JP3376287B2 - Writing, erasing and writing / erasing tools - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a writing / erasing tool in which a writing tool using an erasable image forming material and an erasing tool using an erasing liquid for the image forming material are combined.

[0002]

2. Description of the Related Art In recent years, as office automation has advanced, the amount of various information has increased remarkably, and the output of information by hard copy has also increased accordingly. Hardcopy output is the most basic means of displaying information,
It has excellent versatility and storability. However, in hard copy output, as the amount of information increases, a large amount of paper is used as a recording medium, which leads to an increase in felling of wood, which is a raw material of paper. Forest resources are very important in terms of maintaining the global environment and suppressing the greenhouse effect of carbon dioxide. For this reason, the cutting of new timber is minimized,
The efficient use of the paper resources that we already have is a major issue.

Conventionally, the reuse (recycling) of paper resources is
It is carried out by treating a paper on which an image forming material is printed with a large amount of a bleaching agent and water, and re-filtering the paper fibers to produce a recycled paper of poor quality. Such a method not only raises the cost of recycled paper, but also causes new environmental pollution associated with the treatment of waste liquid.

[0004] In the old days, paper has been reused by correcting the image with a poppy rubber for a pencil and a correction liquid for a writing instrument. However, in these methods, the efficiency of correction is inferior, and the paper surface becomes soiled, so that reuse is limited. Further, recently, rewritable paper and the like for the purpose of reusing hard copy paper have been proposed. However, rewritable paper can be reused but cannot be recycled because it is a special paper in addition to being applicable only to thermal recording.

On the other hand, the present inventors contain a color-developing compound, a color-developing agent, and a decoloring agent that adsorbs these compounds, and can form an image in the same manner as an ordinary image-forming material. In addition, we are developing an image-forming material that can erase images by processing with heat or solvent. By using such an erasable image forming material, it is possible to reuse (reuse) the paper in which the image is erased and returned to the blank state many times, while the deterioration of the paper quality is prevented as much as possible. Then, since the paper may be recycled when the deterioration of the paper quality due to the reuse becomes remarkable, the utilization efficiency of the paper resources is dramatically improved. In this way, the amount of paper used can be substantially reduced, so that the felling of wood can be minimized. Moreover, the high cost of recycled paper and environmental pollution due to waste liquid treatment, which are problems in the current recycling system, can be avoided as much as possible.

By the way, it is sometimes convenient if only a part of an image formed of an erasable image forming material can be erased. For example, when the draft of a manuscript is modified, the case where the original draft is not erased but only the editing part is selectively erased and the rewriting is performed again may be considered. If this kind of work is possible, the manuscript can be sufficiently edited and corrected without leaving stains on it, and the paper can be reused by erasing the original manuscript and the editing part at once. Use efficiency of is improved.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to use an erasable image forming material and its erasing liquid and then selectively erase a part of an image after forming an image. It is to provide a writing / erasing tool that can be erased collectively.

[0008]

A writing instrument according to one aspect of the present invention provides a color-developing compound, a color-developing agent, a first matrix agent, and one of the color-developing compound and the color-developing agent. Writing part using an erasable first image-forming material containing a decoloring agent having a function of decolorizing compound-developing agent interaction to be absorbed by absorbing the color A color-developing compound, a color-developing agent, a second matrix agent, and one of the color-developing compound and the color-developing agent are preferentially adsorbed to reduce the color-developing compound-developing agent interaction. And a second writing section using an erasable second image forming material containing a decoloring agent having an effect of decoloring by means of. An eraser according to another aspect of the present invention is a color-developing compound, a color-developing agent, a first matrix agent, and a color by preferentially adsorbing one of the color-developing compound and the color-developing agent. Writing part using a erasable first image-forming material containing a decolorizing agent having an action of reducing the color-developing agent-decoloring agent interaction, a color-developing compound, and a developing color And a second matrix agent, and has an action of preferentially adsorbing one of the color-developing compound and the color-developing agent to reduce the color-developing compound-developing agent interaction to eliminate the color. An erasing tool for erasing an image written by a writing tool having a second writing part using an erasable second image forming material containing a decoloring agent,
A first matrix agent having an affinity for swelling or dissolving the first matrix agent and having a lower affinity for the second matrix agent than for the first matrix agent;
A first erasing unit using the erasing liquid of
And a second erasing portion using a second erasing liquid having an affinity for swelling or dissolving the matrix agent. A writing / erasing tool according to still another aspect of the present invention is a color-developing compound, a color-developing agent, a matrix agent, and one of the color-developing compound and the color-developing agent that is preferentially adsorbed to produce a color. And a writing part using an erasable image-forming material containing a decoloring agent having a function of decoloring by reducing the interaction of a color-developing agent, and erasing having an affinity for swelling or dissolving the matrix agent. And an erasing section using a liquid. A writing / erasing tool according to still another aspect of the present invention is a color-developing compound, a color developer,
Decoloring having a function of preferentially adsorbing one of the first matrix agent and the color-developing compound and the color-developing agent to reduce the color-developing compound-developing agent interaction to decolorize. A first writing part using an erasable first image forming material containing an agent, a color-developing compound, a developer, a second matrix agent, and the color-developing compound and the developer Second writing using an erasable second image-forming material containing a decoloring agent having the action of preferentially adsorbing one of them to reduce the color-developing compound-developing agent interaction to decolorize Part, and a first erasing liquid having an affinity for swelling or dissolving the first matrix agent and having a lower affinity for the second matrix agent than that for the first matrix agent. Erasing unit and the first and second And having a second erase unit using the second erase liquid having affinity to swell or dissolve the matrix material.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The writing instrument of the present invention may use the image forming material in either liquid or solid form. Writing instruments using the image forming material in the form of liquid ink include a ballpoint pen, a felt-tip pen, a fountain pen, a drawing pen, a marker, a writing pen, and the like. Writing instruments using solid image-forming materials include crayons, colored pencils, chalk and the like. The erasing tool in the present invention uses an erasing liquid, and is typically a marker type erasing pen. The present invention provides a writing instrument having two types of writing sections, an erasing instrument having two types of erasing sections, and a writing / erasing instrument combining one or two types of writing sections and one or two types of erasing sections. set to target.

The image-forming material used in the present invention is colored by using a color-forming compound, a developer and a decolorizer.
Decolorization is possible. Although such an image forming material can be erased by heating or contact with a solvent, the present invention provides an erasing tool using an erasing solvent.

In the present invention, the color-developing compound is a precursor compound of a dye forming color information such as characters and figures, and the color-developing agent is an interaction with the color-developing compound (mainly electron transfer). Is a compound that colors the color-forming compound. The color-developing compound and the color-developing agent develop color when the interaction between them increases, and decolorize when the interaction between them decreases. In the following, the color-developing compound and the color-developing agent in the color-developed state may be referred to as a pigment component. A decolorizing agent preferentially adsorbs one of the dye components (generally, the color developer) when the erasing solvent penetrates into the image forming material to allow the interaction between the color developing compound and the color developing agent. It is a substance that has the effect of reducing and decoloring. Further, the matrix agent is a substance having a function of fixing and holding components such as a color developing compound and a color developing agent on the paper, and is generally classified as a vehicle or a binder. The matrix agent is made of resin or wax.

When the erasing solvent is brought into contact with the image forming material in the color-developed state to erase the color, the following phenomenon occurs. That is, when the solvent is brought into contact with the image forming material that is colored on the paper, the matrix agent (resin or wax) is swollen or partially dissolved by the solvent. As a result, each component in the image-forming material becomes relatively free to move, the developer mixes with the decolorizer, and the interaction between the developer and the color-developing compound is lost and the image is lost. The forming material is decolorized. Then, when the solvent is removed from the paper, the decolored state of the image forming material is fixed while the decoloring agent takes in the developer in an amount exceeding the equilibrium solubility. This decolored state is very stable at room temperature.

As described above, when the matrix agent in the image forming material is swollen or partially dissolved by the erasing solvent, the color is erased in a short time. In the present invention, as will be described in detail later, focusing on the affinity between the matrix agent and the erasing solvent, the writing / erasing tool devised a combination of these,
It is possible to selectively erase a part of an image or all images at once.

Each component used in the present invention will be specifically described below. Examples of the color-forming compound used in the present invention include electron-donating organic substances such as leuco auramine, diaryl phthalide, polyaryl carbinol, acyl auramine, aryl auramine, rhodamine B lactam, indoline, spiropyran, and fluoran. To be
Specifically, crystal violet lactone (CV
L), malachite green lactone, 2-anilino-6
-(N-cyclohexyl-N-methylamino) -3-methylfluorane, 2-anilino-3-methyl-6- (N
-Methyl-N-propylamino) fluorane, 3- [4
-(4-Phenylaminophenyl) aminophenyl] amino-6-methyl-7-chlorofluorane, 2-anilino-6- (N-methyl-N-isobutylamino) -3-
Methylfluorane, 2-anilino-6- (dibutylamino) -3-methylfluorane, 3-chloro-6- (cyclohexylamino) fluorane, 2-chloro-6- (diethylamino) fluorane, 7- (N, N -Dibenzylamino) -3- (N, N-diethylamino) fluorane, 3,6-bis (diethylamino) fluorane, γ-
(4′-nitroanilino) lactam, 3-diethylaminobenzo [a] -fluorane, 3-diethylamino-6
-Methyl-7-aminofluorane, 3-diethylamino-7-xylidinofluorane, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-
Methylindol-3-yl) -4-azaphthalide, 3
-(4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3-diethylamino-7-chloroanilinofluorane, 3-diethylamino-7,8-benzofluorane, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,6-dimethylethoxyfluorane,
3-diethylamino-6-methoxy-7-aminofluorane, DEPM, ATP, ETAC, 2- (2-chloroanilino) -6-dibutylaminofluorane, crystal violet carbinol, malachite green carbinol, N- (2, 3-dichlorophenyl) leuco auramine, N-benzoyl auramine, rhodamine B lactam, N-acetyl auramine, N-phenyl auramine, 2- (phenyliminoethanedilidene) -3,3
-Dimethylindoline, N, 3,3-trimethylindolinobenzospiropyran, 8'-methoxy-N, 3,3
-Trimethylindolinobenzospiropyran, 3-diethylamino-6-methyl-7-chlorofluorane, 3-
Diethylamino-7-methoxyfluorane, 3-diethylamino-6-benzyloxyfluorane, 1,2-benzo-6-diethylaminofluorane, 3,6-di-p
-Toluidino-4,5-dimethylfluorane, phenylhydrazide-γ-lactam, 3-amino-5-methylfluorane and the like can be mentioned. These alone or 2
A mixture of two or more species can be used. Since a colored state of various colors can be obtained by appropriately selecting a color-developing compound, multi-color compatibility is possible.

The color developer used in the present invention includes phenol, phenol metal salt, carboxylic acid metal salt, benzophenone, sulfonic acid, sulfonic acid salt, phosphoric acid, phosphoric acid metal salt, acidic phosphoric acid ester, acidic phosphoric acid. Acidic compounds such as ester metal salts, phosphorous acid, and metal phosphite salts can be mentioned. Specifically, gallic acid; gallic acid esters such as methyl gallate, ethyl gallate, n-propyl gallate, i-propyl gallate, and butyl gallate;
-Dihydroxybenzoic acid, dihydroxybenzoic acid such as methyl 3,5-dihydroxybenzoate and esters thereof; 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 3,5-dihydroxyacetophenone,
Acetophenone derivatives such as 2,3,4-trihydroxyacetophenone; 2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,3
Benzophenone derivatives such as 4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone; 2, Biphenols such as 4'-biphenol and 4,4'-biphenol; 4-[(4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4-
[(3,5-Dimethyl-4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2. 3-benzenetriol, 4,4'-
[1,4-phenylenebis (1-methylethylidene) bis (benzene-1,2,3-triol)], 4,4 '
-[1,4-phenylenebis (1-methylethylidene)
Bis (1,2-benzenediol)], 4,4 ', 4 "
-Ethylidene trisphenol, 4,4 '-(1-methylethylidene) bisphenol, methylene tris-p-
Examples include polyphenols such as cresol. These may be used alone or in combination of two or more.

The decolorizing agent used in the present invention exhibits an adsorbing action on the color developing agent when the erasing solvent penetrates into the image forming material as described above, and after the solvent is removed, the decoloring agent develops. It has the property of making it difficult for the colorant to diffuse and escape. The decoloring agent may be a low molecular weight organic material such as a sterol compound, a cyclic sugar alcohol and its derivative, or a high molecular weight decoloring agent. The decoloring agent may be contained in the image forming material or may be contained in the erasing solvent.

Specific decolorizing agents include animal sterin,
Examples include sterol compounds such as plant sterin and fungal sterin. As animal sterin, cholesterol,
Examples thereof include lanosterol, lanostadier, agnosterol, cholestanol, coprostanol, ostreasterol, actiniasterol, spongosterol, and clionasterol. Examples of bile acids include colanic acid, cholic acid, hyodeoxycholic acid, lithocholic acid and the like. As a plant sterin,
Stegmasterol, α-sitosterol, β-sitosterol, γ-sitosterol, brassicasterol,
Vitamin D etc. are mentioned. As a fungal sterin,
Ergosterol etc. are mentioned. One or more of these may be used. Alternatively, a material that is originally a mixture such as lanolin alcohol may be used.

Examples of the decoloring agent include cholic acid, lithocholic acid, testosterone and cortisone, and derivatives thereof, which have a very high adsorbability for the color developer. Specific examples include cholic acid, cholic acid methyl ester, sodium cholic acid, lithocholic acid, lithocholic acid methyl ester, sodium lithocholic acid, hyodeoxycholic acid, hyodeoxycholic acid methyl ester, testosterone, methyltestosterone, 11α-hydroxymethyl. Testosterone, hydrocortisone, cholesterol methyl carbonate, α-cholestanol may be mentioned. Among these, those having two or more hydroxyl groups are particularly preferable.

As the decoloring agent, a cyclic sugar alcohol and a derivative thereof which are compounds having a high amorphous property and having an action of suppressing phase separation of a composition system (phase separation inhibitor) can also be mentioned.
Specific examples include D-glucose, D-mannose, D
-Galactose, D-fructose, L-sorbose,
L-rhamnose, L-fucose, D-ribodesource, α
-D-glucose = pentaacetate, acetoglucose, diacetone-D-glucose, D-glucuronic acid,
D-galacturonic acid, D-glucosamine, D-fructosamine, D-isosugaric acid, vitamin C, ertorubic acid,
Trehalose, saccharose, maltose, cellobiose, gentiobiose, lactose, melibiose, raffinose, gentianose, merezitose, stachyose, methyl = α-glucopyranoside, salicin, amygdalin, euxanthic acid, 1,2: 5,6-diisopropylidene-D- Examples include mannitol. One or more of these may be used.

As the decoloring agent, a non-aromatic cyclic compound having a hydroxyl group other than the cyclic sugar alcohol, which is a phase separation inhibitor having low amorphousness, and a non-aromatic cyclic compound having 5 or more ring members, or a derivative of the cyclic sugar alcohol may also be used. Can be mentioned. Specific examples include alicyclic monohydric alcohols such as cyclododecanol, hexahydrosalicylic acid, menthol, isomenthol, neomenthol, neoisomenthol, carbomenthol,
α-carbomenthol, piperitol, α-terpineol, β-terpineol, γ-terpineol, 1-
p-menthen-4-ol, isopulegol, dihydrocarbeol, carveol; alicyclic polyhydric alcohol,
For example, 1,4-cyclohexanediol, 1,2-cyclohexanediol, phloroglucitol, quercitol, inositol, 1,2-cyclododecanediol, quinic acid, 1,4-terpine, 1,8-terpine, pinol hydrate. , Betulin; polycyclic alcohol derivatives such as borneol, isoborneol, adamantanol, norborneol, fenchol, camphor, isosorbide; derivatives of cyclic sugar alcohols such as 1,2: 5,6-diisopropylidene-D- Mannitol is mentioned. One or more of these may be used. It is preferable to use a phase separation inhibitor having high amorphousness and a phase separation inhibitor having low amorphousness in combination.

As the polymer decolorizing agent (polymer or oligomer), starch (potato starch, corn starch, rice starch, wheat starch, taro starch, etc.), cellulose, cellulose derivative and the like are preferable.

Next, the combination of the matrix agent and the erasing solvent in the image forming material, which is a feature of the present invention, will be described. Here, a matrix having a high affinity with a wide variety of solvents from a solvent having a high electron donating property (eg, ketone, ether, etc.) to a solvent having a relatively low electron donating property (eg, alcohol, ester, etc.) and swelling or dissolving. The agent is the first matrix agent. On the other hand, a matrix agent that does not have a high affinity with a solvent having a relatively low electron donating property but has a high affinity with a solvent having a high electron donating property and a high solubility and swells or dissolves is used as a second matrix agent. To do.

As the first matrix agent, higher alcohols (1-docosanol, 1-eicosanol, stearyl alcohol, etc.), higher ketones (stearone, 1)
4-heptacosanone) or higher fatty acid ester (such as stearyl alcohol laurate and stearate docosanol ester); aliphatic wax; polyester oligomer; polyvinyl alcohol and its copolymer; oligosaccharide and its derivative; methyl cellulose, ethyl cellulose , And cellulose derivatives such as cellulose acetate. It is preferable that these have a weight average molecular weight of 10 ² to 10 ⁴ . Less than,
A writing instrument having a writing portion using the erasable first image forming material containing a color developable compound, a color developing agent, and a first matrix agent (an erasing agent if necessary) is called an A-type writing instrument.

Examples of the second matrix agent include polystyrene, styrene-acrylate copolymer, polyester and the like. As acrylate monomers constituting the styrene / acrylate copolymer, n-butyl methacrylate, isobutyl methacrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminopropyl methacrylate, 2 -Ethylhexyl acrylate, butyl acrylate-N-
(Ethoxymethyl) acrylamide, ethylene glycol methacrylate, 4-hexafluorobutyl methacrylate) and the like. Hereinafter, what has a writing part using a erasable second image forming material containing a color developable compound, a color developer, and a second matrix agent (an erasing agent if necessary) is referred to as a B-type writing instrument.

On the other hand, an erasing solvent (which may contain a decoloring agent) which has a high affinity for the first matrix agent and causes it to swell or dissolve but has a low affinity for the second matrix agent is used. It is called the erasing liquid of 1. Also,
An erasing solvent (which may contain a decoloring agent) which has a high affinity for the first and second matrix agents and causes both of them to swell or dissolve is referred to as a second erasing liquid.

As the first erasing liquid, water, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, pentyl alcohol, 2-pentyl alcohol,
3-pentyl alcohol, isopentyl alcohol, 1
-Hexanol, 2-hexanol, 3-hexanol, cyclopentanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, glycerin and the like are used. Hereinafter, one having an erasing section using the first erasing liquid is referred to as an a-type erasing tool.

The second erasing liquid contains saturated ethers such as ethyl ether, ethyl propyl ether, ethyl isopropyl ether, isopentyl methyl ether, butyl ethyl ether, dipropyl ether, diisopropyl ether, ethyl isopentyl ether and dibutyl ether. Dipentyl ether, diisopentyl ether, dihexyl ether; unsaturated ethers such as ethyl vinyl ether, allyl ethyl ether, diallyl ether, ethyl propargyl ether; ethers of dihydric alcohols such as 2-methoxyethanol, 2-
Ethoxyethanol, 2-butoxyethanol, 1,2
-Dimethoxyethane, 1,2-diethoxyethane, 1,
2-dibutoxyethane; cyclic ethers such as oxetane, tetrahydrofuran, tetrahydropyran, dioxolane, dioxane, trioxane; saturated ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, isopropyl methyl ketone,
Butyl methyl ketone, ethyl propyl ketone, isobutyl methyl ketone, pinacolone, methyl pentyl ketone,
Butyl ethyl ketone, dipropyl ketone, diisopropyl ketone, hexyl methyl ketone, isohexyl methyl ketone, heptyl methyl ketone, dibutyl ketone; unsaturated ketones such as ethylidene acetone, allyl acetone, mesityl oxide; cyclic ketones such as cyclopentanone , Cyclohexanone, cycloheptanone, cyclooctanone; esters such as ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate,
Isopentyl formate, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, sec-amyl acetate, hexyl acetate, allyl acetate, 2-methoxyethyl acetate, 2
-Ethoxyethyl acetate, 1,2-diacetoxyethane, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, pentyl propionate, isopentyl propionate, sec-amyl propionate, 2-methoxy Propyl acetate, 2-ethoxypropyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, pentyl butyrate, isopentyl butyrate, sec-amyl butyrate, methyl isobutyrate, ethyl isobutyrate, isopropyl isobutyrate, isopropyl isobutyrate Butyl isobutyrate, pentyl isobutyrate, isopentyl isobutyrate, sec-amyl isobutyrate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, methyl valerate Ethyl valerate, valerate propyl,
Examples include isopropyl valerate, butyl valerate, methyl hexanoate, ethyl hexanoate, propyl hexanoate, and isopropyl hexanoate. As a solvent other than the above, methylene chloride, γ-butyrolactone, β-propiolactone, n-methylpyrrolidinone, dimethylformamide,
Dimethylacetamide, dimethyl sulfoxide, etc. are used. Hereinafter, a device having an erasing section using the second erasing liquid is referred to as a b-type erasing tool.

The erasing characteristics of the two erasing tools for the respective images formed by the above two writing tools are as follows, judging from the affinity between the erasing solvent and the matrix agent. That is, the a-type erasing tool can erase the image formed by the A-type writing instrument (containing the first matrix agent), but cannot erase the image formed by the B-type writing instrument (containing the second matrix agent) ( Selective erase). On the other hand, b
The pattern eraser can erase both the images formed by the A-type writing instrument and the B-type writing instrument (collective erase).

The writing / erasing tool of the present invention is
At least two types selected from the group consisting of A-type writing instruments, B-type writing instruments, a-type erasing instruments and b-type erasing instruments are integrated, and various combinations are possible. For example, an Aa type writing tool that integrates an A type writing instrument and an a type erasing instrument
Erase tool, B-type writing and erasing tool that integrates B-type writing tool and b-type erasing tool, AB that combines A-type writing tool and B-type writing tool
A type writing instrument, an ab type erasing instrument that integrates an a type erasing instrument and a b type erasing instrument, an ABab type writing and erasing instrument that integrates all of these.

By using such a writing / erasing tool of the present invention, it becomes possible to selectively erase or collectively erase images formed by two types of writing instruments. Therefore, for example, only the added portion on the original can be selectively erased, so that the additional correction can be made many times, and furthermore, the original original and the added portion can be collectively erased to reuse the paper.

In order to improve the affinity with the matrix agent, another solvent may be mixed with the first erasing liquid or the second erasing liquid. Examples of such a solvent include toluene, ethylbenzene, propylbenzene,
Cumene, butylbenzene, isobutylbenzene, sec
-Butylbenzene, pentylbenzene, diethylbenzene, mesitylene, xylene, cresol, ethylphenol, dimethoxybenzene, dimethoxytoluene, benzyl alcohol, tolylcarbinol, cumyl alcohol, acetophenone, propiophenone, hexane, pentane, heptane, octane, cyclohexane. , Cyclopentane, cycloheptane, cyclooctane, petroleum fractions (petroleum ether, benzine, etc.).

When the image forming material is used as the liquid ink, the solvent for dispersing the image forming material is selected in consideration of the solubility of the developer. For example, nonpolar solvents include toluene, ethylbenzene, propylbenzene, cumene, butylbenzene, isobutylbenzene, s
ec-butylbenzene, pentylbenzene, diethylbenzene, xylene, hexane, pentane, heptane, octane, cyclohexane, cyclopentane, cycloheptane, cyclooctane, octene, decene, dodecene,
Petroleum fractions (petroleum ether, benzine, etc.), polar solvents such as water, limonene, cresol, ethylphenol, dimethoxybenzene, simethoxytoluene, benzyl alcohol, tolylcarbinol, cumyl alcohol, acetophenone, propiophenone are used. .

In the present invention, when the color developing compound interacts with other components other than the color developer to develop a color, a good erased state cannot be obtained. Therefore, for example, the wax or resin used as the matrix agent is desired to have a low content of acidic components, and the acid value is preferably 10 or less. Similarly, the pH of the paper medium on which an image is formed is preferably 7 or higher. Therefore, when an image is formed on recycled paper having a low pH value, the pH of the paper may be adjusted by adding a basic compound or the like to the image forming material.

The dye component (color-developing compound and developer) and the decolorizer may be separated from each other by a phase separation structure or microencapsulation. The phase-separated structure can be realized by separately dispersing the dye component and the decoloring agent in the matrix agent and then mixing them. In the case of microencapsulation, the material to be encapsulated in the shell made of the matrix agent may be a pigment component or a decoloring agent. However, since the decolorizer is blended in a larger amount than the dye component, microcapsulation of the dye component provides an image forming material with less dispersion in production and a good dispersion state.

[0035]

EXAMPLES Examples of the present invention will be described below. Example 1 1 part by weight of crystal violet lactone (CVL) as a color-developing compound, and propyl gallate 1 as a color developer.
Parts by weight, 10 parts by weight of cholic acid as a decoloring agent, 5 parts by weight of 1-docosanol (first matrix agent) as a wax, and 135 parts by weight of cyclohexane as a main solvent, and sufficiently stirred using a paint shaker. The erasable liquid ink 1A (first image forming material) is prepared.

1 part by weight of crystal violet lactone (CVL) as a color-forming compound, 1 part by weight of propyl gallate as a developer, and 10 parts by weight of cholic acid as a decolorizer.
It is erasable by mixing 5 parts by weight of a styrene-acrylate copolymer (second matrix agent) having an acrylate content of 5% as a resin and 135 parts by weight of toluene as a main solvent, and sufficiently stirring using a paint shaker. Liquid ink 1B (second image forming material) is prepared.

On the other hand, an erasing liquid containing isopropyl alcohol as a main component (first erasing liquid) 1a and an erasing liquid containing methyl ethyl ketone (MEK) as a main component (second erasing liquid) 1
Prepare b and. The alcohol-based erasing liquid 1a can erase the liquid ink 1A but cannot erase the liquid ink 1B. The ketone-based erasing liquid 1b can erase both the liquid ink 1A and the liquid ink 1B. In order to improve the erasing performance, for example, 3 wt% of soluble starch is dissolved in the alcohol-based erasing liquid 1a and 5 wt% of cholesterol is dissolved in the ketone-based erasing liquid 1b. Good.

Using the liquid inks 1A and 1B and the erasing liquids 1a and 1b, the marker (AB shown in FIG. 1A is used.
A type marker) and an erasing pen (ab type erasing pen) shown in FIG. 1B are manufactured.

The AB type marker shown in FIG. 1 (A) has the following structure. The liquid inks 1A and 1B are housed in ink holders 6A and 6B, respectively, and these ink holders 6A and 6B are integrally held in a cylindrical body portion 5 with their base ends abutting each other. . Felt holders 2A and 2B are attached to the tip ends of the ink holders 6A and 6B, respectively, and hold the felts 3A and 3B. Liquid ink 1
A and 1B are sucked up by the felts 3A and 3B by a capillary phenomenon, and can be written on the paper at the tips of the felts 3A and 3B. At both ends of the body 5, felt 3
To prevent A and 3B from drying, cap 4
A and 4B are fitted.

The ab type erasing pen shown in FIG. 1B has the following structure. The erasing liquids 1a and 1b are housed in ink holders 6a and 6b, respectively, and these ink holders 6a and 6b are integrally held in a cylindrical body portion 5 with their base ends abutted against each other. . Felt holders 2a and 2b are attached to the tip ends of the ink holders 6a and 6b, respectively, and hold the felts 3a and 3b. The erasing liquids 1a and 1b are sucked up by the felts 3a and 3b due to the capillary phenomenon, and can be applied on the paper at the tip ends of the felts 3a and 3b. Caps 4a and 4b are fitted on both ends of the body 5 in order to prevent the felts 3a and 3b from drying.

The image drawn using the liquid ink 1A of the AB type marker shows the erasing liquid 1a of the ab type marker,
It can also be erased using 1b. An image drawn using the liquid ink 1B of AB type marker cannot be erased by the alcohol type erasing liquid 1a of the ab type marker, but can be erased by the ketone type erasing liquid 1b.

An example of how to use these markers and erasing pen will be described. For example, a draft of a document is created using the liquid ink 1B of the marker, and the draft is added using the liquid ink 1A of the marker. When this alcohol-based erasing liquid 1a is applied by rubbing this paper with felt 3a, liquid ink 1
It is possible to erase only the touched portion by A, and the draft by the liquid ink 1B is not erased. Since the rewriting can be performed again after the erasing of the retouching portion, no stain remains even if the retouching is corrected. Further, when the paper is rubbed with the felt 3b and the ketone-based erasing liquid 1b is applied, the draft and the writing portion can be collectively erased, so that the paper can be reused.

FIG. 2A is an Aa type marker / erasing pen in which a marker portion using the liquid ink 1A and an erasing portion using the alcohol-based erasing liquid 1a are combined, and FIG.
(B) is a Bb type marker / erasing pen in which a marker portion using the liquid ink 1B and an erasing portion using the ketone erasing liquid 1b are combined. Each of these can be used alone for writing and erasing. 2A, the Aa type marker / erasing pen shown in FIG. 2A is used for correction and the Bb type marker / erasing pen shown in FIG. 2B is used for draft / collective erasing. Can be used.

Example 2 1 part by weight of crystal violet lactone (CVL) as a color-developing compound and 2,3,4,4'- as a color developer.
2 parts by weight of tetrahydroxybenzophenone, 10 parts by weight of cholic acid as a decoloring agent, 5 parts by weight of an ester wax as a wax are added to 45 parts by weight of water, and further 5 parts by weight of polyvinyl alcohol and 0.1% of quillaja saponin as a surfactant. Parts by weight were added. After sufficiently stirring this dispersion at 75 ° C., it is gradually cooled to prepare an erasable aqueous ball-point pen ink 1A.

1 part by weight of crystal violet lactone (CVL) as a color developing compound, 1 part by weight of propyl gallate as a developer, and 10 parts by weight of cholic acid as a decolorizer.
5 parts by weight of a styrene / acrylate copolymer having an acrylate content of 5% as a resin and 35 parts by weight of toluene as a main solvent are mixed and sufficiently stirred using a paint shaker to prepare an erasable oil-based ballpoint pen ink 1B. .

On the other hand, as in Example 1, an erasing liquid 1a containing isopropyl alcohol as a main component and an erasing liquid 1b containing methyl ethyl ketone (MEK) as a main component were prepared. The alcohol-based erasing liquid 1a is a ballpoint pen ink
Can be erased, but the ballpoint pen ink 1B cannot be erased. The ketone-based erasing liquid 1b can erase both the ballpoint pen ink 1A and the ballpoint pen ink 1B.

Using these ballpoint pen inks 1A and 1B and the erasing liquids 1a and 1b, the Aa type ballpoint pen / erasing pen shown in FIG. 3A and the Bb type ballpoint pen / erasing pen shown in FIG. 3B are produced.

The Aa type ballpoint pen / erasing pen shown in FIG. 3A has the following structure. Ballpoint pen ink 1
A is stored in the ink core 8A. The base end of the ink core 8A has an ink core bearing 9 provided in the cylindrical body 5.
The pen tip holder 7A attached to the body 5 holds the tip of the pen tip holder 7A. The ink 1A is transferred onto the paper with the rotation of the ball 10A at the tip of the ink core 8A, and writing is performed. The erasing liquid 1a is housed in an ink holder 6a, and the ink holder 6a has a cylindrical body portion 5a.
Is held by. The felt holder 2a is attached to the tip of the ink holder 6a and holds the felt 3a. The erasing liquid 1a is felt 3 due to the capillary phenomenon.
It is sucked up by a and can be applied on the paper at the tip of the felt 3a. Caps 4A and 4a are fitted on both ends of the body 5 to prevent the tip of the ballpoint pen and the felt 3a from drying.

The Bb type ball-point pen / erasing pen shown in FIG. 3 (B) has the same structure as that of FIG. 3 (A) except that the ball-point pen ink 1B and the erasing liquid 1b are used.

The ball-point pen / erasing pen shown in FIGS. 3A and 3B can be used similarly to the marker / erasing pen shown in FIGS. 2A and 2B. Example 3 1 part by weight of crystal violet lactone (CVL) as a color-developing compound and propyl gallate 1 as a developer
By weight, 10 parts by weight of cholic acid as a decoloring agent, 33 parts by weight of 1-docosanol as a wax, and 5 parts by weight of stearyl alcohol are mixed and sufficiently kneaded at 100 ° C. to prepare a solid image-forming material. Pour this solid image-forming material into a mold to make a crayon 13A or colored pencil lead 1.
Process to 3A. The core 13A of the colored pencil is embedded in the wooden shaft to produce the colored pencil 14A.

FIG. 4A shows a crayon / erasing pen.
As shown in this figure, the crayon 13A is held in the cylindrical body portion 5, and is detachably fixed at the tip of the body portion 5 by a fixing tool 12 and a fastening tool 11. The structure on the side of the erasing pen using the alcohol-based erasing liquid 1a is the same as that of the above-described embodiments, and thus the description thereof is omitted. Figure 4
FIG. 4B is a colored pencil / erasing pen, which has the same structure as that of FIG. 4A except that a colored pencil 14A is detachably fixed instead of the crayon 13A. These crayons /
The erasing pen and the colored pencil / erasing pen can also be independently written and erased.

Crayon 13A or lead 1 of colored pencil
The decoloring agent may be removed from the image forming material used in 3A, and a decoloring agent such as soluble starch may be added to the alcohol-based erasing liquid 1a.

FIG. 5 shows a fountain pen / erasing pen, and FIG.
Crayon 13A of (A) or colored pencil 14 of FIG. 4 (B)
Instead of A, a fountain pen 15 is detachably fixed.
The fountain pen 15 has the same liquid ink 1A as that of the first embodiment stored in an ink cartridge 16.

In any of the examples, a writing part using an image forming material containing a matrix agent having a high affinity for a ketone or ether erasing liquid and an erasing part using a ketone or ether erasing liquid are combined. May be.

Example 4 FIGS. 6 and 7 show two types of erasable liquid ink 1A,
1B and two types of erasing liquids 1a and 1b are used to produce ballpoint pens 20A and 20B and erasing pens 21a and 21b, respectively, and an integrated ballpoint / erasing pen is shown.

FIG. 6 shows a BAab type ballpoint pen / erasing pen. In this structure, the base end side of the ballpoint pen 20B also serves as the cap of the inner ballpoint pen 20A, and the erasing pen 21
The base end side of b also serves as the cap of the inner erasing pen 21a.

FIG. 7 shows a BbaA type ballpoint pen / erasing pen. In this structure, the base end side of the ballpoint pen 20B also serves as the cap of the inner erasing pen 21b,
The base end side of A also serves as the cap of the inner erasing pen 21a.

Embodiment 5 FIG. 8 shows a modification of the erase pen. This erasing pen is structurally the same as that in FIG. 1B, and the point that the alcohol-based erasing liquid 1a is used in one erasing pen is also the same as in FIG. 1B, but in the other erasing pen. This is different from FIG. 1B in that an erasing liquid 1c made of a non-polar aromatic solvent is used instead of the ketone erasing liquid. The non-polar aromatic solvent used in the erasing liquid 1c has the property of being able to swell the matrix agent having a low affinity for the alcohol erasing liquid.

Using the erasing pen of FIG. 8, even with an image forming material which cannot be erased only with the alcohol erasing liquid 1a, the matrix agent is first swollen with the erasing liquid 1c made of a non-polar aromatic solvent, and then the alcohol erasing is performed. Erasing becomes possible by using the liquid 1a.

[0060]

As described above in detail, when the writing / erasing tool of the present invention is used, an image is formed by appropriately combining an erasable image forming material and its erasing liquid, and then a part of the image is formed. Can be selectively erased, or all images can be erased collectively. Therefore, the paper can be reused many times, and the paper resources can be efficiently used.

[Brief description of drawings]

FIG. 1 is a diagram showing an AB type marker and an ab type erasing pen according to the present invention.

FIG. 2 is a diagram showing an Aa type marker / erasing pen and a Bb type marker / erasing pen according to the present invention.

FIG. 3 is a diagram showing an Aa type ballpoint pen / erasing pen and a Bb type ballpoint pen / erasing pen according to the present invention.

FIG. 4 is a diagram showing a crayon / erasing pen and a colored pencil / erasing pen according to the present invention.

FIG. 5 is a diagram showing a fountain pen / erasing pen according to the present invention.

FIG. 6 is a diagram showing a BAab type ballpoint pen / erasing pen according to the present invention.

FIG. 7 is a diagram showing a BbaA type ballpoint pen / erasing pen according to the present invention.

FIG. 8 is a diagram showing a modification of the erase pen according to the present invention.

[Explanation of symbols]

1A, 1B ... Liquid ink 1a, 1b, 1c ... Erasing liquid 2A, 2B, 2a, 2b, 2c ... Felt holder 3A, 3B, 3a, 3b, 3c ... felt 4A, 4B, 4a, 4b, 4c ... Cap 5 ... Body 6A, 6B, 6a, 6b, 6c ... Ink holder 7A, 7B ... Nib holder 8A, 8B ... Ink core 9A, 9B ... Ink core bearing 10A, 10B ... Ball 11 ... Fastener 12 ... Fixing tool 13A ... Crayon or colored pencil lead 14A ... Colored pencils 15 ... Fountain pen 16 ... Ink cartridge 20A, 20B ... Ballpoint pen 21a, 21b ... Erase pen

Continuation of the front page (56) Reference JP-A-10-6687 (JP, A) JP-A-2000-19769 (JP, A) JP-A-2000-109896 (JP, A) (58) Fields investigated (Int.Cl) . ⁷ , DB name) B43K 8/02-8/24 B43K 27/08 B43K 29/20 C09D 11/06

Claims (7)

(57) [Claims] 1. A color-developing compound, a color-developing agent, a first matrix agent, and a color-developing compound-developing agent by preferentially adsorbing one of the color-developing compound and the color-developing agent. A first writing part using an erasable first image forming material containing a decolorizing agent having an effect of reducing the interaction and decoloring, and a color developable compound, a color developing agent and a second matrix agent. And an eraser containing a decolorizer having the action of preferentially adsorbing one of the color-developable compound and the color-developing agent to reduce the color-development compound-developing agent interaction to erase the color. And a second writing section using a possible second image forming material. 2. The decolorizing agent comprises (a) a sterol compound, (b) cholic acid, lithocholic acid, testosterone and cortisone and their derivatives, and (c) (c1) a cyclic sugar alcohol and (c2) ring. Non-aromatic cyclic compounds having 5 or more membered rings having hydroxyl groups other than formula sugar alcohols or derivatives of cyclic sugar alcohols,
(D) starch, of cellulose and cellulose derivatives (a), (b), 請, characterized in that at least one selected from the group consisting of (c) and (d)
The writing instrument according to claim 1 . 3. A color-developing compound-developing agent by preferentially adsorbing one of the color-developing compound, the color-developing agent, the first matrix agent, and the color-developing compound and the color-developing agent. A first writing part using an erasable first image forming material containing a decolorizing agent having an action of reducing the interaction to decolorize, a color developable compound, a color developing agent and a second matrix agent. And an eraser containing a decolorizer having the action of preferentially adsorbing one of the color-developable compound and the color-developing agent to reduce the color-development compound-developing agent interaction to erase the color. An erasing tool for erasing an image written by a writing tool having a second writing part using a possible second image forming material, having an affinity for swelling or dissolving the first matrix agent, The affinity for the second matrix agent is the first The first lower affinity for the matrix agent
And a second erasing unit using a second erasing liquid having an affinity for swelling or dissolving the first and second matrix agents. Erase tool. 4. The erasing tool according to claim 3 , wherein the erasing liquid further contains a decoloring agent. 5. The decolorizing agent comprises (a) a sterol compound, (b) cholic acid, lithocholic acid, testosterone and cortisone and derivatives thereof, and (c) (c1) cyclic sugar alcohol and (c2) ring. Non-aromatic cyclic compounds having 5 or more membered rings having hydroxyl groups other than formula sugar alcohols or derivatives of cyclic sugar alcohols,
(D) starch, of cellulose and cellulose derivatives (a), (b), 請, characterized in that at least one selected from the group consisting of (c) and (d)
The eraser according to claim 4 . 6. A color-forming compound, a color developer, a matrix agent,
And one of the color-forming compound and the color developer
Are preferentially adsorbed to cause the interaction between the color-developing compound and the color-developing agent.
Decolorizing agent containing a decoloring agent having a function of reducing and decoloring
It has the affinity to swell or dissolve the matrix agent with the writing part using removable image forming material.
And an erasing section using an erasing liquid
Writing / erasing tool. 7. A color-forming compound, a color-developing agent, and a first matrix.
Agent, and the color-forming compound and the developer
One of them is preferentially adsorbed and the other of the color-developing compound-developing agent
Contains a decolorizer that has the effect of reducing the effect and decoloring
Writing using an erasable first image forming material
Part, color-developing compound, color developer, second matrix agent, and
Priority given to one of the color-forming compound and the color developer
To reduce the color-developing compound-developer interaction.
Erasable by containing an erasing agent that has the effect of erasing
A second writing part using the second image forming material and an affinity for swelling or dissolving the first matrix agent.
And has an affinity for the second matrix agent.
A first having a lower affinity for the first matrix agent
Swelling or dissolving the first erasing part using the second erasing liquid and the first and second matrix agents.
Second erasing using a second erasing liquid having affinity for
A writing / erasing tool having a section.