JP4428564B2 - Drawing material that applies colorant to develop color - Google Patents

Description

  This invention is called shade ink (invisible ink) among paints and paints, and when it is drawn, the color at the time of coloring cannot be imagined, and it is colorless or another color. The present invention relates to a drawing material that reveals the intended color.

  This invention is based on an analytical chemistry technique for detecting metal salts and the like by using a compound that forms a colored complex with a metal salt and colors the compound. In addition, analytical chemistry measurement methods that analyze water quality using a pH indicator whose color changes with pH are used as background technology, and these color reactions or discoloration reactions can be applied for drawing. In the background art, art materials (paints) such as dyes, pigments, paints, etc., which develop the color of the dark ink are used.

In a conventional drawing material called Yin-Shi ink, reaction of hexacyanoferrate (II) or sodium thiocyanate such as yellow blood soda that develops blue or red and a trivalent iron salt such as iron (III) chloride However, there was a drawback in that the color of red was close to brown and lacked in vividness, and the mark with iron chloride turned brown, and the appearance was not clean.
In addition, because there is no material that develops red or yellow color, it has the disadvantage that various colors cannot be created, and it has the feature that it is colored in red and yellow, and the traces of paint and coloring agent are not noticeably discolored. It was a problem to make a drawing material having the properties of shadow ink.
In addition, it is possible to make a drawing material with the properties of shaded ink that can be produced at a low cost by using a material that reacts with a strong color reaction at a very small amount, or a material that reacts with a strong color at a low price. It is a problem.

  In addition, in the art materials in the field of shade ink utilizing the discoloration of a pH indicator due to a conventional pH change, phenolphthalein that develops a color at a relatively high pH (colored red at a pH of 9 or more) or thymolphthalein (blue at a pH of 10 or more) Color development), and after color development, the pH gradually decreases due to the influence of pH buffer components contained in the paper and carbon dioxide (carbon dioxide) in the air, and the color disappears. It was. Further, in order to develop color, it is necessary to handle an alkaline substance having a high pH such as sodium hydroxide, and there is a drawback that the skin is roughened when the highly alkaline substance adheres to the skin. For this reason, it has been a problem to produce a drawing material having the properties of a shaded ink that can change color at a low pH, which is relatively neutral, and can maintain color development.

The present invention has been made in order to solve the above-mentioned problems. In [Claim 1], the following six types (1) to (6) are provided as basic coloring materials for drawing materials (paints and coloring agents). The use of all or part of the coloring reaction is described.
(1) Yellow color reaction by BiI4- ion generation between an iodide such as potassium iodide and a trivalent bismuth salt such as bismuth nitrate, bismuth sulfate or bismuth chloride contained in the color former. (2) Hexacyanoiron (II) salts such as yellow blood soda and yellow blood potassium, and trivalent iron such as iron sulfate (III), iron chloride (III), iron nitrate (III) contained in the color former Blue color reaction by formation of iron (III) hexacyanoferrate (II) (Prussian blue) with salt.
(3) Crimson color due to the formation of a red complex generated between dimethylglyoxime and a divalent nickel salt such as nickel nitrate (II), nickel sulfate (II) or nickel chloride (II) contained in the color former. Color reaction.
(4) Orange color of salicylic acid salts such as salicylic acid, sodium salicylate, potassium salicylate and trivalent iron salts such as iron (III) sulfate, iron (III) chloride, iron (III) nitrate contained in the color former. Color reaction. This reaction gives a magenta color reaction in an aqueous solution, but gives an orange color reaction when applied to paper.
(5) A red color reaction between aluminone and a trivalent iron salt such as iron sulfate (III), iron chloride (III), or iron nitrate (III) contained in the color former. This reaction gives a purple color reaction in an aqueous solution, but gives a very strong red color reaction when applied to paper. Alminone is widely used in the field of analytical chemistry for its red color reaction with trivalent aluminum salts, but as a color reaction, the reaction with trivalent iron salts shows a much stronger reaction. The application uses a reaction with a trivalent iron salt.
(6) Gray or near-black coloration of tannic acid or tannic acid salt and trivalent iron salt such as iron (III) sulfate, iron (III) chloride, iron (III) nitrate contained in the color former reaction. This reaction gives a strong blue-violet color reaction in an aqueous solution, but gives a gray or near-black color reaction when applied to paper.
Note that iodide, hexacyanoferrate (II), dimethylglyoxime, salicylic acid, salicylate, aluminone, tannic acid, and tannate do not cause a color reaction even when mixed with each other, so each is coated. Even if mixed, it does not develop color and can be mixed to produce these intermediate colors.
In addition, dimethylglyoxime and a complex with a divalent nickel salt such as nickel nitrate (II), nickel sulfate (II), nickel chloride (II) contained in the color former, or iron sulfate contained in the aluminum and color former Complexes with trivalent iron salts such as (III), iron chloride (III), iron nitrate (III) give the same red color, so when using aluminone for red color development and not using dimethylglyoxime, The divalent nickel salt on the color former side can be omitted.
These color reactions of (1) to (6) are those that give strong color development with very small amounts of each compound. Considering how to use paints and colorants, this application is intended to be used at low compound concentrations. It is a suitable combination. Further, in consideration of economics at the time of manufacturing the material, coloring can be performed with a small amount of material or an inexpensive material, and as a result, an inexpensive drawing material can be obtained.

  [0005] The yellow color reaction by BiI4- ion formation between the iodide shown in (1) of [0005] and a trivalent bismuth salt shows acidic and remarkable coloration, and the coloration becomes very light in alkaline. . Therefore, the color former of the present invention is devised so that a thin acid such as phosphoric acid or dilute sulfuric acid is added to become an acidic side during coating. However, depending on the material of the paper, the color tends to deteriorate due to the alkaline substance inside the paper, and in order to suppress the deterioration of the color development, as shown in [Claim 2], thiourea, sodium diethyldithiocarbamate or potassium diethyldithiocarbamate Yellow color reaction that occurs between thiourea and trivalent bismuth salt, yellow color reaction that occurs between diethyl dithiocarbamate and trivalent iron salt by adding diethyldithiocarbamate such as Is used as an auxiliary reaction for yellow color development.

The hexacyanoferrate (II) shown in (0005) of [0005] is easily yellowed by long-term storage, and leaves a yellow mark when the yellowed product is applied to paper. Therefore, in [Claim 3], as a measure for preventing this yellowing, a method of adding sulfite and / or diethyldithiocarbamate such as sodium diethyldithiocarbamate to an aqueous solution of hexacyanoferrate (II) showed that. Needless to say, storage in a light-shielding container such as a brown bottle is also effective for preventing yellowing.
The yellowing prevention effect of diethyldithiocarbamate is remarkable, and the hexacyanoferrate (II) aqueous solution once yellowed returns to a colorless and transparent solution when added. However, if too much is added, the blue reaction between hexacyanoferrate (II) and the trivalent iron salt will be hindered, resulting in a dull blue color due to the yellow color reaction. A small amount is used to return the resulting solution to colorless.

Red is created by mixing red and yellow, but this alone does not produce a deep red. Therefore, as shown in [Claim 4], the blue coloration of hexacyanoferrate (II) such as yellow blood soda is assisted, and the effect of reacting with iron (III) salt to strongly develop the deep blue color. Add a small amount of Tyrone, and add a deep blue color to the yellow color of dimethylglyoxime-nickel salt and the yellow color of iodide-bismuth salt to develop a deep red color.
Indigo can be created by adding a small amount of red to blue, but this alone does not produce deep indigo. Therefore, as shown in [Claim 4], the blue coloration of hexacyanoferrate (II) such as yellow blood soda is assisted, and the effect of reacting with iron (III) salt to strongly develop the deep blue color. A small amount of Tyrone is added, and this deep blue is added to the blue color of hexacyanoferrate (II) -iron (III) salt to develop indigo.

[0005] The red color reaction due to the formation of a red complex between dimethylglyoxime shown in (3) of [0005] and a divalent nickel salt is very difficult for water when dimethylglyoxime is neutral or more acidic than neutral. Due to the solubility, good color development is not shown unless it is slightly alkaline. Therefore, as shown in [Claim 5], as an auxiliary material for reliably causing a complex formation reaction with the nickel salt contained in the color former, a water-soluble carbonate such as potassium carbonate or sodium hydroxide can be used. All or any of the water-insoluble hydroxides, calcium carbonates and other water-insoluble carbonates are added to dimethylglyoxime. The color former contains a thin inorganic acid such as phosphoric acid or dilute sulfuric acid and is acidic, but when applied, it is difficult to dissolve in water-soluble carbonates, hydroxides and water mixed with dimethylglyoxime as a paint. The soluble carbonate reacts with the acid and remains weakly alkaline, preventing the precipitation of dimethylglyoxime as insoluble crystals in water, helping to form a red complex with the nickel salt. It should be noted that carbonates that are sparingly soluble in water such as calcium carbonate are used because when dimethylglyoxime and hexacyanoferrate (II) are mixed to develop a purple color, if the alkalinity becomes too strong, the blue color is developed. This is to prevent the phenomenon that the color becomes worse and purple is not produced. In addition, red, which is produced by mixing red and yellow, also has a purpose of preventing this phenomenon, as described in [0006], when yellow is inclined to alkalinity, the yellow color develops and becomes red.
In addition, the gray color reaction caused by the formation of a gray or near-black compound between tannic acid or tannic acid salt shown in (6) of [0005] and a trivalent iron salt produces a good color when it is not neutral or weakly alkaline. Not shown. Accordingly, as shown in [Claim 5], water-soluble carbonates such as potassium carbonate or water are used as auxiliary materials for reliably causing a gray compound formation reaction with the trivalent iron salt contained in the color former. All or any of water-soluble hydroxides such as sodium oxide and water-insoluble carbonates such as calcium carbonate are added to tannic acid or tannate.

Orange can be produced by mixing red and yellow. However, as described in [0009], red and yellow exhibit good color development in the opposite pH range, so that a strong orange of yellow on the paper surface is caused by uneven pH. A portion that develops color and a portion that develops strong orange in red tend to occur, which causes uneven color. In particular, the mixing ratio of orange is subtle. When a little red is strong, it turns red, and when a little yellow is strong, it turns yellow. .
The orange color reaction between the salicylate and the trivalent iron salt shown in (4) of [0005] is used for this purpose, and is used alone to give an orange color without mixing. As described above, this reaction is a red-purple color reaction in an aqueous solution, but becomes orange when applied to paper.

The color former is one of the six reactions shown in [0005], that is, a yellow color reaction by the formation of BiI4- ions between iodide and a trivalent bismuth salt, hexacyanoferrate with hexacyanoferrate (II) and a trivalent iron salt. Blue color reaction due to iron (II) acid iron (III) (Prussian blue) formation, red complex formation reaction generated between dimethylglyoxime and divalent nickel salt, salicylate and trivalent iron salt In order to cause an orange color reaction, a red complex formation reaction between aluminone and a trivalent iron salt, or a gray or near-black color reaction between tannic acid or tannate and a trivalent iron salt, A solution containing bismuth salt, trivalent iron salt, and divalent nickel salt is used. However, when only the reaction of aluminon and a trivalent iron salt is used for red color development and dimethylglyoxime is not used, the divalent nickel salt in the color former can be omitted.
Here, when these are simply dissolved in water, basic bismuth salts precipitate, and when applied to paper, brown substances such as iron hydroxide precipitate from iron (III) salts, resulting in a dirty paper surface. End up.
Therefore, [Claim 6] defines that phosphoric acid is added so that a brown product is not generated from the iron (III) salt. The surplus iron (III) salt that reacts with the salt of the paper and the sulfate radical or nitrate radical binds strongly to the phosphoric acid to become colorless iron phosphate, and does not stain the paper surface brown.
[Claim 7] describes that an inorganic acid such as dilute sulfuric acid is added as a measure for preventing the bismuth salt from easily forming a white precipitate as a basic bismuth salt. By making it acidic, the bismuth salt dissolves as a colorless solution and does not cause precipitation. Since the basic bismuth salt that has become a white precipitate does not contribute to the generation of yellow ions with iodide, it is necessary to prevent the bismuth salt from being precipitated.
Inorganic acids such as dilute sulfuric acid can also be nitric acid, hydrochloric acid, and phosphoric acid, but nitric acid has the effect of reacting with proteins such as the skin to turn brown and is highly dangerous and should be avoided. Hydrochloric acid contains chlorine ions, and iron (III) chloride reacted with iron (III) salt is stronger in yellow than iron (III) sulfate, so it was avoided in order to reduce the color when applied to paper. Better. If phosphoric acid is used extensively, it should be avoided because it interferes with the formation of iron (III) hexacyanoferrate (II) and Prussian blue and weakens the blue color. Accordingly, dilute sulfuric acid is most suitable as an acid to be added to prevent precipitation of bismuth salt. The dilute sulfuric acid concentration will be described later as an example, but a concentration of about 2% can be expected to sufficiently prevent precipitation of bismuth salt.

  Even when the method for preventing precipitation of bismuth salt described in [Claim 7] is used, a small amount of white precipitates are generated when stored for a long period of time, and there is no problem as a coloring action. Deteriorate. Thus, bismuth can be dissolved in glycerin and mixed with an acid such as phosphoric acid or dilute sulfuric acid, an iron (III) salt, or a nickel (II) salt immediately before use, so that it can be used without any precipitate. This method is described in [Claim 8].

[0005] The red color reaction by the formation of a red complex between aluminon and the trivalent iron salt shown in (5) of [0005] is good if it is not neutral or weakly acidic near neutrality or weakly alkaline near neutrality. Not shown. Therefore, as shown in [Claim 9], all of water-soluble hydrogen carbonates such as potassium hydrogen carbonate, water-soluble carbonates such as sodium carbonate, and water-insoluble carbonates such as calcium carbonate as auxiliary materials or Add either to the aluminon. The color former contains a thin inorganic acid such as phosphoric acid or dilute sulfuric acid and is acidic, but when applied, it is difficult to dissolve in water-soluble bicarbonate, water-soluble carbonate or water mixed with aluminon as a paint. The soluble carbonate reacts with the acid and keeps it weakly alkaline, helping the aluminum to form a red complex with the trivalent iron salt. The use of carbonates that are sparingly soluble in water, such as bicarbonate, carbonate and calcium carbonate, increases alkalinity when aluminium and hexacyanoferrate (II) are mixed to produce a purple color. This is for preventing the phenomenon that the color of blue is deteriorated and the color is not purple and becomes red. In particular, bicarbonate increases the concentration only to about 8.5 even when the concentration is increased, and is a material suitable for this application.
Aluminon is red when made into an aqueous solution, but the color becomes inconspicuous when applied to paper in a low concentration state, and the color becomes lighter when mixed with hexacyanoferrate (II).
Examples of the hydrogen carbonate include sodium hydrogen carbonate and ammonium hydrogen carbonate in addition to the potassium hydrogen carbonate described above. Examples of the water-soluble carbonate include carbonic acid other than the sodium carbonate described above. Examples of carbonates in which potassium, ammonium carbonate and the like are hardly soluble in water include magnesium carbonate in addition to the above-described calcium carbonate.

  [0005] The gray color reaction by the formation of a gray or near black compound between tannic acid and trivalent iron salt shown in (6) of [0005] is gray or near black because tannic acid alone is slightly blue. In order to make the color develop better, it is advisable to mix a yellowish iodide with tannic acid.

  In [0005] to [0014], yellow, blue, red, and orange coloring methods, which are basic colors, and red and indigo coloring methods using Tyrone have been described. It can be obtained by mixing the yellow color shown in [2] with the blue color shown in [Claim 1] and [Claim 3]. The purple color can be obtained by mixing the blue color shown in [Claim 1] and [Claim 3] with the red color shown in [Claim 1] and [Claim 5] or [Claim 9]. Obtainable. In addition, as shown in [0009], yellow is weakly acidic and well-colored, red is well-colored on the alkaline side rather than neutral, and blue is too strongly alkaline, and the colors are worsened. However, in order to suppress this and effectively produce each color, the inventions of [Claim 2], [Claim 5] and [Claim 9] have been devised.

[0005] From [0005] to [0015], the description of the part related to the claims of the coloring method using the reaction between a metal salt and a substance that causes a reaction such as formation of a colored complex has been described. If you think that you may develop a little yellow or red, the coloring method is a combination of a pH indicator that has a weak alkaline discoloration point and develops alkaline, yellow, blue, or red and a weakly alkaline coloring agent. Is also applicable. In the following [0016] to [0018], it is described as a method outside the claims that there is such another method.
In the case of such a method, for example, the following compounds having a slightly alkaline discoloration point of about pH 8.5 or below are combined, and at the time of application, very thin hydrochloric acid or the like is added to yellow or yellow as the acidic side below pH 7 Colored in red, and when applied with a weakly alkaline color former, it becomes alkaline with a pH of 7.5 or higher, and each color develops into strong yellow, blue, and red colors. Color can appear. (1) BTB: Yellow / green to blue color at pH 7.6 or higher.
(2) PR: yellow to red at pH 7.5 or higher, red color at pH 8.4 or higher.
(3) NR: Changed from red to yellow at pH 8.0 or higher.
(4) p-NP: Discolored from colorless to yellow at pH 7.0 or higher.
(5) m-NP: Discolored from colorless to yellow at pH 8.5 or higher.
The meanings of the above abbreviations are BTB: bromthymol blue, PR: phenol red, NR: neutral red, p-NP: p-nitrophenol, m-NP: m-nitrophenol.
In addition, although the very thin hydrochloric acid was illustrated as an acid added in order to make it acidity of less than pH 7 at the time of application | coating, this is thin phosphoric acid, thin sulfuric acid, thin nitric acid, a citric acid, an acetic acid, lactic acid, tartaric acid, oxalic acid, etc. However, it can be applied, but it is considered that hydrochloric acid is most suitable because most of the acid volatilizes when dried and the paint is in a neutral state.

  In the color development on the alkaline side of [0016], red and orange can be developed by mixing yellow and red at an appropriate ratio, and green and blue-green can be combined with red and blue by mixing yellow and blue. Indigo and purple can be adjusted by mixing. These mixtures do not react or affect each other and color development does not deteriorate.

An aqueous solution of potassium carbonate is most suitable as the weakly alkaline color former for coloring the paints shown in [0016] and [0017]. Potassium carbonate is widely known as a component of “Kansui” used as food, and even if it is used in a slightly concentrated aqueous solution of about 2%, it does not become highly alkaline and there is no problem in safety. Of course, if you put it in your eyes, nose, ears, wounds, etc., or drink it, it is natural that it is stained and painful due to the irritating nature of alkali, and you should not use it.
When an aqueous solution of potassium carbonate is applied to the paints shown in [0016] and [0017], it becomes alkaline at pH 8.5 or higher, and all the compounds shown in (1) to (5) of [0016] have passed the discoloration point. Color development on the alkaline side. Over time, alkalinity decreases due to neutralization of carbon dioxide in the air, but potassium carbonate reacts with carbon dioxide to become potassium hydrogen carbonate, where it loses hygroscopicity and carbon dioxide absorption stops. To do. The pH at this time is about 8.5, which is a pH that can maintain sufficiently alkaline color development. Therefore, there is little fading due to a change with time.
As the color former, an aqueous potassium carbonate solution is most suitable, but sodium carbonate is also suitable. Sodium hydroxide, potassium hydroxide, and the like are applicable, but are not recommended because they are more alkaline than carbonates such as potassium carbonate. Ammonium carbonate can also be used but is not recommended due to the smell of ammonia.
If phenolphthalein or thymolphthalein is used as the coloring compound as compared with the compound shown in [0016], these have a discoloration point in the pH range that cannot be developed with potassium carbonate. A compound having a higher pH, such as sodium oxide, must be used as a color former, but because of its high alkalinity, there is a higher risk to the human body, and if it adheres to the skin, it strongly Cause roughening. In addition, it absorbs carbon dioxide in the air and the pH tends to drop, and the color disappears immediately due to the discoloration point in the high pH range.

The drawing materials (paints and color formers) shown in [Claim 1] and the drawing materials (paints and colorants) as methods outside the claims shown in [0016] to [0018] are both drawn. The most suitable material for the target paper is a material having a pH of about 7.0. Also, in order to prevent smearing, it is generally suitable to use paper that is highly water-absorbing and that does not allow the water that has been absorbed once to escape to the outside, such as paper called inkjet paper or photoprint paper. ing.
The key points for making such a paper suitable for applying the present invention are: calcium carbonate powder that has a porous and high water absorption property and has a buffer function that does not become excessively acidic, and has a high water absorption property that is once absorbed. Paper with a surface containing a material such as a water-absorbing polymer that has the effect of preventing the paint of the present invention from escaping by the application of a coloring agent is most suitable.

  Further, the same idea can be applied to the material on the paint side. A water-soluble polymer material such as PVA is used as the drawing material (paint and coloring agent) shown in [Claim 1], and [0016] to [0018]. When the paint is once dried, once the paint is dried, the paint material does not flow out immediately even after applying the colorant. The effect is that it is difficult to blur the results.

  In addition, when NR is mixed with p-NP, m-NP and PVA aqueous solution, precipitation is likely to occur. To avoid this, glycerin or glycerin aqueous solution should be used instead of water or ethyl alcohol aqueous solution as a solvent for NR. Is effective.

  In addition, the drawing material (paint and coloring agent) as a method outside the claims shown in [0016] to [0018] is dissolved in water to give colored water, and the color is changed by making it acidic or alkaline. It is possible to provide materials as educational materials with elements of toys and magic that enjoy this discoloration. This can also be used as an indicator aqueous solution whose color changes depending on the pH in the tubular container of “Toy and interior using pH indicator” (Japanese Patent Application No. 2004-061319). Since it is safe and weakly alkaline and can represent three primary colors and various colors derived therefrom, it is suitable as a composition component of an indicator aqueous solution to be placed in a tubular container of Japanese Patent Application No. 2004-061319.

The present invention overcomes the drawbacks of conventional art materials called shade inks that color development is lacking in vividness, the mark applied with the color former is brown, and the appearance is not clean.
Also, since there was no material that develops red or yellow color in the material called the shadow ink, there is a drawback that various colors cannot be created, giving materials that develop red and yellow colors, and various colors by mixing three primary colors. It is something that can be produced.

  In addition, in the art materials in the field of shade ink that utilizes the discoloration of a pH indicator due to a change in pH, phenolphthalein and thymolphthalein that develop color at a relatively high pH are used. There is a disadvantage that the pH gradually decreases due to the influence of the pH buffer component and carbon dioxide in the air (carbon dioxide), and the color disappears. To develop the color, an alkaline substance having a high pH such as sodium hydroxide is used. It has to be handled and has the disadvantage of roughening the skin when highly alkaline substances adhere to the skin. For this reason, discoloration occurs at a pH that is relatively close to neutrality, and even if the color former absorbs carbon dioxide in the air, it remains weakly alkaline, and even if it is weakly alkaline, color development on the alkaline side can be maintained sufficiently. This makes it possible to produce drawing materials, paints and paints having the properties of ink.

  The best mode for carrying out the present invention is most suitable as an art material for drawing a picture on paper and coloring with a color former, a drawing material with a magical character, and a teaching material for teaching science to children and the like.

Examples of drawing materials using the paints and color formers shown in [Claim 1] to [Claim 9] are shown below.
In a dropper-shaped container 1, 0.1 g of potassium iodide, 0.025 g of thiourea, 0.2 g of PVA, and 0.025 g of sodium diethyldithiocarbamate are dissolved per 10 cc of water to obtain a yellow color paint stock solution 1.
In a dropper-shaped container 2, 0.1 g of yellow blood soda, 0.1 g of sodium sulfite, 0.01 g of sodium diethyldithiocarbamate and 0.2 g of PVA are dissolved per 10 cc of water to obtain a blue colored paint stock solution 2. Store in a light-shielding container.
In the eye dropper-shaped container 3, 0.07 g of dimethylglyoxime, 0.05 g of sodium hydroxide, 0.18 g of potassium carbonate and 0.2 g of PVA are dissolved per 10 cc of water, and 0.2 g of calcium carbonate fine powder is mixed well and reddish. Colored paint stock solution 3 is designated. Dimethylglyoxime dissolves well when dissolved in a solution of the above-mentioned sodium hydroxide in about 3 cc of water in advance and then diluted in water.
Prepare a liquid of 50% ethyl alcohol in which 5 cc of water and 5 cc of ethyl alcohol are mixed in an eye dropper-shaped container 4, 0.2 g of salicylic acid is dissolved therein, 2.0 g of calcium carbonate fine powder is mixed, and an orange color is generated. Let it be the paint stock solution 4.
0.2 g of Tyrone per 10 cc of water is dissolved in an eye dropper-shaped container 5, and 0.2 g of sodium sulfite is dissolved to prevent oxidation of Tyrone, thereby obtaining a color developing auxiliary stock solution 5 for red and indigo color development. Store in a light-shielding container.
4.0 g of calcium carbonate fine powder per 10 cc of water is mixed in an eye dropper-shaped container 6 to obtain a paint coloring auxiliary stock solution 6 for red and indigo color development.
In an eye dropper-shaped container 7, 0.26 g of phosphoric acid, 2.0 g of sulfuric acid, 0.66 g of iron (III) sulfate, and 0.66 g of nickel nitrate (II) are dissolved per 100 cc of water to obtain a color former solution 7. Iron (III) sulfate is difficult to dissolve, but completely dissolves if it is warmed slightly and stirred sufficiently.
100 cc of glycerin is prepared in an eye dropper-shaped container 8 and 4.0 g of bismuth (III) nitrate is dissolved to obtain a color former stock solution 8. Bismuth (III) nitrate is difficult to dissolve, but completely dissolves when it is warmed up and stirred sufficiently.

The stock solution 1 to the stock solution 6 prepared in [0026] are mixed at the following ratios to obtain paints of 1 red, 2 orange, 3 yellow, 4 green, 5 blue, 6 indigo, 7 purple, and 8 red, respectively. Since the stock solution 6 is slightly colored when left unmixed, it is better to mix it immediately before coating.
Stock solution 1 Stock solution 2 Stock solution 3 Stock solution 4 Stock solution 5 Stock solution 6 Unit [cc]
1 red 1.1 1.1 0.55 0.55
2 orange 3.3
3 yellow 3.3
4 green 2.6 0.7
5 blue 3.3
6 indigo 2.4 0.5 0.4
7 purple 1.7 1.6
8 red 3.3

The stock solution 7 to the stock solution 8 prepared in [0026] are mixed at the following ratio to obtain a coloring agent 9 for the paint.
Stock solution 7 Stock solution 8 Unit [cc]
Color former 9 3.0 1.0

The paint created in [0027] is applied to a paper such as a commercially available inkjet paper that has good water absorption and is difficult to allow ink that has once absorbed water to flow again. 1 red to 8 red may be mixed with each other to create different colors. Ink paper is suitable because it produces color even with plain paper, but there is paper that does not even develop color, and it tends to bleed when a color former is applied.
When the painted paint is dry, apply the color former 9 created in [0028], and each color will develop and the original intended picture will appear. The coloring agent 9 is applied by using a brush or the like, and it is not too much liquid, not too little, and it is good when it is applied while slowly soaking.
In addition, as the inkjet paper, those from the following manufacturers are good compatibility with the inventor's experience, there is little bleeding, the color is vivid, and the trace of the trace after drawing or after applying the color former is good. The characteristics are shown.
(1) Konica Inkjet Paper KIK100A4SHM
(2) Konica Inkjet Paper KIK100A4SH
(3) APICA Inkjet Paper WP712
(4) Epson inkjet paper KA4250NSF
(5) KOKUYO Inkjet Paper KJ1210N
(6) Sanwa Supply Inkjet Paper JP-DF-120
(7) Victor JVC inkjet paper PF-F110A4F
(8) Fujifilm Inkjet Paper HA450
(9) Fujifilm Inkjet Paper SA4100
In particular, Konica's (1) had good characteristics. In addition, photo print papers and glossy papers from other companies show even better characteristics, but the unit price of the paper is high, and if it is used for the purpose of the present paint, it has a sufficient water absorption level to meet the purpose.

In the drawing material using the paint and color former shown in [Claim 1] to [Claim 9], the divalent nickel salt is omitted from the color former using aluminone, and tannic acid or tannate is used. Examples in which gray or near-black color is developed by using are shown below. In [Example 1], since dimethylglyoxime was used for red color development, it was necessary to include a nickel salt in the color former, but in this case, the nickel salt is unnecessary.
In a dropper-shaped container 1, 0.1 g of potassium iodide, 0.025 g of thiourea, 0.2 g of PVA, and 0.025 g of sodium diethyldithiocarbamate are dissolved per 10 cc of water to obtain a yellow color paint stock solution 1.
In a dropper-shaped container 2, 0.1 g of yellow blood soda, 0.1 g of sodium sulfite, 0.01 g of sodium diethyldithiocarbamate and 0.2 g of PVA are dissolved per 10 cc of water to obtain a blue colored paint stock solution 2. Store in a light-shielding container.
In an eye dropper-shaped container 3, 0.2 g of aluminum and 0.2 g of PVA are dissolved per 10 cc of water to obtain a red color coloring paint stock solution 3.
Prepare a liquid of 50% ethyl alcohol in which 5 cc of water and 5 cc of ethyl alcohol are mixed in an eye dropper-shaped container 4, dissolve 0.2 g of salicylic acid in this, mix 2.0 g of calcium carbonate fine powder, and develop an orange color The paint stock solution 4 is used.
0.2 g of Tyrone per 10 cc of water is dissolved in an eye dropper-shaped container 5, and 0.2 g of sodium sulfite is dissolved to prevent oxidation of Tyrone, thereby obtaining a color developing auxiliary stock solution 5 for red and indigo color development. Store in a light-shielding container.
1.7 g of calcium carbonate per 10 cc of water is mixed in an eye drop-shaped container 6 to obtain a paint coloring auxiliary stock solution 6 for red color development.
Dissolve 0.35 g of phosphoric acid, 2.8 g of sulfuric acid, and 1.1 g of iron (III) sulfate per 100 cc of water in an eye dropper-shaped container 7 to obtain a color former stock solution 7. Iron (III) sulfate is difficult to dissolve, but completely dissolves if it is warmed slightly and stirred sufficiently.
100 cc of glycerin is prepared in an eye dropper-shaped container 8 and 4.0 g of bismuth (III) nitrate is dissolved to obtain a color former stock solution 8. Bismuth (III) nitrate is difficult to dissolve, but completely dissolves when it is warmed up and stirred sufficiently.

Stock solution 1 to stock solution 6 and water prepared in [0027] were mixed at the following ratios, respectively, 1 ′ red, 2 ′ orange, 3 ′ yellow, 4 ′ green, 5 ′ blue, 6 ′ indigo, and 7 ′ purple. 8 'Crimson paint.
Unit [cc]
Stock solution 1 Stock solution 2 Stock solution 3 Stock solution 4 Stock solution 5 Stock solution 6 Water 1 'red 1.0 0.33 0.5 1.0 0.47
2 'orange 3.3
3 'yellow 3.3
4 'green 2.6 0.7
5 'blue 3.3
6 'Indigo 2.85 0.45
7 'purple 1.3 0.5 1.0 0.5
8 'Crimson 0.5 1.0 1.8
Immediately before applying 1 ′ red and 6 ′ indigo, 2.0 g of calcium carbonate fine powder is mixed. When mixed and left, the color is slightly developed, so it is better to mix just before coating.
In addition, 0 ′ black is prepared by mixing reagents in the following ratio. That is, 0 'black dissolves 0.0066 g of potassium iodide and 0.04 g of tannic acid in 3.3 cc of water.

The stock solution 7 to the stock solution 8 prepared in [0030] are mixed at the following ratio to obtain a coloring agent 9 ′ for the paint.
Stock solution 7 Stock solution 8 Unit [cc]
Coloring agent 9 '3.0 1.0

The paint created in [0031] is applied to a paper such as a commercially available inkjet paper that has good water absorption and is difficult to allow ink that has once absorbed water to flow again. 1 'red to 8' red and 0 'black may be mixed with each other to devise a different color. Ink paper is suitable because it produces color even with plain paper, but there is paper that does not even develop color, and it tends to bleed when a color former is applied.
When the painted paint is dry, apply the color former 9 ′ created in [0032], and each color will develop and the originally intended picture will appear. The coloring agent 9 is applied by using a brush or the like, and it is not too much liquid, not too little, and it is good when it is applied while slowly soaking.
As the ink jet paper, the same one as shown in [0029] showed good characteristics.

As an example of a drawing material as a method outside the scope of the claims, an example in the case of a drawing material using a paint and a coloring agent shown in [0018] to [0018] is shown below for comparison with this claim. The contents are shown from [0034] to [0038].
10 cc of 20% ethyl alcohol aqueous solution is prepared in an eye dropper-shaped container A, and 0.02 g of BTB is dissolved. This is referred to as a blue color paint stock solution A.
Prepare 10 cc of 50% ethyl alcohol aqueous solution in eye dropper-shaped container B, and dissolve 0.06 g of BTB. This is referred to as a blue color paint stock solution B.
10 cc of 20% ethyl alcohol aqueous solution is prepared in an eye dropper-shaped container C, and 0.02 g of PR is dissolved. This is designated as a red color paint stock solution C.
Prepare 10 cc of water in an eye dropper-shaped container D and dissolve 0.02 g of NR. This is designated as yellow color paint stock solution D.
Prepare 10 cc of water in an eye dropper-shaped container E and dissolve 0.05 g of p-NP. This is a yellow color paint stock solution E.
In an eye dropper-shaped container F, 10 cc of 50% ethyl alcohol aqueous solution is prepared, and 0.2 g of p-NP is dissolved. This is a yellow color paint stock solution F.
10 cc of 20% ethyl alcohol aqueous solution is prepared in an eye dropper-shaped container G, and 0.05 g of m-NP is dissolved. This is designated as yellow color paint stock solution G.
10 cc of 50% ethyl alcohol aqueous solution is prepared in an eye dropper-shaped container H, and 0.2 g of m-NP is dissolved. This is designated as yellow color paint stock solution H.
Prepare 100 cc of water in an eye dropper-like container I, and dissolve 4.0 g of PVA and 0.5 cc of 35% hydrochloric acid. This is designated as Dilute stock solution I for paint.
10 cc of glycerin is prepared in an eye dropper-shaped container J, and this is used as a thinning solution stock solution J for paint.

The stock solution A to the stock solution J prepared in [0034] are mixed in the following proportions to obtain paints of red, orange, yellow, di green, blue, blue, deep purple and red. Although 10 cc of stock solution C is insufficient, 20 cc is prepared by preparing the same one or by making the ratio the same.
Unit [cc]
Stock solution A Stock solution B Stock solution C Stock solution D Stock solution E Stock solution F Stock solution I Stock solution J
A red 0.6 4.4 1.0 4.0
B Orange 6.0 4.0
Ha Yellow 1.5 4.5 4.0
D Green 2.2 2.3 1.5 4.0
Hot Blue 5.5 0.5 4.0
He Ai 4.5 1.5 4.0
Purple 1.4 0.6 4.0 4.0
Chiku 6.0 4.0
In the above state, red, di-green, blue-blue, deep-blue, purple, and red are yellow as an acidic color, and red and orange are red as an acidic color. The reason why orange and ha yellow were formulated as acidic and red was because the color before coloring and after coloring was the same, so it was thought that it was not interesting, and it was adjusted so that it was not yellow. is there. The paints that are very light yellow before color development and become orange or dark yellow after color development are the following paints of 'Orange' and 'H' yellow. The orange and ha yellow blends have a clearer color change and are considered interesting.
(B) As an example of the blending method of “orange” and “ha” yellow, it is carried out as follows. The stock solutions C, G, H, and I prepared in [0034] are mixed at the following ratios to obtain paints of “orange” and “ha” yellow, respectively.
Stock solution C Stock solution G Stock solution H Stock solution I
B 'Orange' 1.0 3.0 2.0 4.0
C 'Yellow' 4.0 2.0 4.0

  An aqueous solution in which 2.0 g of potassium carbonate is dissolved in 100 cc of water is prepared, and this is used as a color former for the paint.

Apply the paint created in [0035] to a paper such as a commercially available inkjet paper that has good water absorption and that makes it difficult for ink that has been absorbed once to flow again. It is also possible to devise a way to mix different colors from red to chi-red, ro-orange, and ha-yellow to produce different colors. Even plain paper produces color, but there are papers that do not even develop color, and ink jet paper is good because it tends to bleed when a color former is applied.
When the painted paint is dry, apply the color former prepared in [0036], and each color will develop and the original intended picture will appear. When applying the color former, use a brush or the like, do not apply too much liquid, and do not use too little liquid.
As for inkjet paper, I felt that the difference in color tone, color vividness, and discoloration difference when painted by Konica from (1) and (2) was clear. There was no big difference in the items from each manufacturer.
(1) Konica Inkjet Paper KIK100A4SHM
(2) Konica Inkjet Paper KIK100A4SH

  In addition, since the combination of the indicators shown in [0034] and [0035] shows a vivid color development on the alkaline side even if it is weakly alkaline, it is dissolved in water to give colored water, and various colors appear by changing this pH. It can also be used as a toy with magic elements. For example, it can also be used as an indicator aqueous solution whose color changes depending on the pH placed in the tubular container of “Toy and interior using pH indicator” (Japanese Patent Application No. 2004-061319).

The present invention provides various colors in the field of art materials and paints called invisible ink and shadow ink, and provides materials that are not easily faded by the action of carbon dioxide in the air. It can be used as educational material to help children educate children about their interest in chemical reactions, etc. In addition, the coloring material itself can be effectively used because of its abundant shades and characteristics that do not fade easily.
Also, considering the economics of manufacturing the material, it utilizes a color reaction and material that can cause color development with less or less expensive materials. As a result, by applying the present invention An inexpensive painting material can be obtained.

Claims (9)

In drawing materials consisting of paint that does not develop color when applied to paper, etc., and a coloring agent that is applied later to develop the color of the paint, iodide such as potassium iodide, yellow blood, etc. Hexacyanoiron (II) acid salt such as soda, dimethylglyoxime, salicylic acid salt such as salicylic acid and sodium salicylate, aurin tricarboxylic acid triammonium salt (hereinafter abbreviated as aluminon), aurin tricarboxylic acid salt, tannic acid or tannic acid salt Use a mixture of all or any of the appropriate ratios, and use a trivalent iron salt such as iron (III) sulfate, a divalent nickel salt such as nickel nitrate, or a bismuth nitrate as a color former to be applied later. Using a mixture of all or any of the valent bismuth salts with paint and color former Drawing material that would give the various color by the formation of such colored complex that takes place between. In the drawing material according to claim 1, among the paints that do not develop color when applied to paper or the like, an iodide such as potassium iodide that develops yellow color, and a colorant that is applied later to develop the paint As a material for assisting color development by reaction with a bismuth salt as a coloring material, a drawing material characterized by adding to the iodide in the paint either or both of diethyldithiocarbamate such as sodium thiourea and diethyldithiocarbamate . In the drawing material of [Claim 1], among the paints that do not develop color when applied to paper or the like, hexacyanoiron (II) acid salt such as yellow blood soda that develops a blue color by reaction with iron (III) salt As an auxiliary material for preventing yellowing during storage, hexacyanoferrate (II) in the paint is added to either or both of sulfite such as sodium sulfite and diethyldithiocarbamate such as sodium diethyldithiocarbamate. A drawing material characterized by being added. Among the paints that do not develop color when applied to paper or the like in the drawing material of [Claim 1], the reaction of hexacyanoferrate (II) and iron (III) salt such as yellow blood soda that develops blue color Dissolve 4,5-dihydroxybenzene-1,3-disulfonic acid disodium (hereinafter abbreviated as Tyrone) into the paint, which has the effect of assisting the color development by iron and reacting with iron (III) salt to develop a deep blue color. A drawing material characterized by being added. In the drawing material of [Claim 1], among the paints that do not develop color when applied to paper or the like, the water solubility of dimethylglyoxime that forms a red color by forming a complex with a divalent nickel salt Paper of tannic acid or tannic acid salt as a supplementary material to ensure the reaction with the color former and to form a gray or near black color by forming a compound with the trivalent iron salt As an auxiliary material to maintain good color developability when applied to the surface, water-soluble carbonates such as potassium carbonate, water-soluble hydroxides such as sodium hydroxide, and water-insoluble carbonates such as calcium carbonate A drawing material, wherein all or any of the salts is added to dimethylglyoxime or tannic acid or tannate in the paint. In the drawing material of [Claim 1], a trivalent iron salt paper such as iron (III) sulfate is used as a color former to be applied later in order to develop a color that does not develop color when applied to paper or the like. A drawing material comprising phosphoric acid having an effect of suppressing brown discoloration due to a change with time after coating. In the drawing material of [Claim 1], the coloring agent to be applied later in order to develop a color that does not develop color when applied to paper or the like is changed from a trivalent bismuth salt such as bismuth nitrate to water. A drawing material comprising an inorganic acid such as dilute sulfuric acid having a function of suppressing the generation of a soluble basic salt. In the drawing material of [Claim 1], as a method of preparing a color former which is applied later to develop a color which does not develop color when applied to paper or the like, dilute sulfuric acid, phosphoric acid, iron sulfate (III ) And other trivalent iron salts, nickel nitrate and other divalent nickel salts or all of them are dissolved, and trivalent bismuth salts such as bismuth nitrate dissolved in glycerin or glycerin aqueous solution are colored. A drawing material characterized by suppressing the generation of a hardly soluble salt of bismuth by mixing immediately before using the agent. In the drawing material of [Claim 1], among the paints that do not develop color when applied to paper or the like, an aluminon that forms a red complex color with a trivalent iron salt is applied to the paper. As an auxiliary material for maintaining good color development when color is developed, water-soluble hydrogen carbonates such as potassium hydrogen carbonate, water-soluble carbonates such as sodium carbonate, and water-insoluble carbonates such as calcium carbonate A drawing material characterized in that all or any of them is added to aluminon in the paint.