Application No. 2008-275844). Incorporated herein by reference.

T ₁ complete color development temperature T ₂ color development start temperature T ₃ color erase start temperature T ₄ complete color erase temperature ΔH hysteresis width 1 multicolor writing instrument (marking pen)
2 Ink Occlusion Body 3 Pen Tip 4 Shaft Cylinder 5 Cap 6 Friction Body 31 Connection Portion

Claims (10)

1. A writing instrument in which one of fiber tips, felt tips, and plastic tips is connected to one or both ends of an ink occlusion body accommodated in a shaft cylinder as a pen tip, and a pigment system having a different color tone in the longitudinal direction of the ink occlusion body A plurality of inks are filled, and the pigment-based ink is a thermochromic ink using a thermochromic microcapsule pigment, or a non-color-changing pigment is suspended in a gently aggregated state with a water-soluble polymer flocculant. A multicolor writing instrument characterized by being a cohesive ink.
2. One of the fiber tip, felt tip, and plastic tip provided with a plurality of connecting portions and one writing tip for applying ink derived from each connecting portion, and each connecting portion has the same ink It is connected to the end of the occlusion body, and is filled with pigment-based inks of different color tones extending in the longitudinal direction extending from each connection portion of the ink occlusion body, and the pigment-based ink is a thermochromic microcapsule pigment A multicolor writing instrument, wherein the ink is a thermochromic ink using a non-color-changing pigment or a cohesive ink in which a non-color-changing pigment is suspended in a gradual aggregation state with a water-soluble polymer flocculant.
3. The multicolor writing instrument according to claim 1 or 2, wherein the pigment-based ink is a thermochromic ink using a thermochromic microcapsule pigment.
4. The multicolor writing instrument according to any one of claims 1 to 3, wherein the thermochromic ink is decolored by heating, and the color tone of the colored state is different from the color tone of other inks.
5. 3. The multicolor writing instrument according to claim 1, wherein the pigment-based ink is a pigment-based cohesive ink in which a pigment is suspended in a gently aggregated state with a water-soluble polymer flocculant.
6. The multicolor writing instrument according to any one of claims 1 to 5, wherein the polymer flocculant is a water-soluble cellulose derivative.
7. The multicolor writing instrument according to any one of claims 1 to 6, wherein each ink contains a comb-type polymer dispersant having a carboxyl group.
8. The multicolor writing instrument according to any one of claims 1 to 7, wherein each ink contains an organic nitrogen sulfur compound.
9. The multicolor writing instrument according to any one of claims 1 to 8, wherein a difference in viscosity of each ink filled in the ink occlusion body is within 8 mPa · s.
10. The multicolor writing instrument according to any one of claims 1 to 9, wherein a writing tip shape of the nib is a chisel shape.

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