JPS6123119B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a writing instrument that can write or print in multiple colors by applying direct current to ink. Conventionally, in order to write or print in multiple colors, it is common to prepare writing instruments that can write or print in each color depending on the purpose of use (color tone), and use each writing instrument while selecting the appropriate one. This is the usage form. As a special example, there is a usage form in which multiple colored inks are built into one writing instrument, and writing or printing in the desired tone is done with different pens depending on the purpose of use. Incorporating this requires a complicated structure, and furthermore complicates writing or printing operations. For these reasons, it has been a long-held dream to develop a writing instrument that can write or print in multiple colors with a simple operation. As a result of continuing research from this point of view, the inventor of the present invention used a material that exhibits a color change through an electrochemical redox reaction as an ink component. It has been discovered that by configuring a writing instrument so that it can conduct electricity, and passing a direct current through the ink to change the color of the ink, it is possible to write or print in multiple tones. That is, the present invention provides a writing section, an ink passage through which ink flows into the writing section, and at least one material that undergoes an electrochemical redox reaction and exhibits a color change.
An ink storage section containing an ink containing a different type of ink or a supporting electrolyte is provided, an electrode is installed in the ink passage corresponding to the writing section, and a direct current is applied to the ink between the writing section and the electrodes. This is a writing instrument characterized by changing the color of the ink. In the writing instrument of the present invention, in order to apply direct current to the ink, the writing part can also serve as the anode or cathode of the electrode, the direct current can be installed in the writing instrument, or it can be installed outside the writing instrument. Power may be supplied to both poles via lead wires. The color tone of the ink used in the present invention can be changed by changing the polarity of the electrodes and by changing the voltage applied. You may change it more than that. Next, a material that electrochemically undergoes a redox reaction and exhibits a color change, which is a feature of the writing instrument of the present invention, and an ink containing the material will be described. The following materials can be used for the aforementioned materials: (1) Bipyridinium compounds and related compounds Here, R ₁ , R′ ₁ , R″ ₁ , R ₂ , R″ ₂ are H, alkyl group (carbon number: 1 to 12), phenyl group, benzyl group, and X ^- is Cl ^- , Br ^- , F ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , NO ₃ ^-
etc. Here, R ₁ and R ₂ are H, alkyl group (number of carbon atoms:
1 to 12), phenyl group, benzyl group, and X ^- is
These include Cl ^- , Br ^- , F ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , NO ₃ ^- and the like. (2) Styrylpyridine compound Here, R is an alkyl group (carbon number: 1 to 12)
So, X is Cl, Br, F, I, salicylic acid, para-aminosalicylic acid, and Z is

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[Formula] etc. (3) Tetrazolium salts Tetrazolium blue, nitrotetrazolium blue, TC-nitro-tetrazolium blue,
Neo-tetrazolium blue, dotite INT,
Dotite MTT, tetranitrotetrazolium blue, blue tetrazolium, tetrazolium violet, 2,3,5-triphenyltetrazolium chloride (all trade names manufactured by Dojin Pharmaceutical Chemical Research Institute, Ltd.) (4) Metal indicators Dotite berylon -, Dotite BPR, Dotite BT, Dotite Calcichrome, Dotite Chalcone, Dotite Calmagite, Dotite Chromazurol S, Dotite Sulfonado -
, dotite dinitrohydroxyazo, dotite di-SNADNS-4, dotite GCR,
Dotite GTB, Dotite HABT, Dotite HNB, Dotite Mogallion, Dotite
MTB, dotite tomlexide, dotite
PACH, Dotite PAN, Dotite PPC, Dotite PR, Dotite PV, Dotite SCR, Dotite α-SNADNS-4, Dotite
SPADNS, dotite stilbazo, dotite sulfoazo, dotite XO, dotite variamine blue 13 hydrochloride (all trade names manufactured by Jinyaku Chemical Co., Ltd.) (5) Acid-base indicators Methyl violet, methyl violet
6B, metanyl yellow, thymol blue, metacresol purple, trapeoline-OO, alizarin yellow R, methyl yellow, bromphenol blue, congo red, methyl orange, methyl red, bromcresol green, lacmoid, bromcresol purple, alizarin, bromthymol blue, phenol red Redox indicators Safranine, indigo carmine, methylene blue, 2,4-diaminodiphenylamine, diphenylamine, xylene cyanol FF, erioglaucine A, Setoglaucine O, Amaranth,
Benzopurpurin 4B, etc. (7) Organic dyes Basic dyes, acid dyes, acid mordant dyes, direct dyes, etc. For example, crystal violet, methyl violet, Briant green, primocyanine 6GX, methylene blue, methylene brown, methylene green, malachite green, quinaldine blue, pinacyanol chloride, naphthol yellow S, quinoline yellow, indigo carmine, lissamine green. V, amaranth,
Naphthol Blue Black B, Brilliant Blue FCF, Eriochrome Black T, Eriochrome Gray SGL, Alizarin Red S, Brilliant Yellow, Brilliant Blue 6BX, Erythrosine B, Patent Blue, Patent Blue A, Orange, Auramine O, Safranin T, Chrysoidin FB, rhodamine B, benzopurpurin
4B, Congo Red, Curcumin S, Chalcon, Eriochrome Blue SE, Chrome Red B,
Alizarin Yellow R, Indigosol O, Orange, Xylene Cyanol FF, Lacmoid,
Alizarin yellow GG etc. (8) Metal chelate compounds A Ligand components
N'-dibenzyloxamide) Thiazoles (2-mercaptobenzothiazole) Aromatic thiophenols (Toluene-3,4-
dithiol) β-diketones (acetylacetone, benzoylacetone) Aromatic monohydroxy compounds (salicylic acid,
sulfosalicylic acid) Aromatic polyhydroxy compounds (resorcinol,
Catechol, gallic acid, dihydrocybenzenesulfonic acid, chromotropic acid, dihydroxynaphthalenesulfonic acid, alizarin, quinizarin, quinalizarin) Oximes (α-acroinoxime, α-benzoinoxime) Guanidines (guanidine, diphenylguanidine) α -Dioximes (dimethylglyoxime, α
-benzylglyoxime, α-furyloxime, ethylmethylglyoxime) Pyridines (α,α′-dipyridyl, o-phenanthroline, 4,7-diphenyl-1,10-
Phenanthroline, 4,7-dihydroxy-
Oxines (8-hydroxyquinoline, dichloro-8-hydroxyquinoline, dibromo-8-hydroquinoline) Oxines (salicylaldoxime) , α-benzoin oxime) Amino acids (glycine, glycylglycine, alanine, valine, leucine, lysine, methionine, serine, threonine), etc. B Metal components aluminum, barium, calcium, cobalt, copper, gallium, germanium, indium, iron , magnesium, manganese, molybdenum, nickel, titanium, tungsten, vanadium, zinc, zirconium, etc. Here, the metal chelate compound is a compound obtained from the ligand component A and the metal component B. The above examples are merely examples of materials that undergo electrochemical redox reactions and exhibit color changes; in short, any material that exhibits such a phenomenon may be used. The material is dissolved in water, an organic solvent, or a mixture thereof to form an ink. In this case, the material is dissolved in a solvent at a concentration of several percent or less,
The electrical conductivity is preferably about 10 millimoh/cm or more.
In general, when using ink with an electrical conductivity of about 10 millimos/cm or more, the power supply voltage for color change can be operated at a low voltage of 20 to 30 V or less, which is safe for the human body and requires less energy. etc., the practical value is greatly improved. The color tones of handwriting before and after energization of ink using representative compounds among the above compounds are shown below.

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[Table] Next, the ink in which the supporting electrolyte is dissolved, which is another feature of the writing instrument of the present invention, will be explained. As mentioned above, when the electrical conductivity of the ink is 10 mmoh/cm or less, it is necessary to increase the electrical conductivity of the ink to 10 mmoh/cm or more by dissolving the supporting electrolyte. Here, the supporting electrolytes include the following, including organic and inorganic ones.
NaCl, KCl, LiCl, KBr, KCNS, LiAlCl ₄ ,
LiClO ₄ , NaClO ₄ , LiBF ₄ , KPF ₆ , Na ₂ SO ₄ ,
(CH ₃ ) ⁴ NCl, (CH ₃ ) ₄ NBr, (CH ₃ ) ₄ NI,
(C ₂ H ₅ ) ₄ NCl, (C ₂ H ₅ ) ₄ NBr, (C ₂ H ₅ ) ₄ NI,
(C ₃ H ₇ ) ₄ NCl, (C ₃ H ₇ ) ₄ NBr, (C ₃ H ₇ ) ₄ NI,
(C ₄ H ₉ ) ₄ NCl, (C ₄ H ₉ ) ₄ NBr, (C ₄ H ₉ ) ₄ NI,
TCNQ, Li ⁺ TCNQ〓, Quinolinium TCNQ〓・
TCNQ゜, (C ₄ H ₉ ) ₄ N ⁺・TCNQ〓・TCNQ゜,
(C ₄ H ₉ ) NClO ₄ , (C ₄ H ₉ ) ₄ NBF ₄ , polyacrylamide, polyvinylpyrrolidone, polyglycine, polyvinylimidazole, polyimidazole, polysodium methacrylate, polysodium acrylate, polyvinyl N-methylpyridinium Iodide et al. Incidentally, the ink may be prepared by blending one type of each of the above-mentioned materials, or may further be blended by combining several types of various materials. Any combination of materials may be used. The writing instrument of the present invention is used for handwriting, such as a fountain pen, a similar product, a pipe pen, a pipe pen, a pen for an industrial recorder, etc., and has a multicolor writing function. Next, embodiments of the writing implement of the present invention will be described. In the fountain pen type embodiment shown in FIG.
Fix the pen core 3 inside the neck tube 2 where the pen 1 is attached.
An ink groove 4 serving as an ink passage is located below the pen 1, and an electrode 5 made of platinum or the like is placed in the ink groove 4 facing the pen 1. A DC power source 9 such as a battery is connected to the shaft tube 7.
A switch 11 having an operating section 10 is attached to the outside, and the pen 1 and the electrode 5 are separately connected to the switch 11 via a lead wire 8, and the DC power source 9 is connected to the switch 11 via the lead wire 8. An ink cylinder 6 serving as an ink reservoir containing the ink 12 containing the material that undergoes the electrochemical redox reaction and exhibits a color change is attached to the open end of the pen core 3;
The ink 12 flows out of the ink groove 4 of the pen core 3.
When the switch 11 is turned on, a current flows between the pen 1 and the electrode 5 through the ink 12 existing between them, and the color tone of the ink 12 changes.
You can obtain handwriting with a different tone than before turning on. In the pipe _pen type of the _embodiment shown in FIG _.
An electrode ₅₁ made of platinum or the like exposed from the tip of the core ₃₁ is placed facing the pen ₁₁ . A DC power source ₉₁ such as a current is connected to the shaft cylinder ₇₁ and an operating unit 1 is provided externally.
Install switch 11 ₁ with 0 ₁ , pen 1 ₁
and electrode ₅₁ are separately connected to switch ₁₁₁ via lead wire ₈₁ , and DC power source ₉₁ is connected to switch ₁₁₁ via lead wire ₈₁ . The ink cylinder ₆₁ , which serves as an ink reservoir containing the ink 12 in the above embodiment, is attached to the open end of the core ₃₁ , and the ink 12 flows out through the ink groove ₄₁ , which serves as an ink passage in the core ₃₁ . . When the switch ₁₁₁ is turned on, current flows between the pen ₁₁ and the electrode ₅₁ through the ink 12 present therebetween. When the switch 11 ₁ is turned on, current flows between the pen 1 ₁ and the electrode 5 ₁ through the ink 12 existing between them, and the color tone of the ink 12 changes.
You can obtain handwriting with a different tone than before turning on ₁ . Next, an example of the use of the ink used in the present invention will be explained. Usage example 1 Dissolve 2.5 parts of sodium phosphomolybutate and 0.5 part of glycerin in 7 parts of water to make ink. The handwriting of this ink is yellow, but when a voltage of 2 volts is applied, the handwriting becomes blue. Usage example 2 EDTA-Na-Fe() 2 parts Sodium bathophenanthroline sulfonate
Dissolve 2 parts in 10 parts of water to make ink. The handwriting of this ink is pale yellow, but when a voltage of 1.5 volts is applied, the handwriting becomes red. Usage example 3: Dissolve 2 parts of Dotite SPADNS and 2 parts of KCl in 90 parts of water to make ink. The handwriting of this ink is red, but when a voltage of 5 volts is applied, the handwriting becomes purple. Usage example 4: Dissolve 2 parts of Dotite XO (CH ₃ ) ₄ NCl in 100 parts of water to make ink. The handwriting of this ink is orange, but when a voltage of 6 volts is applied, the handwriting becomes purple. Usage Example 5 Dissolve 2 parts of Dotite Chromazurol S (C ₂ H ₅ ) ₄ NCl in 100 parts of water to make ink. The handwriting of this ink is brown, but when a voltage of 6 volts is applied, the handwriting turns purple. Usage example 6 Dissolve 3 parts of orange, 2 parts of (CH ₃ ) NCl, and 3 parts of glycerin in 100 parts of water to make ink. The handwriting of this ink is orange, but when a voltage of 6 volts is applied, the handwriting becomes red. Usage example 7 EDTA-Na-Mn 2 parts Dotite Chromazurol S 2 parts KCl Dissolve 0.5 parts in 100 parts of water to make ink. The handwriting of this ink is maroon, but when a voltage of 8 volts is applied, the handwriting becomes red. Usage example 8 Dissolve 2 parts of Dotite GCR and 3 parts of aluminum alum in 100 parts of water to make ink. The handwriting of this ink is yellow-orange, but when a voltage of 6 volts is applied, the handwriting becomes red. Usage example 9 Dissolve 2 parts of Congo Red, 1 part of LiCl, and 2 parts of ethylene glycol in 95 parts of water to make ink. The handwriting of this ink is brownish-brown, but when a voltage of +12 volts is applied, the handwriting becomes black, and when the polarity is reversed and a voltage of -12 volts is applied, the handwriting becomes red. Usage example 10 Dissolve 2 parts of Chromazurol S (C ₂ H ₅ ) ₄ NBr 0.5 part and 1 part of diethylene glycol in 95 parts of water to make ink. The handwriting of this ink is purple, but when a voltage of +12 volts is applied, the handwriting becomes orange, and when the polarity is reversed and a voltage of -12 volts is applied, the handwriting becomes brown. Example 11 Ink is prepared by dissolving 2 parts of pyrocathule violet, 1 part of LiCl, and 2 parts of ethylene glycol in 95 parts of water. The handwriting of this ink is brown, but when a voltage of +12 volts is applied, the handwriting becomes brown, and when the polarity is reversed and a voltage of -12 volts is applied, the handwriting becomes blue-black.

[Brief explanation of the drawing]

FIG. 1 shows a fountain pen type embodiment of the present invention, and FIG. 2 shows a pipe pen type embodiment of the present invention. 1,1 ₁ ...pen, 2,2 ₁ ...neck barrel, 3...
Pen core, 3 ₁ ... core, 4, 4 ₁ ... ink groove,
5,5 ₁ ...electrode, 6,6 ₁ ...ink cylinder, 7,
7 ₁ ... shaft cylinder, 8, 8 ₁ ... lead wire, 9, 9 ₁
...DC power supply, 11,11 ₁ ...Switch, 12
……ink.

Claims (1)

[Scope of Claims] 1. A writing section, an ink passage through which ink flows into the writing section, and an ink storage section containing ink containing at least one kind of material that undergoes an electrochemical redox reaction and exhibits a color change. A writing instrument further comprising an electrode installed in the ink passage corresponding to the writing section, and a DC electrode passing current through the ink between the section and the electrode to change the color of the ink. . 2. A writing section, an ink passage through which ink flows into the writing section, and an ink storage section containing ink containing at least one type of material that electrochemically undergoes a redox reaction and exhibits a color change and a supporting electrolyte. The writing instrument further comprises an electrode installed in the ink passage corresponding to the writing part, and a direct current is applied to the ink between the writing part and the electrode to change the color of the ink.