JPH089705B2 - Reversible thermosensitive recording material Writing ink - 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 ink for writing on an image-forming heat-sensitive recording material, and more particularly to a reversible heat-sensitive recording material capable of forming and erasing an image by the difference in thermal energy. For ink.

[0002]

2. Description of the Related Art Reversible thermosensitive recording materials have hitherto been disclosed in JP-A-58-191190, JP-A-60-193691, JP-A-3666666 and JP-A-54-119377.
JP-A No. 63-39377, JP-A No. 63-41186, JP-A No. 4-30916, and International Publication WO 90/11898. Furthermore, from the applicant of this patent, Japanese Patent Application No. 3-255401, Japanese Patent Application No. 4-54625, Japanese Patent Application No.
62740, Japanese Patent Application No. 4-201264, Japanese Patent Application No. 4-244654, etc. have been filed.

All of these techniques relate to a reversible heat-sensitive recording material capable of printing by heating for a short time by a heat-sensitive recording head and erasing by heating for a relatively long time by a heat roll or the like. . One application of these reversible thermosensitive recording materials is a recording medium that can be repeatedly used in thermal printers such as personal computers and word processors. Such a recording medium is convenient for checking the input, but if you correct the corrected part after printing with a normal writing instrument, the added part cannot be erased and the medium cannot be reused. There was a problem. Further, since it requires heating for a short time of several milliseconds or less for printing, it is impossible to use a hot pen.

[0004]

As described above, a means which can be added to a reversible thermosensitive recording material after printing on the reversible thermosensitive recording material for the purpose of correction, etc., and which can be easily erased, has been heretofore known. It wasn't issued.

An object of the present invention is to solve the problems of the above-mentioned prior art, to perform rewriting on a reversible thermosensitive recording material after printing, and to erase the printed portion and the retouched portion at the same time. An object of the present invention is to provide an ink for writing reversible heat-sensitive recording material.

[0006]

Means for Solving the Problems The above-mentioned object is an ink in which an amine complex salt of an organic acid and a leuco dye are dissolved in an organic solvent, and a handwritten character written with the above ink after heat-sensitive recording of a reversible heat-sensitive recording material is used. This can be achieved by using a reversible thermosensitive recording material writing ink, which is an ink that can be erased by heating together with a thermosensitive recording image.

Examples of the organic acid include 2-bis (p
-Hydroxyphenyl) acetic acid can be used.

The amine compound forming a complex salt with the above organic acid is a compound containing one or more amino groups in the molecule and forms a complex salt with the above organic acid.
Among these compounds, particularly excellent decoloring properties can be obtained when the following compounds are used.

(A) A linear or branched alkylamine having an alkyl group having 8 or more carbon atoms, such as octylamine, decylamine, laurylamine, tetradecylamine, cetylamine, stearylamine, 4,4-
Dipropyloctylamine, 5-ethyldodecylamine, 2,6-diethyldecylamine, 2,4,6-tributyloctylamine, etc.

(B) An ether-containing alkylamine having a linear or branched alkyl group containing an ether bond,
For example, methoxypropylamine, ethoxypropylamine, 2-ethylhexaoxypropylamine, dodecyloxypropylamine and the like.

(C) Thioether-containing alkylamines having a linear or branched alkyl group containing a thioether bond, such as metathioxypropylamine, ethatioxypropylamine, 2-ethylhexyltioxypropylamine, dodecyltioxy. Propylamine etc.

(D) Secondary or tertiary amines, for example,
Dioctylamine, N-ethyldecylamine, N, N-methylhexadecylamine, tributylamine, etc.

The above leuco dyes include, for example, crystal violet lactone, 3-indolino-3-p-dimethylaminophenyl-6-dimethylaminophthalide, 3-diethylamino-7-chlorofluorane,
2- (2-fluorophenylamino) -6-diethylaminofluorane, 2- (2-fluorophenylamino) -6-di-n-butylaminofluorane, 3-diethylamino-7
-Cyclohexylaminofluorane, 3-diethylamino-5-methyl-7-t-butylfluorane, 3-diethylamino-6-methyl-7-p-butylanilinofluorane, 3-cyclohexylamino-6-chlorofluorane ,
2-anilino-3-methyl-6- (N-ethyl-p-toluidino) fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-7-cyclohexylaminofluorane, 3-N -Methylcyclohexylamino-6
-Methyl-7-anilinofluorane, 3-N-ethylbenzylamino-6-methyl-7-anilinofluorane and the like can be mentioned.

The organic solvent may be a single solvent such as alcohols, ketones, benzene, toluene and xylene, or a mixture of some of these.

As the writing instrument, any felt pen, hollow pen, fountain pen, pen, etc. can be used as long as it can use liquid ink.

[0016]

[Function] A mixture of a complex salt of an organic acid and an amine compound and a leuco dye has a property of developing color by heating for a short time and decoloring by heating for a relatively long time, and the mixture is dispersed in a resin. Thus, a technique for forming a reversible heat-sensitive layer of a reversible heat-sensitive recording material exists as a conventional technique. When dissolved in a solvent that can dissolve both the complex salt and the leuco dye, these components undergo a chemical reaction at room temperature to form a colored state, and writing can be performed using this colored solution as an ink. When the medium thus written is heated for a relatively long time through a heating roll or the like, the written portion is discolored and the trace of the writing disappears. Therefore, even if writing is performed on the surface of the reversible thermosensitive recording material on which printing is performed, the written portion is erased together with the printed portion in the process of erasing the color.

By selecting the type of leuco dye, black, blue, red, green, etc. inks can be obtained.

[0018]

EXAMPLES The reversible thermosensitive recording material writing ink of the present invention will be specifically described below with reference to examples.

First, both solutions A and B having the following composition were prepared, and then 1 part of solution A and 3 parts of solution B were mixed and coated on a white polyester film and dried to prepare a reversible thermosensitive recording sheet. .

Liquid A 2-Amino-3-methyl-6-dibutylaminofluorane: 6 parts Acrylic resin (Dianal BR-106 made by Mitsubishi Rayon): 3 parts Toluene: 21 parts Liquid gallic acid / stearylamine (complex salt) )… 9 parts Acrylic resin (Mitsubishi Rayon's Dianal BR-106)… 3 parts Toluene… 38 parts This reversible thermosensitive recording sheet can print on a normal thermal printer in the same way as thermal paper, and 100 to 120 The printed portion can be erased by passing it through a hot roll heated to ° C.

Next, the ink for writing according to the present invention having the following composition was prepared.

2-bis (p-hydroxyphenyl) acetic acid / laurylamine (complex salt) 3 parts 3- (isobutylethylamino) -6-methyl-7-p-butylanilinofluorane 1 part methanol 27 parts 2-butanone ... 9 parts 2-bis (p-
Hydroxyphenyl) acetic acid laurylamine and 3- (isobutylethylamino) -6-methyl-7-p-butylanilinofluorane are dissolved to obtain a dark brown solution. This solution can be written using a hollow pen, a pen, a fountain pen, a felt pen, or the like.

Here, after printing on the reversible thermosensitive recording sheet by using a thermal printer (AP-850 manufactured by Seiko Epson Corporation), writing is carried out by a hollow pen containing the above-mentioned writing ink of the present invention. It was possible to edit with a clear black color. By passing this through a hot roll at 110 ° C., it was possible to erase not only the printed portion but also the added portion.

In addition to the above, heat-sensitive materials such as reversible heat-sensitive recording materials utilizing reversible reactions of various leuco dyes and reversible heat-sensitive recording materials of a type in which low molecules are dispersed in a polymer are used. Anything can be written and erased as long as it can be printed by a recording head and erased by a hot plate or a heat roll.

In the above example, the case where 3- (isobutylethylamino) -6-methyl-7-p-butylanilinofluorane was used as the leuco dye of the writing ink was explained. By using the leuco dye, inks of various colors can be obtained.

Red: 3-Diethylamino-7-methylfluorane Blue: Crystal violet lactone Green: 3-Ethylhexylamino-7-anilinofluorane

[0027]

As described above, by using the reversible thermosensitive recording material writing ink as the ink having the constitution of the present invention, the problems of the prior art can be solved and a reversible thermosensitive recording material can be obtained. It was possible to provide a reversible thermosensitive recording material-addition ink capable of performing addition after printing and erasing the printed portion and the added portion at the same time. As a result, it becomes possible to add and correct a document printed with a reversible thermosensitive recording material, and it becomes possible to make the correction easy to understand when it is used for test printing of a personal computer, a word processor or the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Daiji Sugiuchi 3819 Noborito, Tama-ku, Kawasaki-shi, Kanagawa Sliontec Co., Ltd. (72) Inventor Rinko Takayama 3819, Noboto, Tama-ku, Kawasaki, Kanagawa (72) ) Inventor Kazuyoshi Yatsuka 3819 Noborito, Tama-ku, Kawasaki City, Kanagawa Prefecture Sliontech Co., Ltd.

Claims (1)

[Claims] 1. An ink comprising an amine complex salt of an organic acid and a leuco dye dissolved in an organic solvent, wherein the organic acid of the amine complex salt of the organic acid is 2-bis (p-hydroxyphenyl) acetic acid. The amine compound forming a complex salt with is a compound containing one or more amino groups in the molecule, and (a) a linear or branched alkylamine having an alkyl group having 8 or more carbon atoms or (b) an ether bond. An ether-containing alkylamine having a linear or branched alkyl group containing (c) a thioetheralkylamine containing a linear or branched alkyl group containing a (iii) thioether bond, or (d) a secondary or tertiary amine, which is reversible Reversible thermosensitive recording, characterized in that after the thermosensitive recording of the thermosensitive recording material, the handwritten character using the ink is an ink that can be erased by heating together with the thermosensitive recording image Ink for recording materials.