JP2009023297A - Writing instrument set - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a writing instrument set being excellent in a memorization learning application, and consisting of a writing instrument which can eliminate the hand writing without using a reducing agent or an eraser, and at the same time, perform the re-writing on the eliminated section, and a light transmissive sheet which can conceal a desired location without coloring at a high concentration. <P>SOLUTION: This writing instrument set comprises the writing instrument which houses an ink being erasable by heating, and the light transmissive sheet. In the writing instrument set, with the hand writing under a colored state by the writing instrument when the writing is performed on the surface of a black printed image being formed on a surface to be written, the printed image is visible. At the same time, the light transmissive sheet has luminous property and keeps the visible light transmittance in a range of 0.2 to 50. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a writing instrument set. Specifically, the present invention relates to a writing instrument set including a writing instrument and a light-transmitting sheet.

Conventionally, in learning to memorize a desired part among display parts that are black-printed on a paper such as a textbook or a reference book, a ground color obtained by darkening the desired display part in order to improve learning efficiency A learning method of concealing and temporarily concealing is widely used (see, for example, Patent Document 1).
In the method, after applying one color of the complementary color pair to a desired display portion using an applicator, the application portion is temporarily placed by overlapping a light-transmitting sheet colored in the other color of the complementary color pair. Although it is concealed, the applicator is filled with ink that can be erased with a reducing agent or eraser for the purpose of correcting the wrongly applied part or erasing the applied part after memorizing it. (For example, refer to Patent Documents 2 and 3).
JP 57-37389 A Japanese Patent Publication No.57-5427 JP-A-9-179483

In the learning method, mainly red or green ink is used, and the coating portion is concealed as black by mixing colors, so that the light-transmitting sheet needs to be colored at a high concentration.
Therefore, when performing the memorization learning by superimposing the sheets, it is difficult to read the printed portion of the paper (the portion where the ink is not applied). In addition, when there are characters printed in the same color as the sheet or a subtractive mixed color in the printing unit, these characters may not be visible and may hinder learning.

Further, when an ink that can be erased by a reducing agent is used as the ink, the portion of the paper on which the reducing agent is applied is damaged, and the ink cannot be applied to the same portion again.
Also, when using an ink that can be erased by an eraser as the ink, although it can be rewritten to the same location, the handwriting spreads at the time of erasure, the ink penetrates the paper surface and cannot be erased cleanly, There was a problem such as smearing the surroundings with a scrap.

  The present invention can erase handwriting without using a reducing agent or an eraser, and can also be used for learning memorization consisting of a writing instrument that can be rewritten on the erased portion and a light-transmitting sheet that can conceal a desired portion without coloring at a high density. The present invention provides a writing instrument set excellent in application.

The present invention is a writing instrument set comprising a writing instrument containing a light erasable ink by heating and a light-transmitting sheet, and the handwriting in a colored state by the writing instrument is written on the surface of the black printed image formed on the writing surface. In this case, the printed image can be visually recognized, and the light-transmitting sheet is required to have glitter and have a visible light transmittance in the range of 0.2 to 50.
Further, the writing lightness value of the colored state by the writing instrument is in the range of 2.6 to 7.0, and the writing instrument comprises (a) an electron-donating color-forming organic compound, and (b) an electron-accepting compound. And (c) a microcapsule pigment that contains a reversible thermochromic composition comprising at least a reaction medium that controls the color reaction of (i) and (b), and changes color from colored to colorless by heating. Accommodating ink, the microcapsule pigment is a pigment that exhibits a large hysteresis characteristic with respect to a color density-temperature curve, exhibits a tautomerism between a colored state and a colorless state, and a holding temperature range in which both states can be selected is in a normal temperature range. There, in the pigment process temperature increases from colored state, begins decolorized to reach the temperature T _3, become completely colorless state at a temperature T ₄ or more temperature range than the temperature T _3, the temperature from the colorless state In the process but descending, begins to coloration reached temperature T ₂ lower than the temperature T _3, become completely colored state at a low temperature T ₁ of the following temperature range than temperature T _2, the temperature T ₂ and the temperature T ₃ It shows a hysteresis characteristic that can maintain a colored state or a colorless state in a temperature range between, temperature T ₁ is in the range of −30 to 10 ° C., and temperature T ₄ is in the range of 50 to 100 ° C.
Furthermore, it is a requirement that the light transmissive sheet is formed by applying, sticking or containing a glittering material to a transparent resin sheet.

  According to the present invention, a writing instrument set excellent in memorization learning application that can erase the handwriting with certainty, rewrite the erased part, and reliably recognize characters other than the concealed part through the light-transmitting sheet is provided. it can.

  The writing instrument set is suitable for memorization learning composed of a writing instrument containing ink that can be decolored by heating, and a light-transmitting sheet having glitter.

The writing instrument contains ink that can be erased by heating, and can be easily erased by heating by means such as rubbing.
The ink has a lightness that allows the printed image to be visually recognized in a colored state when written on the surface of a black printed image printed on paper.
In particular, the lightness value of the colored handwriting by the writing instrument is preferably in the range of 2.6 to 7.0, and if it is less than 2.6, the printed image of the writing portion is difficult to visually recognize. If it exceeds 0, the printed image of the writing part can be visually recognized, but the printed image can be visually recognized even when the light-transmitting sheets are stacked, so that the memorization application is not satisfied.

As the colorant to be blended in the ink, any conventionally known composition can be used as long as it exhibits a heat decoloring property. In particular, (a) an electron-donating color-forming organic compound, (b) A pigment in which a microcapsule encapsulates a reversible thermochromic composition containing at least three essential components of the reaction medium that determines the temperature at which the color reaction of the above and (c) occurs is effective.
Among the reversible thermochromic compositions, the compositions that can be decolored by heating are described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398, and the like. The color changes before and after the temperature (discoloration point), shows a decolored state in the temperature range above the high temperature side discoloration point, and develops a color state in the temperature range below the low temperature side discoloration point. There is only one specific state, and the other state is maintained while the heat or cold required to develop that state is applied, but if the heat or cold is no longer applied, The composition which has the characteristic ((DELTA) H = 1-7 degreeC) with a comparatively small hysteresis width | variety which returns to the state exhibited in a region can be illustrated.
In addition, large hysteresis characteristics described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, and the like. (ΔH = 8 to 70 ° C.), and the shape of the curve plotting the change in color density due to the temperature change is from the higher temperature side than the color change temperature range, contrary to the case where the temperature is raised from the lower temperature side than the color change temperature range. Use a reversible thermochromic composition that changes color by following a path that differs greatly from that of lowering, and can store and retain the color development state in the low temperature range or the decoloration state in the high temperature range in the specific temperature range. You can also.

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., and , complete decoloring temperature _{T 4} of the frictional heat generated by friction body, the temperature obtained from the hair dryer familiar heating body, i.e. 50 to 100 ° C., preferably specific to a range of 55 to 95 ° C., the ΔH value 40-80 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).
The writing instrument applied in the present invention contains an ink containing a microcapsule pigment encapsulating a reversible thermochromic composition in a colored state, and the handwriting formed by the writing instrument can be easily erased by touch or the like. It is preferable that the configuration is not performed, and it is preferable that the erased handwriting does not appear again.
Therefore, the above-described temperature setting of T ₁ and T ₄ is an extremely important requirement.

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

As the electron-accepting compound of component (b), a group of compounds having active protons, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as an acid in the composition and cause component (a) to develop color), electrons There is a group of compounds having pores.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Or what has an amide group, a halogen group, etc., phenol-aldehyde condensation resin etc., such as a bis type and a tris type phenol, are mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

Specific examples are given below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -3-methylbu 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxyphenyl) n-heptane, , 1-bis (4-hydroxyphenyl) n-octane, 1,1-bis (4-hydroxyphenyl) n-nonane, 1,1-bis (4-hydroxyphenyl) n-decane, 1,1-bis ( 4-hydroxyphenyl) n-dodecane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ethylpropionate, 2,2-bis (4-hydroxyphenyl)- 4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) n-heptane, 2,2-bis It is 4-hydroxyphenyl) n- nonane.
As the compound having a phenolic hydroxyl group, a compound having a phenolic hydroxyl group having at least 3 benzene rings and having a molecular weight of 250 or more, preferably a molecular weight of 250 to 500, or 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. 2 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-t-butyl-4-hydroxyphenyl) sulfide, bis ( 3,5-t-butyl-4-hydroxyphenyl) sulfide, bis (3-pentyl-4-hydroxyphenyl) sulfide, bis (3-hexyl-4-hydroxyphenyl) sulfide, bis (3-heptyl-4-hydride) Xylphenyl) sulfide, bis (5-octyl-2-hydroxyphenyl) Rufido, and the like.
The compound having a phenolic hydroxyl group can develop the most effective thermochromic property, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

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 large hysteresis characteristic regarding the color density-temperature curve (a curve plotting a change in color density due to a temperature change changes the temperature from the low temperature side to the high temperature side and the high temperature side to the low temperature side). A carboxylic acid ester compound that exhibits a ΔT value (melting point-cloud point) of 5 ° C. or higher and lower than 50 ° C., which can form a reversible thermochromic composition that exhibits color memory, and 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 number of carbon atoms, 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.

As the 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.
Further, arylalkyl ketones having 12 to 24 carbon atoms in total, 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-pentylacetophene Emissions, cyclohexyl 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, decane diol dimethyl ether, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, undecane diol diethyl ether Etc.

  Furthermore, the compounds described in JP-A-2006-137886 and JP-A-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 In a system having a value of 0.5 μm or less, it is difficult to show coloration at a high concentration. 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) / 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 during color development are unavoidable, 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 microcapsule pigment can be blended in an amount of 2 to 50% by weight (preferably 3 to 40% by weight, more preferably 4 to 30% by weight) based on the total amount of the ink composition. If it is less than 2% by weight, the color density is insufficient, and if it exceeds 50% by weight, the ink outflow is reduced and the writing property is impaired.

As the reversible thermochromic ink applied to the present invention, an ink in which a microcapsule pigment exhibiting a colored state is dispersed in a vehicle is effective, and the vehicle is preferably an aqueous vehicle, but may be an oil vehicle. .
Specific examples include a shear-thinning ink containing a shear-thinning agent and an aggregating ink obtained by suspending a reversibly thermochromic microcapsule pigment in a gentle aggregation state with a water-soluble polymer flocculant. Furthermore, there is an ink in which the specific gravity difference between the reversible thermochromic pigment and the vehicle is adjusted to 0.05 or less.

By adding the shear thinning agent, it is possible to suppress the aggregation / sedimentation of the microcapsule pigment and to suppress the bleeding of the handwriting. Even if writing on the material, the handwriting does not bleed and a good handwriting can be formed.
Furthermore, when the writing instrument to be filled with the ink is in the form of a ballpoint pen, it prevents ink leakage from the gap between the ball and the tip when not in use, or the ink when the writing tip is left upward (upright state). Backflow can be prevented.
The viscosity of the ink added with the shear thinning agent is 20 to 300 mPa · s at a shear rate of 3.84S ⁻¹ measured by an E-type rotational viscometer at 20 ° C. It is preferable that the viscosity index is 0.1 to 0.9.
By showing the above-mentioned viscosity range and shear thinning index, it is possible to further leak ink and prevent ink backflow.
The shear thinning index (n) is expressed by an empirical formula T = Kj ⁿ (K is a non-Newtonian viscosity coefficient) obtained from rheological measurement by a viscometer such as a shear stress value (T) and a shear rate value (j). It is a value calculated by fitting.

  Examples of the shear thinning agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 to 8 million) whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose, guar gum, locust bean gum and derivatives thereof , Hydroxyethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 mainly composed of alkyl esters of methacrylic acid, thickening agent having gelling ability extracted from seaweed such as glucomannan, agar and carrageenan Sugars, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polio Shi polyoxyethylene alkyl ether-polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ether, nonionic HLB value, such as fatty acid amide is 8-12 surfactants, salts of dialkyl or dialkenyl sulfosuccinic acid. Examples thereof include a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.

As the water-soluble polymer flocculant, a nonionic water-soluble polymer compound is preferably used.
Specific examples include polyvinyl pyrrolidone, polyethylene oxide, water-soluble polysaccharides, nonionic water-soluble cellulose derivatives, and the like. Among these, specific examples of water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, and specific examples of nonionic water-soluble cellulose derivatives include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxy Examples thereof include propylmethylcellulose.
In the reversible thermochromic ink of the present invention, any water-soluble polymer exhibiting a loose bridging action between pigment particles can be applied, but the nonionic water-soluble cellulose derivative is most effective. Works.
The polymer flocculant can be blended in an amount of 0.05 to 20% by weight based on the total amount of the ink composition.

  Examples of water-soluble organic solvents added together with water in the ink include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, and propylene glycol. , Butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrole Don, N- methyl-2-pyrrolidone.

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

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

The ink is put into practical use by filling a writing instrument such as a marking pen or a ballpoint pen with a marking pen tip or a ballpoint pen tip attached to the writing tip.
In particular, the writing instrument is more preferably used in the form of a marking pen because it is easy to paint a printed image in a character form at a time.

  When filling the ball-point pen, the structure and shape of the ball-point pen itself are not particularly limited. For example, the ball-point pen has an ink containing tube filled with shear-thinning ink in the shaft cylinder, and the ink containing tube has a ball at the tip portion. An example is a ball-point pen that communicates with the tip mounted on the ink-jet head and has a liquid stopper for backflow prevention in close contact with the end face of the ink.

The ballpoint pen tip will be described in more detail. A tip formed by holding a ball in a ball holding portion obtained by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, or a metal material is cut by a drill or the like A chip formed by holding the ball in the ball holding part formed by the above, a chip provided with a resin ball receiving seat inside a metal or plastic chip, or a ball held by the chip is moved forward by a spring body Energized items can be applied.
The ball is 0.2 to 3.0 mm, preferably 0.3 to 2.0 mm, more preferably 0.4 to 1.6 mm, such as cemented carbide, stainless steel, ruby, ceramic, resin, and rubber. A thing of a diameter is applicable.
In addition, the writing instrument filled with the ink of the present invention includes those provided with a rolling mechanism for forming a handwriting by the same rolling action as the ball.

For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon is used as the ink storage tube for storing the ink.
Furthermore, by using a transparent, colored transparent, or translucent molded body as the ink containing tube, the ink color, the remaining amount of ink, and the like can be confirmed.
In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member.
The ink storage tube may be a refill type in which the refill is stored in a shaft tube, or the shaft tube itself having a tip attached to a tip is used as an ink container, and ink is directly applied to the shaft tube. It may be filled.

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

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

  In addition, when filling a marking pen, the structure and shape of the marking pen itself are not particularly limited. For example, a fiber in which an ink occlusion body made of a fiber converging body is built in a shaft cylinder and a capillary gap is formed. A marking in which a pen tip made of a processed body is mounted on a shaft cylinder directly or via a relay member, and the ink occlusion body of the marking pen in which the ink occlusion body and the pen tip are connected is impregnated with cohesive ink. An example is a marking pen in which a pen tip and an ink storage tube are arranged via a pen or a valve body that is opened when the pen tip is pressed, and ink is directly stored in the ink storage tube.

The nib is a porous member having continuous vents selected from the range of generally used porosity of 30 to 70%, such as a resin processed body of fibers, a fusion processed body of heat-meltable fibers, and a felt body. One end is processed into a shape corresponding to the purpose such as a bullet shape, a rectangular shape, a chisel shape, etc.
The chisel-shaped pen body has versatility that can form marks with a constant line width for fine writing or for thick writing by changing the contact position on the writing surface. It is possible to construct a writing instrument that is excellent in convenience and capable of forming a handwriting with a good thermochromic property.
The ink occlusion body is formed by converging crimped fibers in the longitudinal direction, and is configured to be included in a covering body such as a plastic cylinder or a film and to adjust the porosity to a range of approximately 40 to 90%. Is done.
The valve body can be of a general-purpose pumping type, but is preferably set to a spring pressure that can be released by writing pressure.

  Furthermore, the form of the ballpoint pen and the marking pen is not limited to those described above, and a composite writing instrument (a double-headed type or a nib with a pen point with a different form or a pen point with which a different color tone is derived) is attached. It may be a pay-out type or the like.

The handwriting obtained by writing on the recording medium using the writing tool described above can change the color tone from a colored state to a colorless 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 (styrene-butadiene-styrene copolymer), SEBS resin (styrene-ethylene-butylene-styrene block copolymer) and the like are preferably used. SBS resin or SEBS resin is more preferably used because the resin tends to adhere to the parts erased by rubbing and the handwriting may be repelled when writing repeatedly. 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.

When the rubbing part of the rubbing member is pressed on the glass plate with a load of 500 g, the contact area between the glass plate and the rubbing member becomes 12 mm ² or less, and when the rubbing member is pressed with a load of 1000 g, The contact area of the member is formed to be 15 mm ² or less.
Thereby, it is possible to surely select only a small area portion of the handwriting by the writing instrument and easily discolor the scratch.
In any of the above loads, the contact area of the scraping member when pressed against the glass plate is preferably 0.5 mm ² or more in consideration of the strength and formability of the scraping member.
As the glass plate, a float glass plate having a smooth surface and having transparency that allows the contact portion to be visually recognized from the back surface when a rubbing member is brought into contact with the surface is used.
The shape of the rubbing member may be any shape as long as it satisfies the above conditions, but a constant contact area can be obtained regardless of the contact angle with the handwriting, and only the target portion can be obtained without rubbing a wide area. A pyramid, a cone, and the like are preferable because they can be scraped, and the tip is preferably a convex curved surface.

The light-transmitting sheet used together with the writing instrument is provided with glitter, and is applied to a sheet-like material molded by adding a glitter material in a transparent resin, or a sheet-like material molded with a transparent resin. It can be obtained by forming a glitter layer by sticking.
The glitter is effective as long as it emits reflected light, interference light, or both reflected light and interference light, specifically, metallic luster, pearl luster, luster, hologram, etc. It is.
Specific examples of the glittering material include metal powders such as aluminum, copper, brass, gold, silver, chromium, and nickel, and pearlescent pigments (for example, natural mica, synthetic mica, glass fragments, and titanium oxide on the surface of titanium oxide). Coated with a metal oxide such as cholesteric liquid crystal type pigment, pigment coated with silicon oxide with metal oxide, pigment coated with iron oxide or aluminum surface with silicon oxide and iron oxide, and glitter film In addition, finely pulverized iridic films, hologram films and the like are used.

  It is preferable that the light-transmitting sheet having the glitter has a visible light transmittance in the range of 0.2 to 50. If it is less than 0.2, it is difficult to visually recognize the printed image when the light transmissive sheets are stacked. If it exceeds 50, the printed image can be visually recognized when the light transmissive sheets are stacked, but the printed image of the writing portion. Since it can visually recognize, it becomes the structure which does not satisfy | fill a memorization use.

  The size and thickness of the sheet are not particularly limited, and examples include those having the size and thickness of an underlay, rulers, and those having a size and thickness of a strip. In addition, the sheet can be colored in a state where the light transmission is maintained.

Examples are shown below, but the present invention is not limited to these examples.
In addition, the part in an Example is a weight part.
The lightness value of the handwriting is measured with a color difference meter (TC-3600, manufactured by Tokyo Denshoku Co., Ltd.), and the visible light transmittance of the sheet is measured with a spectrophotometer (U-3210, manufactured by Hitachi, Ltd.). ) To obtain an intermediate value between the maximum value and the minimum value at 400 to 700 nm.
Example 1 (see FIGS. 1 and 2)
Preparation of reversible thermochromic ink (i) 4.5 parts of 2- (2-chloroamino) -6-di-n-butylaminofluorane as component (4), 4,4 '-(2-methyl) as component (b) Color memory consisting of 4.5 parts of propylidene) bisphenol, 7.5 parts of 2,2-bis (4′-hydroxyphenyl) hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) Microcapsule pigment (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle diameter) : 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, color change from black to colorless) 25.7 parts, succinoglycan 0.2 parts, urea 5.5 parts, 7.5 parts glycerin, nonionic permeability imparting agent 0 0.03 parts, reversible thermochromic ink consisting of 0.15 parts of modified silicone antifoaming agent, 0.1 parts of antifungal agent, 0.5 parts of lubricant, 0.5 parts of triethanolamine and 59.82 parts of water. Was prepared.

Preparation of writing instrument The ink 4 (cooled to -20 ° C. or lower in advance and colored the microcapsule pigment in black and then left at room temperature) is placed on a polypropylene pipe (ink containing cylinder 21) having an inner diameter of 4.4 mm. The resin was sucked and filled and connected to the ballpoint pen tip 3 through the resin holder 22.
Next, an ink backflow prevention body 5 (liquid stopper) having a viscoelastic property mainly composed of polybutene was filled from the rear part of the polypropylene pipe, and a tail plug 23 was fitted to the rear part of the pipe to obtain a refill 2. Further, the refill 2 is incorporated into a shaft cylinder 6 (comprised of a front shaft cylinder and a rear shaft cylinder), and after a cap 7 is fitted, a deaeration process is performed by a centrifugal process to perform a reversible thermochromic ballpoint pen (writing instrument 1). Got.
The ball-point pen tip 3 has a stainless steel ball having a diameter of 1.0 mm held at the tip of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface. It is biased forward by a spring body.
In addition, a SEBS resin member having a convex curved top is mounted as a rubbing member 8 on the rear portion of the rear barrel 6, and the rubbing member 8 is placed on an electronic balance so that the convex curved surface is on the rubbing member 8. The contact area between the scraping member 8 and the transparent glass plate that is visually recognized by pressing the glass plate vertically with a load of 500 g and 1000 g after contacting the transparent glass plate in parallel with the weighing pan of the electronic balance. results of measurement of the contact area when the contact area at the time when pressed with a load of 500g is pressed with a load of 3.2 mm ^2, 1000 g was 4.9 mm ^2.
The black handwriting colored by the writing instrument 1 had a lightness value of 3.2.

Production of glittering light-transmitting sheet On the surface of a transparent resin sheet (130 mm × 30 mm, thickness 0.5 mm), a golden pearl luster pigment [manufactured by Nippon Sheet Glass Co., Ltd., trade name: Metashine RCFSX-5450TS (6041), A glittering light-transmitting sheet was obtained by providing a nacreous layer having an average thickness of 5 ± 2 μm and an average particle size of 450 ± 145 μm] and an acrylic polyol resin having a thickness of about 50 μm.
The visible light transmittance of the obtained sheet was 10%.

Preparation of writing instrument set A writing instrument set was obtained by combining the reversible thermochromic ballpoint pen and a glittering light-transmitting sheet.
When the ballpoint pen was used to form (fill) the handwriting on the character so as to conceal the black character (printed image) printed on the paper surface of the reference book, the printed image of the portion was surely visible. It was. In addition, by superimposing a glittering light-transmitting sheet on the printed image, only the black characters of the handwriting portion cannot be seen through the sheet, and the other portion (black printing that is not painted with a writing instrument is overlapped). Since this was visible, it was excellent for memorization purposes.
If the handwriting is rubbed on the handwriting using the attached rubbing member after it has been mistakenly written or memorized, the handwriting (painted portion) will be discolored and will not be visible, and this state should be maintained at room temperature. I was able to. In addition, when there are many writing parts, all the handwriting is easily discolored by heating the entire handwriting using a desk lamp (light), and this state is maintained at room temperature. , It became visible as if it had returned to the state before entry.
Furthermore, the same place could be painted again using the writing instrument, and a writing instrument set for memorization excellent in convenience was obtained.

Example 2
Preparation of reversible thermochromic ink (i) 1.5 parts 2- (2-chloroamino) -6-di-n-butylaminofluorane as component (4) 4,4 '-(2-methyl) as component (b) Propyridene) Color consisting of 3.0 parts of bisphenol, 5.0 parts of 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) microcapsule pigment _(T 1 containing therein a reversible thermal discoloration composition having a memory _{property: -20 ℃, T 2: -8} ℃, T 3: 49 ℃, T 4: 60 ℃, average particle size: 2.5 [mu] m , Reversible thermochromic composition / wall film = 2.8 / 1.0, color change from black to colorless) 20.0 parts, 0.5 parts of hydroxyethyl cellulose, 15.0 parts of glycerin, 0. 02 parts, 1.0 part of preservative, water 3.38 parts, by adding 10% dilute phosphoric acid solution 0.1 parts uniformly performed stirring to obtain a reversible thermochromic ink to adjust the pH of the ink to about 5.6.

Preparation of the writing instrument The ink (previously cooled to -20 ° C or less and colored the microcapsule pigment in black and then left at room temperature) and a stirring body are incorporated in the shaft cylinder, and a valve mechanism is interposed. A marking pen body [chisel type fiber pen tip (porosity of about 53%)] was attached to the tip to obtain a reversible thermochromic marking pen.
The valve mechanism is composed of a valve seat, a valve body, and a metal spring that urges the valve body to press against the valve seat, and the valve opens with the pressure applied to the pen body during writing. is there.
The marking pen is provided with a detachable cap. A SEBS resin member having a convex curved top is attached as a rubbing member to the rear end of the shaft cylinder, and the rubbing member is electronic so that the convex curved surface is on the top. Place the transparent glass plate on the balance, bring the transparent glass plate into contact with the weighing pan of the electronic balance in parallel, and then press the glass plate vertically with a load of 500 g and 1000 g. a result of measuring the contact area with the glass plate, the contact area at the time when the contact area at the time when pressed with a load of 500g is pressed with a load of 3.2 mm ^2, 1000 g was 4.9 mm ^2.
The black handwriting colored by the writing instrument had a lightness value of 3.9.

Preparation of glittering light-transmitting sheet On the surface of a transparent resin sheet (130 mm × 30 mm, thickness 0.5 mm), a golden metallic luster pigment (Merck, trade name: Iriodin 205, average particle diameter 10-60 μm) and acrylic A glittering light-transmitting sheet was obtained by providing a metallic luster layer having a thickness of about 40 μm composed of an acid ester resin.
The visible light transmittance of the obtained sheet was 10%.

Preparation of writing instrument set A writing instrument set was obtained by combining the reversible thermochromic marking pen and a glittering light-transmitting sheet.
When the marking pen is used to form (fill) the handwriting on the character so as to conceal the black character (printed image) printed on the paper surface of the reference book, the printed image of the portion can be surely seen. there were. In addition, by superimposing a glittering light-transmitting sheet on the printed image, only the black characters of the handwriting portion cannot be seen through the sheet, and the other portion (black printing that is not painted with a writing instrument is overlapped). Since this was visible, it was excellent for memorization purposes.
If the handwriting is rubbed on the handwriting using the attached rubbing member after it has been mistakenly written or memorized, the handwriting (painted portion) will be discolored and will not be visible, and this state should be maintained at room temperature. I was able to. In addition, when there are many writing parts, all the handwriting is easily discolored by heating the entire handwriting using a desk lamp (light), and this state is maintained at room temperature. , It became visible as if it had returned to the state before entry.
Furthermore, the same place could be painted again using the writing instrument, and a writing instrument set for memorization excellent in convenience was obtained.

Example 3
Preparation of reversible thermochromic ink (i) 4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl] -3- (1-ethyl-2-methyl-1H) as component -Indol-3-yl) -1 (3H) -isobenzofuranone 2.0 parts, (ro) component 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 parts, 4,4 ' -Microcapsule pigment encapsulating a reversible thermochromic composition having color memory composed of 3.0 parts of (2-methylpropylidene) bisphenol and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) _{(T 1: -16 ℃, T} 2: -8 ℃, T 3: 48 ℃, T 4: 58 ℃, ΔH: 65 ℃, average particle size: 2.5 [mu] m, the reversible thermochromic composition / wall membrane = 2.6 / 1.0, from blue (Colorlessly changes color) 12 parts, glycerin 5 parts, antifungal agent 0.7 parts, antifoaming agent 0.1 part, water 74.2 parts uniformly dispersed in an aqueous medium, hydroxy A reversible thermochromic ink in which the reversible thermochromic pigment was suspended in a gently aggregated state was prepared by adding 8 parts of a 5% by weight aqueous solution of ethyl cellulose to the dispersed liquid while stirring.

Preparation of writing instrument The reversibly thermochromic ink (preliminarily cooled to -16 ° C. or lower to develop a microcapsule pigment in a fiber-focused ink occlusion body (porosity of about 80%) covered with a polyester resin sliver. A polyester fiber resin processing pen body (porosity of about 50%) that is impregnated immediately after being uniformly stirred and accommodated in the shaft cylinder and attached to the tip of the shaft cylinder. It assembled in the contact state and obtained the reversible thermochromic marking pen.
The shaft tube is provided with a SEBS resin member having a rubbing portion as a convex curved surface as a rubbing member at the rear, and the rubbing member 8 is placed on an electronic balance so that the convex curved surface is on the rubbing member. Contact between the scraping member 8 and the transparent glass plate, which is visually recognized by pressing the glass plate vertically with a load of 500 g and 1000 g after bringing the transparent glass plate into contact with the weighing pan of the electronic balance on 8 As a result of measuring the area, the contact area when pressed with a load of 500 g was 3.0 mm ² , and the contact area when pressed with a load of 1000 g was 4.5 mm ² .
The blue handwriting colored by the writing instrument had a lightness value of 5.2.

Preparation of glittering light-transmitting sheet In PE resin, a silver pearl luster pigment [Merck, trade name: Iriodin 120, average particle size 5 to 25 μm] was mixed and melt-kneaded with an extruder, and then the thickness By forming into 0.5 mm and cutting into 130 mm × 30 mm, a glittering light-transmitting sheet was obtained.
The visible light transmittance of the obtained sheet was 1.4%.

Preparation of writing instrument set A writing instrument set was obtained by combining the reversible thermochromic marking pen and a glittering light-transmitting sheet.
When a blue handwriting is formed (filled) on a character so as to conceal the black character (printed image) printed on the paper surface of the reference book using the marking pen, the printed image of the portion can be surely seen Met. In addition, by superimposing a glittering light-transmitting sheet on the printed image, only the black characters of the handwriting portion cannot be seen through the sheet, and the other portion (black printing that is not painted with a writing instrument is overlapped). Since this was visible, it was excellent for memorization purposes.
If the handwriting is rubbed on the handwriting using the attached rubbing member after it has been mistakenly written or memorized, the handwriting (painted portion) will be discolored and will not be visible, and this state should be maintained at room temperature. I was able to. In addition, when there are many writing parts, all the handwriting is easily discolored by heating the entire handwriting using a desk lamp (light), and this state is maintained at room temperature. , It became visible as if it had returned to the state before entry.
Furthermore, the same place could be painted again using the writing instrument, and a writing instrument set for memorization excellent in convenience was obtained.

Comparative Example 1
Preparation of writing instrument A marking pen-shaped writing instrument was obtained with the same configuration except that the ink composition of Example 2 was changed to 4.0 parts of microcapsule pigment and 79.38 parts of water.
The black handwriting of the colored state by the obtained writing instrument had a lightness value of 7.6.

Preparation of Writing Instrument Set A writing instrument set was obtained by combining the reversible thermochromic marking pen and the glittering light transmissive sheet of Example 2.
When the marking pen is used to form (fill) the handwriting on the character so as to conceal the black character (printed image) printed on the paper surface of the reference book, the printed image of the portion can be surely seen. However, even when the glittering light-transmitting sheet was superimposed on the printed image, the black characters in the handwriting portion could be visually recognized through the sheet, so that the printed image could not be used for memorization purposes.

Comparative Example 2
Preparation of Writing Instruments A marking pen-shaped writing instrument was obtained with the same configuration except that 40 parts of the microcapsule pigment and 43.38 parts of water were used in the ink composition of Example 2.
The black handwriting of the colored state obtained by the writing instrument had a lightness value of 2.2.

Preparation of Writing Instrument Set A writing instrument set was obtained by combining the reversible thermochromic marking pen and the glittering light transmissive sheet of Example 2.
Using the marking pen, when a handwriting was formed (filled) on a character so as to conceal the black character (printed image) printed on the paper of the reference book, the printed image of the portion became invisible . Therefore, it cannot be used for memorization purposes.

Comparative Example 3
Preparation of glittering light-transmitting sheet On the surface of a transparent resin sheet (130 mm × 30 mm, thickness 0.5 mm), a golden metallic luster pigment (Merck, trade name: Iriodin 205, average particle diameter 10-60 μm) and acrylic Two types of glittering light-transmitting sheets were obtained by providing a pearly luster layer having a thickness of about 200 μm and 10 μm comprising an acid ester resin.
The visible light transmittance of the obtained sheet was 0.1% and 82%.

Preparation of Writing Instrument Set A writing instrument set was obtained by combining the reversible thermochromic marking pen obtained in Example 2 and a glittering light transmissive sheet.
When the marking pen is used to form (fill) the handwriting on the character so as to conceal the black character (printed image) printed on the paper surface of the reference book, the printed image of the portion can be surely seen. there were.
In addition, when two kinds of glittering light-transmitting sheets are superimposed on the printed image, when the transmittance is 82%, black characters in the handwriting portion can be visually recognized through the sheet, and the transmittance is 0.1%. As for the thing, the other part (the part on which the sheet | seat was piled up among the black printing which is not painted with the writing instrument) was also invisible. Therefore, none can be used for memorization purposes.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition used for this invention. It is longitudinal section explanatory drawing which shows an example of the writing instrument used for this invention.

Explanation of symbols

T ₁ complete color development temperature T ₂ color development start temperature T ₃ color erase start temperature T ₄ complete color erase temperature ΔH hysteresis width 1 writing instrument (ballpoint pen)
2 Refill 21 Ink receiving cylinder 22 Holder 23 Tail plug 3 Ballpoint pen tip 4 Thermochromic ink 5 Ink backflow preventer 6 Shaft cylinder 7 Cap 8 Scraping member

Claims (5)

  In a writing instrument set comprising a writing instrument that contains ink that can be erased by heating, and a light-transmitting sheet, the printing is performed when the handwriting in a colored state by the writing instrument is written on the surface of a black printed image formed on the writing surface. A writing instrument set, wherein an image is visible, and the light-transmitting sheet has glitter and has a visible light transmittance of 0.2 to 50.   The writing instrument set according to claim 1, wherein a handwriting brightness value in a colored state by the writing instrument is in a range of 2.6 to 7.0.   The writing instrument comprises at least (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b). The writing instrument set according to claim 1 or 2, which contains an ink containing a microcapsule pigment that contains a reversible thermochromic composition and changes its color from colored to colorless by heating. The microcapsule pigment is a pigment that exhibits a large hysteresis characteristic with respect to a color density-temperature curve, exhibits a tautomerism between a colored state and a colorless state, and a holding temperature range in which both states can be selected is in a normal temperature range, and the pigment is colored in the process of temperature from the state rises, beginning decolorized to reach the temperature T _3, become completely colorless state at a temperature T ₄ or more temperature range than the temperature T _3, in the process of temperature is lowered from colorless state, the began to color to reach a lower temperature T ₂ than the temperature T _3, become completely colored state at a low temperature T ₁ of the following temperature range than temperature T _2, colored state at a temperature range between the temperature T ₂ and the temperature T ₃ or show the hysteresis characteristics of the colorless state can be maintained, temperatures _{T 1} is in the range of -30～10 ° C., writing instrument set according to claim 3, wherein the temperature _{T 4} is in the range of 50 to 100 ° C.. The writing instrument set according to any one of claims 1 to 4, wherein the light-transmitting sheet is formed by applying, sticking, or containing a glittering material to a transparent resin sheet.

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