JP3156832U - Writing sheet set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a writing sheet excellent in convenience and reusability in which a desired portion can be quickly erased without being contaminated at the time of error correction, and the erased portion can be rewritten, and a wide range can be easily and surely erased. Provide set. An explanation unit displaying a writing instrument containing ink that can be erased by heating and a writing sheet written by the writing instrument, wherein the writing sheet heats a handwriting formed by the writing instrument. Have The explanation part of the writing sheet is formed of thermochromic ink. The writing sheet has an image formed of non-color-changing ink. [Selection] Figure 1

Description

  The present invention relates to a writing sheet set. More specifically, the present invention relates to a writing sheet set that can be erased by heating an image written on the sheet using an attached writing instrument.

  Conventionally, as a writing sheet filled in with writing instruments, memo papers with memorandums and messages, order forms that convey requirements such as order contents, application forms, FAX transmission forms, and delivery instructions with parts at factories, etc. An instruction card or the like describing information is disclosed (for example, see Patent Documents 1 and 2).

A general-purpose writing instrument such as an oil-based ballpoint pen or a pencil is used to fill in the memo paper or order form. However, if the entry content is incorrect, it is necessary to use a correction fluid or an eraser to correct the error.
Since the correction liquid takes time to dry, it cannot be rewritten immediately after application.Eraser erases residue by rubbing and spreads the handwriting at the time of rubbing to stain the periphery of the erased portion. was there. Also, when reusing, it is necessary to erase all of the entered parts, so it takes time and effort to erase using correction liquid and eraser.
For this reason, the memo paper and purchase order are rarely reused, and are often discarded after being used once.
In addition, since the instruction card is used via a member consumer and a member supplier, the reusability is further low.
Utility Model Registration No. 3041722 JP-A-8-324162

  The present invention is designed for writing with excellent convenience and reusability that allows easy and reliable erasing of a wide area, as well as quick erasing of the desired part after quickly erasing the surrounding area without smearing the periphery when correcting errors. A sheet set is provided.

The present invention consists of a writing instrument containing ink that can be erased by heating, and a writing sheet written by the writing instrument, and the explanation unit displays that the writing sheet heats a handwriting formed by the writing instrument. It is a requirement to have
Furthermore, the description part of the writing sheet is formed of thermochromic ink, the writing sheet is paper having ink permeability, and the writing sheet is formed of non-color-changing ink. It is a requirement to have
Furthermore, the writing instrument comprises (a) an electron donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b). Containing an ink containing a microcapsule pigment that changes color from colorless to colorless by heating, encapsulating at least a reversible thermochromic composition, wherein the microcapsule pigment exhibits a large hysteresis characteristic with respect to a color density-temperature curve. exhibit photochromic colored state and colorless state, the holding temperature range both states can coexist are pigments in the normal temperature range, the pigment in the process of temperature increase from the colored state, decolorized to reach the temperature T ₃ First, become completely colorless state at a temperature T ₄ or more temperature range from the temperature T _3, in the process the temperature decreases from the colorless state, it begins to color to reach 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, shows a hysteresis characteristic colored state or a colorless state can be maintained in the temperature range between the temperature T ₂ and the temperature T _3, temperatures T ₁ is It is in the range of −30 to 10 ° C., the temperature T ₄ is in the range of 30 to 80 ° C., and the writing instrument is provided with a scraping member.

  The present invention provides a writing sheet set excellent in convenience and reusability in which handwriting can be quickly rewritten at a part where handwriting is partially erased, and the entire handwriting can be erased easily and reliably.

  The writing sheet has an explanation part that indicates that the handwriting formed by the attached writing instrument (a writing instrument that contains ink that can be erased by heating) is heated, so that the user who confirmed the explanation part formed it. The handwriting can be surely erased by heating. At that time, since it can be easily erased partially or entirely by the heating method, it is suitable for correction of errors and reuse after batch erasure.

  The explanation part is formed with non-color-changing ink, so that the written state can be maintained even after the entire writing sheet is heated, and the whole sheet is heated by forming with thermo-chromic ink. It becomes a form that can be erased together with the handwriting. In this case, since the entire surface of the sheet is blank, the writing sheet can be reused for other purposes (such as printing).

In addition, the writing sheet includes, together with the explanation part, an image formed of non-color-changeable ink (a frame, a ruled line, characters, numbers, etc., for simplifying the written item or assisting the written item. Can also be provided. The non-color-changing image is a combination of a frame, a ruled line, letters, numbers, etc., such as a memo paper, an order form, an application form, a FAX transmission form, a delivery instruction card, a test answer sheet, a voting ticket, a medical examination table, etc. Since the format can be freely formed, it is possible to reduce the amount of writing that the user fills in in order to transmit the desired contents, and to be a guide for determining the position and size of the handwriting.
Further, by forming the non-color-changing image with the thermochromic ink, the whole surface can be erased together with the handwriting when the whole surface of the sheet is heated. Also in this case, since the entire surface of the sheet is blank, the writing sheet can be reused for other purposes (such as printing).

  As the writing sheet, a sheet having ink permeability is applied so that the handwriting formed by the attached writing tool is reliably fixed. When the ink does not penetrate at all, the handwriting spreads when the handwriting is rubbed, and the area around the rubbed part is soiled without being completely decolored.

As a material for the writing sheet, a material having general ink permeability can be applied, for example, natural pulp paper such as fine paper, art paper, cast paper, coated paper, wood pulp, synthetic pulp, synthetic resin film. , Non-woven fabrics and woven fabrics made of synthetic fibers, natural fibers, pulp fibers, glass fibers, synthetic paper, laminated paper with synthetic resin laminated on one or both sides, metal foil, or composite sheets combining these It is possible to use.
At that time, it is also possible to use a material having improved ink permeability by embossing or the like on the surface of the sheet having low permeability.

  The writing sheet is applied as a single-sheet form or a booklet form including a plurality of sheets. In that case, it can be used by sticking to a hard material such as a resin plate or cardboard, or a removable adhesive part can be provided. Further, it is possible to form a cut portion or the like.

The writing instrument applied to the writing sheet set contains ink that can be decolored by heating.
As the colorant blended in the ink, conventionally known (a) electron donating color-forming organic compound, (b) electron accepting compound, and (c) the occurrence temperature of the color reaction of both of them. A pigment in which a reversible thermochromic composition containing at least three essential components of the reaction medium to be determined is encapsulated in a microcapsule 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 first hue and can co-exist two phases of the second color, the temperature range between T ₂ and T ₃ is a large area of the difference in color density Is a substantial discoloration temperature range (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} frictional heat generated by friction body, the temperature obtained from the hair dryer familiar heating body, i.e. 30 to 80 ° C., preferably 50 to 80 ° C., and more preferably specific in the range of 60-80 ° C. However, by specifying the ΔH value at 40 to 60 ° 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 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. 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, decanediol dimethyl ether, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, undecane diol diethyl ether Etc.

〔式中、Ｒ_１は水素原子又はメチル基を示し、ｍは０〜２の整数を示し、Ｘ_１、Ｘ_２のいずれか一方は−（ＣＨ_２）_ｎＯＣＯＲ_２又は−（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２は水素原子、炭素数１〜４のアルキル基、メトキシ基、又は、ハロゲンを示し、ｒ及びｐは１〜３の整数を示す。〕

〔式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示す。〕 More preferably, the component (c) is represented by the following general formula (1) described in JP-A-2006-137886 and the following general formula (2) described in JP-A-2006-188660. The compounds shown are used.

[Wherein, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and _one of X ₁ and X ₂ represents — (CH ₂ ) _n OCOR ₂ or — (CH ₂ ) _n COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom, 1 to 4 carbon atoms An alkyl group, a methoxy group, or halogen, and r and p each represent an integer of 1 to 3. ]

[Wherein, R represents an alkyl group or an alkenyl group having 8 or more carbon atoms. ]

Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R ₁ is a hydrogen atom, and , M is more preferably 0.
In the formula (2), R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.

The form of the microcapsule pigment applied to the present invention does not refuse application of a circular cross section, but a non-circular cross section 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 exhibit 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) / 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 showing 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.
Any water-soluble polymer that exhibits a gentle bridging action between pigment particles in the reversible thermochromic ink of the present invention can be applied. Among these, the nonionic water-soluble cellulose derivatives are 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.

  In addition, when the ink of the present invention is filled in a ballpoint pen, a higher fatty acid such as oleic acid, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, thiophosphorous acid tri (alkoxycarbonylmethyl ester) ) 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 preferably used in the form of a ballpoint pen because it is used for writing answers to details in a puzzle.

  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 ballpoint pen that communicates with the tip attached to the ink and further 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 balls are 0.2 to 3.0 mm, preferably 0.3 to 1.5 mm, more preferably 0.4 to 1.0 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 the 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 attached to a shaft cylinder directly or via a relay member, and the ink occlusion body of a 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.
In addition, 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 a writing sheet in the form of a memo or an order form using the writing instrument described above changes the color tone from a colored state to a colorless state by rubbing with a finger or applying heating means such as a heating tool. be able to.
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), etc. 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.

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.
Example 1 (see FIGS. 1 and 2)
Preparation of reversible thermochromic ink (i) 1.0 part of 1,2-benz-6- (N-ethyl-N-isoamylamino) fluorane as component, 1,3-dimethyl-6-diethylaminofluorane 2.0 Part (b), 1,1-bis (4′-hydroxyphenyl) 2-ethylhexane 8.0 parts, (c) color memory comprising 40.0 parts palmitic acid-4-methylbenzyl as component (c) A microcapsule pigment (T ₁ : −2 ° C., T ₂ : 10 ° C., T ₃ : 35 ° C., T ₄ : 48 ° C., average particle size: 2.5 μm, reversible thermochromic) Composition / wall membrane = 2.6 / 1.0, color change from red to colorless) 12.5 parts, succinoglycan (shear thinning agent) 0.33 parts, urea 10 parts, glycerin 10 parts , 0.6 part of a nonionic permeability imparting agent, Sex silicone anti-foaming agent 0.1 parts, 0.1 parts of a fungicide, to prepare a reversible thermochromic ink comprising water 66.37 parts.

Preparation of Writing Instruments The ink 4 (previously cooled to −2 ° C. or lower to develop a red color of the microcapsule pigment and 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 0.7 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.
Further, a SEBS resin member having a convex curve-shaped top is attached to the top of the cap 7 as a scraping member 8. The scraping member 8 is placed on an electronic balance so that the convex curved surface is on top, and is transparent on the scraping member 8. After the glass plate was brought into contact with the weighing pan of the electronic balance in a parallel state, the contact area between the scraping member 8 and the transparent glass plate, which was visually recognized by pressing the glass plate vertically with a load of 500 g and 1000 g, was measured. As a result, the contact area when pressed with a load of 500 g was 2.4 mm ² , and the contact area when pressed with a load of 1000 g was 4.0 mm ² .

Preparation of a writing sheet set The reversible thermochromic ballpoint pen (writing instrument 1) and "Please rub the handwriting with the attached scraping body. It can be erased." A writing sheet set was obtained by combining with memo paper made of high-quality paper (JISB5 size).
When writing a message or memorandum, etc. with red handwriting on a memo paper using the ballpoint pen, if the wrong place (red handwriting) is scraped from above with the scraping member 8, the character is discolored and visually recognized. lost. Since this state could be maintained at room temperature, the characters could be written again in the area where the scratch was erased.
Also, after the memo paper is buried, by heating the entire handwriting using a hair dryer, all the handwriting is decolored and is not visually recognized, and this state is maintained at room temperature, so the memo paper forms the handwriting Visualized as returning to the previous print. Therefore, a writing sheet set excellent in convenience and reusability, which can easily correct the handwriting and return it to a reusable state, was obtained.

Example 2
Preparation of reversible thermochromic ink (i) 2- (butylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2-3-g] pyrimidine-5,1 ′ (3′H) -isobenzofuran] -3-one 2.0 parts, (ro) component 2,2-bis (4′-hydroxyphenyl) hexafluoropropane 5.0 parts, 4,4 ′-( A microcapsule pigment (T) containing 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) ₁ : −16 ° C., T ₂ : −8 ° C., T ₃ : 48 ° C., T ₄ : 58 ° C., ΔH: 65 ° C., average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2. 6 / 1.0, pink to colorless After being uniformly dispersed in an aqueous medium consisting of 12 parts, 5 parts of glycerin, 0.7 parts of an antifungal agent, 0.1 part of a silicone-based antifoaming agent, and 74.2 parts of water, Hydroxyethyl cellulose (Union Carbide Japan Co., Ltd., trade name: Cellosize WP-09L, water-soluble polymer flocculant) 5 parts by weight of 8 wt% aqueous solution was added to the dispersed liquid while stirring, A reversible thermochromic ink was prepared by suspending a reversible thermochromic pigment in a gentle aggregate state.

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 (writing instrument).
The shaft tube is provided with a silicone resin member having a rubbing part as a rubbing portion as a rubbing member at the rear, and the rubbing member 8 is placed on an electronic balance so that the convex curving 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 .

Preparation of writing sheet set The reversible thermochromic marking pen (writing instrument), the ballpoint pen prepared in Example 1,
A non-color-changing black ink prints an image that says "Please rub the handwriting with the attached scraping body. It can be erased" at the bottom, and an image with multiple requirements (messages) in the frame. A writing sheet set was obtained by combining with a message memo consisting of high-quality paper (JISB7 size) printed on the upper half. In addition, the message memo can be provided with a detachable (reattachable) sticking portion, and a plurality of sheets can be formed as a set.
Using the marking pen, when the inside of the frame in which the desired requirements are written is painted with pink handwriting, the portion that is mistakenly painted (pink handwriting) is scraped from above with a scraping member. Disappeared and disappeared. Since this state could be maintained at room temperature, it was possible to show the other requirements by filling the other frame with the non-colored portion where the scratches were erased.
In addition, when a name or time is written with a red handwriting in the blank area below the frame using a ballpoint pen, if the wrong place (red handwriting) is scraped from above with a scraping member, the character will be erased. Disappeared. Since this state could be maintained at room temperature, the characters could be written again in the area where the scratch was erased.
In addition, after using the said message memo, all the handwriting was discolored and became invisible by heating the whole handwriting using the desk light (light). Since this state is maintained at room temperature, the message memo appears as if it had returned to the printed matter before handwriting formation. Therefore, a writing sheet set excellent in convenience and reusability, which can easily correct the handwriting and return it to a reusable state, was obtained.

Example 3
Preparation of a writing sheet set A writing sheet set was obtained in the same manner except that the printed image of the message memo used in Example 2 (frame body with description and requirements) printed with thermochromic black ink. It was.
As a result, writing and rubbing can be performed in the same manner as in Example 2, and after using the message memo, all the handwriting and marks can be obtained by heating the entire surface with a desk lamp (light). The image disappeared and became invisible. Since this state is maintained at room temperature, the message memo is visually recognized as a blank sheet. Therefore, a writing sheet set excellent in convenience and reusability, which can be easily returned to a state where it can be reused as memo paper or printing paper, was obtained.

Example 4 (see FIG. 3)
Preparation of reversible thermochromic ink (i) 4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H) as component -Indol-3-yl) -1 (3H) -isobenzofuranone 1.0 part, 2- (N-methylanilino) -6- (N-ethyl-Np-tolylamino) fluorane 4.0 parts, ) Component of 2,2-bis (4′-hydroxyphenyl) hexafluoropropane, 4.0 parts of 4,4 ′-(2-methylpropylidene) bisphenol, and component (c) capric acid-4 A microcapsule pigment (T ₁ : −18 ° C., T ₂ : −9 ° C., T ₃ : 42 ° C., T) containing a reversible thermochromic composition having color memory composed of 50.0 parts of benzyloxyphenylethyl ₄ : 63 ° C. Average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.8 / 1.0, color change from blue-green to colorless) 12.5 parts, xanthan gum (shear thinning agent) 0. Reversible heat consisting of 33 parts, 10 parts urea, 10 parts glycerin, 0.6 parts nonionic permeability imparting agent, 0.1 part modified silicone antifoaming agent, 0.1 part antifungal agent, 66.37 parts water A color changing ink was prepared.

Preparation of writing instrument The above ink 4 (previously cooled to −18 ° C. or less to make the microcapsule pigment color green and left at room temperature) was sucked and filled into a polypropylene pipe 21 having an inner diameter of 4.4 mm, and resin The ball-point pen tip 3 was connected via a holder 22 made of.
Next, from the rear part of the polypropylene pipe 21, the ink backflow prevention body 5 (liquid stopper) having a viscoelasticity mainly composed of polybutene is filled, and the tail plug 23 is fitted to the rear part of the pipe, and the front shaft cylinder After the rear barrel was assembled and the cap 7 was fitted, a degassing process was performed by centrifugation to obtain a reversible thermochromic ballpoint pen 1.
The ball-point pen tip 3 has a stainless steel ball having a diameter of 0.7 mm held by a ball holding portion formed by cutting a metal material, and the ball is urged forward by a spring body. Is.
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.

Preparation of a writing sheet set The reversible thermochromic ballpoint pen 1 (writing instrument) and non-color-changing black ink print the image “Please rub the handwriting with the attached scraping material. Combined with a writing sheet in the form of an order form consisting of high-quality paper (JISA4 size) printed on the entire surface of the frame with multiple product numbers in the frame and a space for entering the quantity of the corresponding product. A writing sheet set was obtained.
When the quantity and date are written with green handwriting on the order form using the ballpoint pen, if the wrong place (green handwriting) is scraped from above with the scraping member 8, the letters are erased and visually recognized. lost. Since this state could be maintained at room temperature, the characters could be written again in the area where the scratch was erased.
In addition, after using the sales order, all the handwriting is discolored and not visually recognized by heating the whole with a copying machine, and this state is maintained at room temperature. Visualized as if returning to print. Therefore, a writing sheet set excellent in convenience and reusability, which can easily correct the handwriting and return it to a reusable state, was obtained.

Example 5
Preparation of reversible thermochromic ink and preparation of writing instrument (a) 2,5-part 1,3-dimethyl-6-diethylaminofluorane as component, 2,2-bis (4'-hydroxyphenyl) hexa as component (b) Reversible color memory comprising 5.0 parts of fluoropropane, 4.0 parts of 4,4 '-(2-methylpropylidene) bisphenol, and 50.0 parts of 4-benzyloxyphenylethyl laurate as component (c) Microcapsule pigment encapsulating a thermochromic composition (T ₁ : −8 ° C., T ₂ : −1 ° C., T ₃ : 52 ° C., T ₄ : 65 ° C., ΔH: 63 ° C., average particle size: 2.5 μm) , Reversible thermochromic composition / wall film = 2.6 / 1.0, color change from orange to colorless) 12.5 parts, succinoglycan (shear thinning agent), 10 parts urea , 10 parts glycerin, nonio In Example 4, a reversible thermochromic ink comprising 0.6 part of a water-based permeability imparting agent, 0.1 part of a modified silicone antifoaming agent, 0.1 part of an antifungal agent and 66.37 parts of water was prepared. An orange ballpoint pen was obtained by incorporating the ballpoint pen in the form used.
In addition, 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (a) and 1,1-bis (4′-hydroxyphenyl) n-decane as component (b) 4.5 parts, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) Microcapsule pigment encapsulating thermochromic composition (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2.5 μm) Reversible thermochromic composition / wall film = 2.6 / 1.0, color change from black to colorless) 25.7 parts, succinoglycan (shear thinning agent) 0.2 parts, urea 5. 5 parts, glycerin 7.5 parts, imparting nonionic permeability Reversible thermochromic property comprising 0.03 part, modified silicone-based antifoaming agent 0.15 part, antifungal agent 0.1 part, lubricant 0.5 part, triethanolamine 0.5 part, water 59.82 part An ink was prepared and incorporated in the ballpoint pen of the form used in Example 4 to obtain a black ballpoint pen.
Furthermore, as component (i), 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide (2.0 parts), (b) component As bis (3-methyl-4-hydroxyphenyl) sulfide 8.0 parts, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 parts, (ha) component 4-benzyloxyphenyl caprate A microcapsule pigment (T ₁ : −14 ° C., T ₂ : −6 ° C., T ₃ : 48 ° C., T ₄ : 60 ° C.) encapsulating a reversible thermochromic composition having color memory consisting of 50.0 parts of ethyl. , ΔH: 64 ° C., average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0, color change from blue to colorless) 25.7 parts, succinoglycan (shear Thickening agent) .2 parts, 5.5 parts of urea, 7.5 parts of glycerin, 0.03 part of nonionic permeability imparting agent, 0.15 part of modified silicone antifoaming agent, 0.1 part of antifungal agent, lubricant A reversible thermochromic ink consisting of 5 parts, 0.5 parts of triethanolamine and 59.82 parts of water was prepared and incorporated into the ballpoint pen of the form used in Example 4 to obtain a blue ballpoint pen.

Preparation of writing sheet set A writing instrument set was prepared using the ballpoint pens (red, green) prepared in Examples 1 and 4 together with the three color ballpoint pens (orange, black, blue). In addition, a high quality paper (JISA4 size) printed on the edge with non-color-changing black ink is printed on a polyethylene resin plate (thickness 1 mm). A writing sheet in the form of a memo formed by sticking to was prepared and combined with the writing instrument set to obtain a writing sheet set.
When writing a message, memorandum, picture, etc. on a memo sheet with colorful handwriting using each of the ballpoint pens, if the portion (handwriting) to be corrected is scraped from above with a scraping member, the handwriting will be discolored. No longer visible. Since this state could be maintained at room temperature, it was possible to write again at the location where the scratch was erased.
In addition, after using the memo sheet, by heating the entire surface using desk lighting (light), all the handwriting is decolored and is not visible, and this state is maintained at room temperature, It appears as if the memo sheet had returned to the state before the handwriting was formed. Therefore, a writing sheet set excellent in convenience and reusability, which can easily correct the handwriting and return it to a reusable state, was obtained.

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 the sheet set for writing of this invention. It is longitudinal section explanatory drawing which shows an example of the writing instrument used for the sheet set for writing of this invention.

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 (7)

  A writing instrument containing ink that can be erased by heating, and a writing sheet written by the writing instrument, the writing sheet having an explanation section that indicates that the handwriting formed by the writing instrument is heated. Characteristic sheet set for writing.   The writing sheet set according to claim 1, wherein the explanation part of the writing sheet is formed of thermochromic ink.   The writing sheet set according to claim 1, wherein the writing sheet is paper having ink permeability.   The writing sheet set according to any one of claims 1 to 3, wherein the writing sheet has an image formed of non-color-changing ink.   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 sheet set according to claim 1, which contains an ink containing a microcapsule pigment which encapsulates 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 has a holding temperature range in which both states can coexist in a normal temperature range. 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., the writing sheet set according to claim 5, wherein the temperature _{T 4} is in the range of 30 to 80 ° C..   The writing sheet set according to any one of claims 1 to 6, wherein the writing instrument includes a scraping member.

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