JP4874886B2 - Mark sheet writing instrument, Mark sheet writing instrument set - Google Patents

Description

  The present invention relates to a writing instrument for mark sheets and a writing instrument set for mark sheets. Specifically, the present invention relates to a writing instrument for a mark sheet for marking a mark sheet paper, and a writing instrument set for a mark sheet.

Conventionally, pencils and mechanical pencils have been used as writing instruments used to mark mark sheets.
In the case of marking using the pencil or mechanical pencil, it takes time and effort to repeatedly mark the same portion in order to obtain a desired color density.
In order to solve the above problem, it is disclosed to write on a mark sheet using an ink for an infrared absorbing marker (for example, see Patent Document 1).
By using the infrared absorbing marker ink, it is possible to save the trouble of repeatedly marking the same part, but it is not possible to erase if the wrong part is marked, so it is necessary to rewrite a new mark sheet.
On the other hand, if you make a mistake in marking a pencil or mechanical pencil, you can erase the handwriting by erasing it with an eraser and mark it elsewhere, but if the eraser is attached to the paper, the mark sheet When reading the sensor, the sensor may react to extinguish and make accurate reading difficult.
JP-A-60-20975

  The present invention eliminates the trouble of repeatedly marking the same portion, and can be erased without generating eraser scraps when erasing, and enables accurate reading of the sensor during reading of the mark sheet, and writing instrument for mark sheet Provide a set.

The present invention is a writing instrument for marking on mark sheet paper, the writing instrument comprising (a) an electron-donating near-infrared absorbing organic compound, (b) an electron-accepting compound, and (c) the (a) and (b). A reversible thermochromic near-infrared absorbing composition that changes color from colored to colorless upon heating, and a friction member. Require a writing instrument for mark sheets.
Furthermore, using the microcapsule pigment encapsulating the reversible thermochromic near-infrared absorbing composition in a capsule wall film as a colorant, the reversible thermochromic near-infrared absorbing composition or microcapsule pigment, The color density-temperature curve exhibits a large hysteresis characteristic, exhibits a tautomerism between the colored state and the colorless state, the holding temperature range of both states is in the normal temperature range, and in the process where the temperature rises from the colored state, the temperature T ₃ reaches the start to decoloring, become completely colorless state at a temperature T ₄ or more temperature range than 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 , becomes completely colored state at a low temperature T ₁ of the following temperature range than temperature T _2, a hysteresis characteristic colored state and the colorless state in a temperature range between the temperature T ₂ and the temperature T ₃ is selectively retained And, temperatures _{T 1} is in the range of -30 to 0 ° C., the temperature _{T 4} to a requirement such as in the range of 45 to 95 ° C..
And (b) an electron-donating near-infrared absorbing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b). The mark sheet writing instrument set comprising a mark sheet writing instrument using a reversible thermochromic near-infrared absorbing composition that changes color from colored to colorless upon heating as a colorant and a friction body is a requirement.

  The present invention eliminates the trouble of repeatedly marking the same part as in a pencil or mechanical pencil, and can be erased without generating an eraser scrap when erasing, enabling accurate reading of the sensor when reading a mark sheet. It is possible to provide a writing instrument for mark sheets and a writing instrument set for mark sheets that are highly practical.

The writing instrument for the mark sheet uses a colorant that can be erased by heating.
The colorant includes at least three essential components of (i) an electron-donating near-infrared absorbing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction of the both occurs. A reversible thermochromic near-infrared absorbing composition that is discolored by heating, or a microcapsule pigment in which the reversible thermochromic near-infrared absorbing composition is encapsulated in a capsule wall film is effective.
Examples of the reversible thermochromic near-infrared absorbing composition include a reversible thermochromic near-infrared absorbing composition described in JP-A-63-145388 and JP-A-10-237436. In contrast to the case of increasing the temperature from the lower temperature side than the color change temperature range, the shape of the curve showing the large hysteresis characteristics (ΔH = 5 to 80 ° C.) and plotting the change in color density due to temperature change is the color change temperature range. Reversible heat with color memory that changes color by following a path that differs greatly from that when descending from a higher temperature side, and can maintain a colored state at a low temperature range or a decolored state at a high temperature range at a specific temperature range. A color-changing near-infrared absorbing composition is used.

The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic near-infrared absorbing composition will be described.
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 a density at a temperature T ₄ (hereinafter referred to as a complete decoloring temperature) that reaches a completely decolored state, and B is a temperature T ₃ (hereinafter referred to as a decoloring start temperature) that starts decoloring. C represents a density at a temperature T ₂ at which color development starts (hereinafter referred to as a color development start temperature), and D represents a temperature T ₁ at which a complete color development state is reached (hereinafter referred to as a complete color development state). This is a point indicating a density at a color development temperature).
Discoloration temperature region is a temperature region between the T ₁ and T _4, both states of the colored state and the decolored state can coexist, a temperature range between T ₂ and T ₃ is a large area of the difference in color density It is a real discoloration 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 large, it is easy to maintain each state before and after the color change.

Specific examples thermochromic near infrared absorption composition having a color-memory property, complete coloring temperature T ₁ of the freezing compartment, a temperature obtained only in a cold region or the like, i.e. -30 to 0 ° C., preferably −30 to −5 ° C., more preferably −30 to −10 ° C., and the temperature at which the complete decoloring temperature T ₄ is obtained from frictional heat generated by the friction body, that is, 45 to 95 ° C., preferably 50 to 90 ° C. Preferably, by specifying the range of 60 to 80 ° C. and specifying the ΔH value of 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 to the present invention is a reversible thermochromic near infrared absorbing composition in a colored state, or a microcapsule pigment containing the reversible thermochromic near infrared absorbing composition as a colorant, It is preferable that the handwriting formed by the writing instrument is not easily erased by finger touch or the like, 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.

Examples of the components (A), (B), and (C) are given below.
As the component (a) of the present invention, that is, the electron donating near infrared absorbing organic compound, compounds described in JP-A Nos. 63-145388 and 10-237436 can be used.

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. Alternatively, those having an amide group, a halogen group, etc., and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

Specific examples are given below.
Phenol, o-cresol, tertiary 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.
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). Carboxyl having a ΔT value (melting point-cloud point) of 5 ° C. or more and less than 50 ° C., which can form a reversible thermochromic near-infrared absorbing composition exhibiting color memory, which changes color by changing to the side) Acid ester compounds, for example, carboxylic acid esters containing a substituted aromatic ring in the molecule, esters of carboxylic acid containing an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, carboxylic acid ester containing a cyclohexyl group in the molecule , An ester of a fatty acid having 6 or more carbon atoms and an unsubstituted aromatic alcohol or phenol, a fatty acid having 8 or more carbon atoms and a branched aliphatic alcohol or ester, Esters of carboxylic acid and aromatic alcohol or branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurine, trimyristin, tri Stearin, 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, may be mentioned 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し、ｍ及びｎはそれぞれ１〜３の整数を示し、Ｘ及びＹはそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ハロゲンを示す。〕 Furthermore, as the component (c), a compound represented by the following general formula (1) described in JP-A-2006-137886, or a general formula (described below) described in JP-A-2006-188660 ( The compound represented by 2) is preferably 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 alkenyl group having 8 or more carbon atoms, m and n each represents an integer of 1 to 3, X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon The alkoxy group of number 1-4, and a halogen are shown. ]

Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, a reversible thermochromic near-infrared absorbing composition having a wider hysteresis width can be obtained, and further R ₁ is a hydrogen atom. It is more preferable that m is 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.
Examples of the compound include octanoic acid-4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, dodecanoic acid-4- Benzyloxyphenylethyl, tridecanoic acid-4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid-4- Benzyloxyphenylethyl, octadecanoic acid-4-benzyloxyphenylethyl, 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-didecanoic acid Phenylmethyl, dodecanoic acid 1,1-diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecanoic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid Examples include 1,1-diphenylmethyl and 1,1-diphenylmethyl octadecanoate.

The form of the microcapsule pigment encapsulating the reversible thermochromic near-infrared absorbing composition does not refuse application of a circular cross-section, but a non-circular cross-section is effective.
The handwriting formed by writing, the microcapsule pigment is closely oriented and fixed in close contact with the writing surface on the long diameter side (maximum outer diameter side), and exhibits a high concentration of color development. The microcapsule pigment is slightly elastically deformed into a shape that relieves the external force against the external force caused by friction by a friction body such as rubber, and the destruction of the wall film of the microcapsule is suppressed and the thermal discoloration function is not impaired It can be expressed effectively.
Here, the non-circular cross-sectional shape microcapsule pigment has an average value of the maximum outer diameter of 0.5 to 5.0 μm, preferably 1 to 4 μm, more preferably 1 to 3 μm, and reversible heat. Color-changing composition: wall film = 7: 1 to 1: 1 (mass ratio), preferably 6: 1 to 1: 1.
If the average value of the maximum outer diameter of the microcapsule pigment (including those having a circular cross-sectional shape) exceeds 5.0 μm, the outflow from the capillary gap tends to be reduced, and the average value of the maximum outer diameter is less than 0.5 μm. In this case, it becomes difficult to show high color density.
When the ratio of the reversible thermochromic composition to the wall film is larger than the above range, the thickness of the wall film becomes too thin, and the resistance to pressure and heat tends to decrease, and the ratio of the wall film to the reversible thermochromic composition When the value is larger than the above range, color density and sharpness during color development tend to be reduced.

  Microencapsulation of the reversible thermochromic near-infrared absorbing composition includes interfacial polymerization, interfacial polycondensation, in situ polymerization, in-liquid curing coating, phase separation from aqueous solution, and phase separation from organic solvent. Method, melt dispersion cooling method, air suspension coating method, spray drying method and the like, which are appropriately selected according to the application. Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

  When the microcapsule pigment is dispersed in a vehicle and used as an ink composition, it is blended in an amount of 2 to 50% by mass (preferably 3 to 40% by mass, more preferably 4 to 30% by mass) based on the total amount of the ink composition. can do. If it is less than 2% by mass, the color density is insufficient, and if it exceeds 50% by mass, the ink outflow is reduced and the writing property is impaired.

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 in which a microcapsule pigment is suspended in a gentle agglomerated state with a water-soluble polymer flocculant. Furthermore, the ink which adjusted the specific gravity difference of a microcapsule pigment and a vehicle to be 0.05 or less can be mentioned.

By adding the shear thinning agent, it is possible to suppress agglomeration and sedimentation of the microcapsule pigment, and it is possible to suppress bleeding of the handwriting, so that a good handwriting can be formed.
Furthermore, when the writing instrument filled with the ink is in the form of a ballpoint pen, ink leakage from the gap between the ball and the tip when not in use is prevented, or the ink flows backward when the writing tip is left upward (upright state). Can be prevented.

  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.

Examples of the water-soluble polymer flocculant include polyvinyl pyrrolidone, polyethylene oxide, water-soluble polysaccharides, water-soluble cellulose derivatives and the like. Specific examples of water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, and specific examples of water-soluble cellulose derivatives include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, etc. Can be mentioned.
Any water-soluble polymer flocculant that exhibits a gentle bridging action between pigment particles can be applied to the ink, and among these, a water-soluble cellulose derivative works most effectively.
The polymer flocculant can be blended in an amount of 0.05 to 20% by mass based on the total amount of the ink composition.

Water and, if necessary, a water-soluble organic solvent can be added to the ink.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolide And the like can be given.

  In addition, when the ink 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), Thiophosphorous acid triesters such as thiophosphorous acid tri (alkoxycarbonylethyl ester), phosphoric acid monoester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether or phosphorus of polyoxyethylene alkyl aryl ether It is preferable to prevent wear of the ball seat by adding a lubricant such as an acid diester or a metal salt, ammonium salt, amine salt or alkanolamine salt thereof.

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 fixing properties and viscosity to the paper surface.
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 sodium phosphate, defoamers, dispersing agents, a surfactant may be added a fluorine-based surfactant or a nonionic improve the ink permeability.

  The ink is filled into 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 tip of the writing to obtain a writing instrument for a mark sheet.

  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 0.3 to 3.0 mm, preferably 0.4 to 1.5 mm, more preferably 0.5 to 1.0 mm, such as cemented carbide, stainless steel, ruby, ceramic, resin, and rubber. A thing of a diameter is applicable.

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.
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.

The non-volatile liquid and / or the hardly volatile liquid is preferably thickened to a suitable viscosity by adding a thickener. As the thickener, the surface is treated with hydrophobic silica, and the surface is methylated. Fine particle silica, aluminum silicate, swellable mica, hydrophobic thickener such as bentonite and montmorillonite, fatty acid metal soap such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, Examples thereof include fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, dextrin compounds such as fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow prevention body and the solid ink backflow prevention body 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 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.

  Further, as a writing instrument for another form of mark sheet, the reversible thermochromic near infrared absorbing composition, or a crayon using a microcapsule pigment encapsulating the reversible thermochromic near infrared absorbing composition as a colorant, Examples include pencils and mechanical pencils that contain lead cores and mechanical pencil cores.

The handwriting obtained by writing on the writing surface using the mark sheet writing tool can be changed from a colored state to a colorless state by applying a friction member provided on the writing tool or a friction body different from the writing tool.
The friction member or the friction body is preferably an elastic body such as an elastomer or a plastic foam which is rich in elasticity and can generate frictional heat by generating appropriate friction during friction. Wood, metal, and fabric may be used.
As the material of the friction member and the friction body, silicone resin, SBS resin (styrene-butadiene-styrene copolymer), SEBS resin (styrene-ethylene-butylene-styrene block copolymer) and the like are preferable. Since the resin easily adheres to the portion erased by friction and the handwriting may be repelled when writing repeatedly, SBS resin or SEBS resin is more preferably used.
The friction member is excellent in portability by being fixed to a writing instrument.
Examples of the location where the friction member is fixed include a cap tip (top) or a shaft tube tip (portion where no writing tip is provided).
The friction body is combined with a writing instrument for a mark sheet to obtain a writing instrument set for a mark sheet.
In addition, the writing instrument mentioned above is used for the writing instrument for mark sheets which comprises the writing instrument set for mark sheets.

The writing instrument for a mark sheet of the present invention is composed of a writing instrument and a friction member attached to the writing instrument, and the writing instrument set for a mark sheet is composed of a writing instrument and a separate friction body. Uses a writing instrument to fill a mark sheet to be marked, and when correcting, erases the handwriting by rubbing the mark using a friction member or friction body, and marks a new part.
The sheet that has been marked as described above is set in a reading device and read. Note that at the time of reading, the marked portion is read accurately by the sensor, and the corrected portion (erased portion) is not read by the sensor.

Examples are shown below, but the present invention is not limited to these examples.
In addition, the part in an Example is a mass part.
Example 1
Preparation of writing instruments for mark sheets (see Fig. 2)
(A) Bis 3,3- [1- (4-dimethylaminophenyl) -1- (4-methoxyphenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide as a component; 0 parts, 4.0 parts of 4,4 '-(2-methylpropylidene) bisphenol as component (b), 6.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, component (c) As a microcapsule pigment (T ₁ : −20 ° C., T ₂ : −8 ° C., T ₃ : 45) containing a reversible thermochromic near-infrared absorbing composition comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as ° C., T ₄ : 58 ° C., ΔH: 65.5 ° C., average particle size: 2.5 μm, reversible thermochromic near-infrared absorbing composition: wall film = 2.6: 1.0, color from black to colorless Variable) 25.0 parts, thickener 0.2 parts, wetting agent 13. Part, a permeability imparting agent 0.03 part, a system antifoaming agent 0.15 part, an antifungal agent 0.1 part, a lubricant 0.5 part, and water 61.02 parts were prepared. .
The ink 4 (cooled and colored microcapsule pigment in black) was sucked and filled into a polypropylene pipe (ink containing pipe 21) and connected to the ballpoint pen tip 3 through a resin holder 22.
Next, an ink backflow prevention body 5 (liquid stopper) 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 (consisting 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 obtain a writing instrument 1 for a mark sheet (ballpoint pen). It was.
The ball-point pen tip has a stainless steel ball having a diameter of 0.5 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, and the ball is a spring It is energized forward by the body.
In addition, a SEBS resin member having a convex curved top as a friction member 8 is attached to the rear cylinder end.

Example 2
Preparation of writing instrument for mark sheet (i) Bis 3,3- [1- (4-dimethylaminophenyl) -1- (4-methoxyphenyl) ethylene-2-yl] -4,5,6,7-tetra as a component 4.0 parts of chlorophthalide, 4.0 parts of 4,4 '-(2-methylpropylidene) bisphenol as component (b), 6.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane Microcapsule pigment (T ₁ : −20 ° C., T ₂ : −8 ° C.) containing a reversible thermochromic near-infrared absorbing composition comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) , T ₃ : 45 ° C., T ₄ : 58 ° C., ΔH: 65.5 ° C., average particle size: 2.5 μm, reversible thermochromic near-infrared absorbing composition: wall film = 2.6: 1.0, 10.0 parts, increased in color from black to colorless 0.3 parts of agent, 13.0 parts of wetting agent, 0.03 part of permeability imparting agent, 0.15 part of antifoaming agent, 0.1 part of antifungal agent, 0.5 part of lubricant, 75.92 of water A reversible thermochromic ink consisting of parts was prepared.
The ink (cooled and microcapsule pigment was colored black) was sucked into a polypropylene pipe (ink containing pipe) and connected to the ballpoint pen tip 3 through a resin holder.
Next, an ink backflow prevention body (liquid stopper) was filled from the rear part of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to obtain a refill. Further, the refill was incorporated into a shaft cylinder (consisting of a front shaft cylinder and a rear shaft cylinder), a cap was fitted, and then a deaeration process was performed by a centrifugal process to obtain a writing instrument for a mark sheet (ballpoint pen).
The ball-point pen tip has a stainless steel ball having a diameter of 0.5 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, and the ball is a spring It is energized forward by the body.
In addition, a SEBS resin member having a convex curved top as a friction member is attached to the rear cylinder end.

Example 3
Preparation of writing instrument for mark sheet (i) 3.0 parts of 2,4-dimethyl-6-[(4-dimethylamino) anilino] -fluorane as component, 4,4 '-(2-methylpropylidene as component (b) ) Reversible thermochromic property comprising 4.0 parts of bisphenol, 6.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c). Microcapsule pigment encapsulating a near-infrared absorbing composition (T ₁ : −20 ° C., T ₂ : −7 ° C., T ₃ : 42 ° C., T ₄ : 56 ° C., ΔH: 62.5 ° C., average particle size: 2.5 μm, reversible thermochromic near-infrared absorbing composition: wall film = 2.6: 1.0, color change from dark green to colorless) 25.0 parts, thickener 0.2 parts, wetting agent 13.0 parts, permeability imparting agent 0.03 parts, system antifoaming agent 0 15 parts, 0.1 parts of a fungicide, 0.5 parts of a lubricant, to prepare a reversible thermochromic ink comprising water 61.02 parts.
The ink (cooled and microcapsule pigment was colored black) was sucked and filled into a polypropylene pipe (ink containing pipe) and connected to a ballpoint pen tip through a resin holder.
Next, an ink backflow prevention body (liquid stopper) was filled from the rear part of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to obtain a refill. Further, the refill was incorporated into a shaft cylinder (consisting of a front shaft cylinder and a rear shaft cylinder), a cap was fitted, and then a deaeration process was performed by a centrifugal process to obtain a writing instrument for a mark sheet (ballpoint pen).
The ball-point pen tip has a stainless steel ball having a diameter of 0.5 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, and the ball is a spring It is energized forward by the body.
In addition, a SEBS resin member having a convex curved top as a friction member is attached to the rear cylinder end.

Example 4
Preparation of writing instrument for mark sheet (A) 3.0 parts of 3- (4-dimethylaminophenyl) -3- [bis-1,1- (p-dimethylaminophenyl) -ethyleno-2] phthalide as component (b) 4,4 '-(2-methylpropylidene) bisphenol as component, 6.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, (ha) 4-benzyl caprate as component Microcapsule pigment (T ₁ : −20 ° C., T ₂ : −8 ° C., T ₃ : 41 ° C., T ₄ : 54 encapsulating a reversible thermochromic near-infrared absorbing composition comprising 50.0 parts of oxyphenylethyl ° C, ΔH: 61.5 ° C, average particle size: 2.5 μm, reversible thermochromic composition: wall film = 2.6: 1.0, color change from green to colorless) 25.0 parts, thickening Agent 0.2 parts, wetting agent 13.0 parts, permeability A reversible thermochromic ink comprising 0.03 part of an imparting agent, 0.15 part of an antifoaming agent, 0.1 part of an antifungal agent, 0.5 part of a lubricant and 61.02 parts of water was prepared.
The ink (cooled and microcapsule pigment was colored black) was sucked and filled into a polypropylene pipe (ink containing pipe) and connected to a ballpoint pen tip through a resin holder.
Next, an ink backflow prevention body (liquid stopper) was filled from the rear part of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to obtain a refill. Further, the refill was incorporated into a shaft cylinder (consisting of a front shaft cylinder and a rear shaft cylinder), a cap was fitted, and then a deaeration process was performed by a centrifugal process to obtain a writing instrument for a mark sheet (ballpoint pen).
The ball-point pen tip has a stainless steel ball having a diameter of 0.5 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, and the ball is a spring It is energized forward by the body.
In addition, a SEBS resin member having a convex curved top as a friction member is attached to the rear cylinder end.

Comparative Example 1
A reversible thermochromic ink was prepared in the same manner except that the component (a) in Example 1 was changed to 4.0 parts of 2- (2-chloroamino) -6-dibutylaminofluorane.
A writing instrument for a mark sheet (ballpoint pen) was obtained using the ink.

Using the mark sheet writing tools obtained in Examples 1 to 4 and Comparative Example 1, writing was performed on mark sheet paper.
As a result of reading the mark sheet paper set in a mark sheet reader (Pearson NUC, Opscan Insight 4), the mark sheet paper filled in with the writing implements of Examples 1 to 4 was normally readable. On the other hand, the mark sheet paper filled with the writing instrument of Comparative Example 1 was unreadable.

After the handwriting entered on each mark sheet paper was erased by rubbing with a friction member attached to the writing instrument, the result was set in the mark sheet reader (Pearson NUC, Opscan Insight 4) and read. It was unreadable.
Therefore, the handwriting entered with the writing tools for mark sheets of Examples 1 to 4 absorbs near-infrared light only in the colored state (colored), and can be read with a mark sheet reader, and near-infrared in the decolored state (colorless). Since it is not absorbed efficiently, it is impossible to read with a mark sheet reader, whereas the handwriting entered with the mark sheet writing tool of the comparative example is efficient in both the colored state (colored) and the decolored state (colorless). Since it does not absorb near infrared light, it cannot be read with a mark sheet reader.

Example 5
Preparation of writing instrument for mark sheet (i) Bis 3,3- [1- (4-dimethylaminophenyl) -1- (4-methoxyphenyl) ethylene-2-yl] -4,5,6,7-tetra as a component 4.0 parts of chlorophthalide, 4.0 parts of 4,4 '-(2-methylpropylidene) bisphenol as component (b), 6.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane Microcapsule pigment (T ₁ : −20 ° C., T ₂ : −8 ° C.) containing a reversible thermochromic near-infrared absorbing composition comprising 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) , T ₃ : 45 ° C., T ₄ : 58 ° C., ΔH: 65.5 ° C., average particle size: 2.5 μm, reversible thermochromic near-infrared absorbing composition: wall film = 2.6: 1.0, 10.0 parts, increased in color from black to colorless 0.3 parts of agent, 13.0 parts of wetting agent, 0.03 part of permeability imparting agent, 0.15 part of antifoaming agent, 0.1 part of antifungal agent, 0.5 part of lubricant, 75.92 of water A reversible thermochromic ink consisting of parts was prepared.
The ink (cooled and microcapsule pigment was colored black) was sucked into a polypropylene pipe (ink containing pipe) and connected to the ballpoint pen tip 3 through a resin holder.
Next, an ink backflow prevention body (liquid stopper) was filled from the rear part of the polypropylene pipe, and a tail plug was fitted to the rear part of the pipe to obtain a refill. Further, the refill was incorporated into a shaft cylinder (consisting of a front shaft cylinder and a rear shaft cylinder), a cap was fitted, and then a deaeration process was performed by a centrifugal process to obtain a writing instrument for a mark sheet (ballpoint pen).
The ball-point pen tip has a stainless steel ball having a diameter of 0.5 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, and the ball is a spring It is energized forward by the body.

Production of friction body A rectangular friction body was obtained using a rectangular SEBS resin as the friction body.

Production of Mark Sheet Writing Instrument Set A mark sheet writing instrument set was obtained by combining the mark sheet writing instrument and a friction body.
After writing on the mark sheet paper using the writing instrument for mark sheets, the mark sheet paper was normally readable as a result of reading by setting in a mark sheet reader.
After the handwriting written on each mark sheet paper was erased by rubbing with a friction body, it was set in a mark sheet reader and read.

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 for mark sheets of this invention.

Explanation of symbols

T ₁ complete color development temperature T ₂ color development start temperature T ₃ color erasure start temperature T ₄ complete color erasure temperature ΔH hysteresis width 1 writing tool for mark sheet 2 refill 21 ink containing tube 22 holder 23 tail plug 3 ballpoint pen tip 4 ink 5 ink backflow preventer 6 Shaft cylinder 7 Cap 8 Friction member

Claims (4)

  A writing instrument for marking on mark sheet paper, wherein the writing instrument comprises (a) an electron-donating near-infrared absorbing organic compound, (b) an electron-accepting compound, and (c) the colors of (a) and (b). A writing instrument for a mark sheet, which comprises at least a reaction medium for controlling a reaction, uses a reversible thermochromic near-infrared absorbing composition that changes color from colored to colorless by heating, and includes a friction member.   The writing instrument for a mark sheet according to claim 1, wherein a microcapsule pigment in which the reversible thermochromic near-infrared absorbing composition is encapsulated in a capsule wall film is used as a colorant. The reversible thermochromic near-infrared absorbing composition or microcapsule pigment exhibits a large hysteresis characteristic with respect to a color density-temperature curve and exhibits a tautomerism between a colored state and a colorless state, and both holding temperature ranges are in a normal temperature range. There, in the course of temperature increase from the 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 is lowered from the colorless state in the process, begins to coloration reached temperature T ₂ lower than the temperature T _3, becomes completely colored state at a low temperature T ₁ of the following temperature range than temperature T _2, the temperature range between the temperature T ₂ and the temperature T ₃ 3. A hysteresis characteristic in which a colored state and a colorless state are selectively maintained at a temperature T ₁ is in a range of −30 to 0 ° C., and a temperature T ₄ is in a range of 45 to 95 ° C. 3. Mark sheet brush Ingredients.   (B) an electron-donating near-infrared absorbing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b) above. A writing instrument set for a mark sheet comprising a reversible thermochromic near-infrared absorbing composition that changes color from colored to colorless as a colorant, and a friction sheet.

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