JP2006130684A - Tarnishable scientific interior - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a teaching material having effects for educating a scientific phenomenon by making an interior, a display, a toy and an accessory taking pleasure in the change of color such as sudden change of colors and succesive change of colors without through man power and moreover by giving surprise to spectators by equipping with the elements of magic and stirring up interest in the principle of this phenomenon. <P>SOLUTION: After at least two kinds of solution, which starts a clockwork reaction, an oscillating reaction or an acid/alkali generating reaction, are blended together, a resultant solution is introduced in a tubular container so as to cause the sudden color change in the solution at a certain position of the tubular container through the clockwork reaction, the oscillating reaction or the like while the solution flows in the tubular container. By contriving the form of the container, the state, in which the behaviour of the color change in the liquid is intelligible, is formed and by contriving the solutions to blend with, the change of the shape of the dripping liquid can be enjoyed by small amount of chemicals. As an annexed effect, the density of the minute copper ion and vitamine C can be measured. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  This invention uses a chemical reaction phenomenon known as a clock reaction, a vibration reaction, a reaction that generates an acidic or alkaline substance, and enjoys color changes in interiors, displays, toys, accessories (hereinafter, interiors, displays, toys, The general term for accessories is called "interior etc.").

  In addition, the present invention uses a change in the state of the polymer compound to create a visually interesting solid, and uses a clock reaction, a vibration reaction, a reaction that generates an acidic or alkaline substance, It relates to interiors that enjoy color changes.

  This invention provides a method for easily and quantitatively measuring the content of ascorbic acid (vitamin C) contained in fruit juices, soft drinks, juices, etc., and the amount of copper ions contained in water. The present invention relates to a quantitative measurement technique and interiors and the like to which this technique is applied.

The present invention is based on a chemical phenomenon such as a clock reaction known as a Landolt reaction or an oscillation reaction known as a Belousov-Zhabotinsky reaction, for example.
Further, the background art is an analytical chemistry method applied to water quality analysis using a pH indicator whose color changes with pH.
Furthermore, the present invention is based on a chemical reaction such as a bond mediated by calcium ions or the like of a polymer material.
Japanese Patent Application No. 2004-77964 Japanese Patent Application No. 2004-177997 Japanese Patent Application No. 2004-61319

In conventional interiors that change the color by applying an acid / alkaline indicator whose color changes depending on pH, the indicator solution is simply mixed with an acidic or alkaline aqueous solution to cause discoloration. It was obvious that the audience was showing, and there was a drawback that the audience was not surprised at the performance.
An educational program that does not make you feel as if you are showing chemical changes or chemical reactions, but shows a phenomenon that is difficult to understand, like a magic trick, makes you interested in the cause of the phenomenon, and teaches it. The challenge was to provide toys or educational materials with various elements.

In interiors that change the color using the iodine starch reaction, it is clear that when an iodine-containing solution and a starch solution are mixed, the reaction occurs immediately and simply shows a chemical reaction. There was a drawback of lack of surprise.
In addition, for educational aspects such as giving children interest in and teaching scientific phenomena from the presentation of discoloration, there was a drawback that the surprise of discoloration presentation was insufficient. .

In conventional interiors where the color changes due to a chemical reaction, it is necessary to produce reagents by mixing them with human hands, so it is not possible to produce a reaction that continuously changes colors without human intervention. In order to operate as an interior or the like, it has been a problem to show chemical changes continuously without human intervention.
In the [Specification] [0027] section of Japanese Patent Application No. 2004-77964, an automatic device that continuously shows chemical changes without manual intervention was described. Electricity is used to realize this automatic device. It was necessary to create a mechanism that can show chemical changes continuously so that it can be manufactured simply and easily.
In addition, in [Claim 2] of Japanese Patent Application No. 2004-177997, a method for slowly generating an acidic solution or an alkaline solution is defined. However, the periodate used is relatively expensive, Formaldehyde used in combination is harmful to the human body, and -t-butyl chloride used in another combination is poor in water solubility, and when diluting it before hydrolysis, water solubility such as acetone There are drawbacks, such as the need to use organic solvents and the need for care, and the challenge is to create “toys or interiors” using inexpensive, highly safe, and easy-to-handle materials. It was.

  In addition, in conventional interiors where the color changes due to a chemical reaction, the color change of the solution is shown, but the liquid changes to a solid, and this does not involve a change in the form of the substance such as a color change due to the chemical reaction, There is a drawback that the phenomenon to be produced is monotonous, and it has been a challenge to produce an interesting combination of various chemical phenomena such as changes in the state of substances.

  Furthermore, with the simple quantitative method of ascorbic acid (vitamin C) defined in [Claim 7], [Claim 8], and [Claim 9] of Japanese Patent Application No. 2004-77964, the time until the completion of the clock reaction is measured. It was a challenge to provide a method that can more easily determine the approximate vitamin C content immediately and visually.

The present invention has been made in order to solve the above-mentioned problems. In [Claim 1], a clock reaction or vibration reaction is initiated, and in [Claim 2], a solution that initiates a reaction in which hydrogen ions or hydroxide ions are generated. Is defined as mixing and flowing into a tubular container. As a method for mixing the solutions, for example, there is a means for adjusting the flow rate of each solution filled in the tank with a pinch cock or the like, for example, receiving each solution with a funnel and mixing the solutions here.
When a mixed solution that starts a clock reaction or a vibration reaction is passed through a tubular container, the initial color at the beginning of the flow is completely different from the color after the reaction has occurred. For example, triiodide ion I3- (known as the Landolt reaction) In the clock reaction in which iodine I2 and iodine ion I- are generated), the solution is a colorless and transparent solution immediately after being introduced into the tubular container, but after the reaction, red or yellow which is the color of triiodide ion (iodine). When a trace amount of starch is mixed in the solution, a very deep blue-purple or red-purple color is given.
Changes in the state of the clock reaction or vibration reaction occur suddenly after a certain period of time, so if you come to a certain position in the middle of flowing through the tubular container, the color suddenly changes without doing anything, like a magic trick A production effect that makes you feel strange.
In the reaction in which hydrogen ions or hydroxide ions are generated as described in [Claim 2], if the alkalinity or acidity of the indicator is increased beyond the region where the indicator changes color, the pH until the indicator changes color is reached. There is no color change, and a phenomenon similar to the clock reaction can be developed, in which the chemical reaction proceeds and the color changes suddenly when the pH of the indicator changes.
As the tubular container to be used, a colorless and transparent one is effective.

Examples of a mixture of substances that cause a clock reaction or vibration reaction or a reaction that generates hydrogen ions or hydroxide ions include the following (1) to (10) and [Claim 14].
(1) Clock reaction (Landolt reaction) in which triiodide ion (iodine) is generated by mixing sulfite or bisulfite with acidified iodate
(2) Clock reaction in which triiodide ion (iodine) is generated by mixing thiosulfate, iodide and acidified hydrogen peroxide (3) Triiodine by mixing iodide, thiosulfate and peroxodisulfate (4) Generation and disappearance of triiodide ions (iodine) by mixing malonic acid catalyzed by divalent manganese salt with acidified hydrogen peroxide and iodate Oscillating reaction appearing alternately (Briggs-Rauscher reaction)
(5) Reaction in which hydrogen ions (H +, hydrochloric acid) are generated by hydrolysis by mixing tert-butyl chloride and water (clock) Reaction (6) Hydroxyl ion (OH-) by mixing thiosulfate and periodate (Clock) reaction (7) (7) Hydroxyl ion (OH-) reaction by mixing thin formaldehyde aqueous solution with thin sulfite or bisulfite (Clock) reaction (8) Ferroin solution with cerium salt as catalyst Oxidation-reduction indicator, vibrational reaction of malonic acid, bromate and bromide in an acidic solution (Belousov-Zhabotinsky reaction)
(9) Vibration reaction in which tannic acid, bromate and bromide react in acidic solution using ferroin solution as redox indicator (10) Bivalent manganese salt as catalyst and ferroin solution as redox indicator Oscillating reaction in which generation and disappearance of bromine by malonic acid and bromate in an acidic solution alternate (11) Ethyl acetoacetate in an acidic solution using a divalent manganese salt as a catalyst and a ferroin solution as a redox indicator In addition, among the above reactions, (7) is a hydroxide ion (OH−) by mixing aldehydes such as benzaldehyde and a thin sulfite or bisulfite instead of formaldehyde. ) Is initiated. The benzaldehyde mentioned here is naturally contained in almonds and apricot seeds, and is the main component of the almond fragrance, and is used in trace amounts for flavoring similar to almonds and coconuts. Nevertheless, it has the advantage of being less harmful than formaldehyde. However, it is sparingly soluble in water and requires a method such as dissolving in alcohols.

Among these, in the generation of triiodide ions (iodine) of [0011] items (1) to (4), if a small amount of starch aqueous solution is added, a very blue-purple to red-purple color due to iodine starch reaction is obtained. In the reaction (5) to (7) in which hydrogen ions or hydroxide ions are generated, a pH indicator that shows various colors depending on the pH of the aqueous solution is added to make the initial pH of the aqueous solution suitable. By adjusting the value, you can produce various color changes. Above all, when a pH indicator that defines all seven colors of rainbow depending on the degree of acid and alkali as defined in [Claim 16] to [Claim 18] is used, a very colorful interior is produced. be able to. A description of these claims will be given later.
[0011] Items (8) to (11) show that when ferroin is used as an oxidation-reduction indicator, green, blue, purple and red return to green and green to blue, purple and red again. The reaction is repeated, and various color changes and periodic vibration phenomena can be produced. Further, when ferroin is not used, it is possible to produce a vibration phenomenon that vibrates between red of bromine and colorless of bromine ions.
By adding scientific explanations of these phenomena, the three primary colors of color, the concept of acid / alkali, the concept of pH, which is the strength of acid / alkali, the iodine ion by oxidation-reduction, and triiodide, are enjoyed with interest. It is also effective for educational aspects such as teaching children and educating students about scientific content such as ion generation and color formation by iodine starch reaction, and oxidation-reduction reaction that causes a vibrational reaction.
As shown in specific examples of solution formulation in [Example 1] to [Example 4] and [Example 7], the amount of chemicals used in these reactions is compared to the amount of the solution to be prepared. Therefore, it is very rare, and there are many substances that are frequently used in daily life. Consideration is also given to economic efficiency and environmental impact during disposal.

  The solution flowing in the tubular container (1 in FIG. 1) defined in [Claim 1] or [Claim 2] is mixed into the solution as shown in (2) in FIG. If the solution lump is separated by the mixed air and the boundary is clear, when the discoloration due to the clock reaction or vibration reaction occurs, the entire lump suddenly changes color, making it visually interesting and highly effective. .

In order for air to be mixed as described in the section [0013], when introducing the solution into the tubular container, it is necessary to ensure a route for air to be mixed at the same time, and the introduced solution travels along the wall of the tubular container. There is a need for a means to prevent the air from flowing gently and to force the mixed air down with the solution.
The method defined in [Claim 3] is for making sure that air is mixed as described above, and that the solution introduced into the tubular container is made into small lumps separated by air, and color change is caused for each small lumps. is there. [Claim 3] A container (3 in FIG. 1) having a wide inlet and a narrow outlet (hereinafter referred to as a funnel when an abbreviation is used), that is, when the solution is introduced from the funnel A into the tubular container, the funnel A When the outer wall of the tip of the tube is in contact with the inner wall of the tubular container, the introduced solution gently flows along the inner wall of the tubular container, and the air that is introduced together escapes to the outside through the outer wall of the funnel A and the like. Result. Also, if there is a gap between the outer wall at the tip of the funnel A and the inner wall of the tubular container, when the solution is introduced, air is introduced together through this gap, and the air mass is pushed downward together with the solution. The solution introduced into the tubular container can be made to flow as a small mass separated by air.
As shown in [Claim 3], as one method for preventing a contact between the outer wall at the tip of the funnel A and the inner wall of the tubular container and for providing a gap between the outer wall at the tip of the funnel A and the inner wall of the tubular container. For example, by winding a wire-like object such as a wire (4 in FIG. 1), a thread, a rubber string or the like around the tip of the funnel A and inserting it into a tubular container, these requirements can be achieved and the object can be achieved. .
The main point of [Claim 3] is to prevent the inner wall of the tubular container and the tip of the funnel A from touching as described above, and the wire shown in (1) of [Claim 3] as described above It is convenient to wind a thread-like material such as a thread or rubber string, but in addition to this, as shown in (2) of [Claim 3], a protrusion is provided on the outer periphery except for the vicinity of the tip of the funnel A. [ As in (3) of [3], a protrusion is provided on the inner wall side of the tubular container and the funnel A is inserted. As in (4) of [Claim 3], a part of the inner wall of the tubular container is recessed inward. The purpose can also be achieved by inserting the funnel A.
The solution to be introduced into the tubular container is preferably as shown in [Claim 1] or [Claim 2]. For example, as defined in [Claim 9], as shown in (5 of FIG. 1). When the mixture of the solution C and the solution D as shown in (6 in FIG. 1) is used, the effect of the demonstration is high, but this is not restrictive.
In addition, as shown in [Claim 4], instead of mixing the solution with the funnel A, the funnel B (7 in FIG. 1) installed separately from the funnel A receives these two or more solutions, By aligning the position of the funnel B so that the mixed solution is dropped on the discharge port of the funnel A, the mixed solution is dropped at the discharge port of the funnel A with a momentum. 3], the operation of “mixing air reliably into the solution and making the solution introduced into the tubular container into small lumps separated by air” can be caused more reliably.

An aqueous solution of alginate known as sodium alginate or potassium alginate which is a polymer material specified in [Claim 5] is calcium hydrogen phosphate, calcium nitrate, calcium chloride, calcium bromide, calcium iodide, lactic acid. It reacts with calcium salts such as calcium and calcium acetate to take in calcium ions and bind them through these calcium ions as a medium to produce a highly viscous solid.
It is generally known that the above-mentioned calcium salts cause the same phenomenon even if they are strontium salt, barium salt, magnesium salt, beryllium salt, and radium salt, respectively, and the solidity of the generated solid is the best strontium salt Then, the calcium salt is good.
Carrageenan, which is very often used in foods such as jelly, has a chemical structure very similar to alginic acid, and, like alginate, reacts with calcium and potassium salts and takes in calcium or potassium ions. These calcium ions or potassium ions bind to each other to produce a highly viscous solid. A characteristic feature of carrageenan is that it produces a highly viscous solid through this potassium salt, but it has the same effect as alginate as a characteristic. Therefore, in the following explanation, alginate is used as an example. explain.
In general, potassium salts are more water-soluble than calcium salts, and are easy to handle.
Alginate and carrageenan are safe organic polymer materials that are known as substances constituting seaweeds such as kombu, cedar and tsunomata, and are also used as foods.

  When an alginate aqueous solution is dropped onto an aqueous solution of calcium salt, strontium salt, magnesium salt, barium salt, etc., the outside of the dropped droplet first solidifies instantly to form a thin film, and as time passes, If the solution components enter the interior due to the permeation phenomenon and the entire dropped droplet is solidified, and the substance existing inside and outside the membrane causes a chemical reaction, the reaction gradually occurs toward the inside. After a certain period of time, the reaction is completed for the entire droplet.

  However, due to the principle of osmotic pressure, substances existing inside the membrane also diffuse to the outside, and when a small amount of substance inside the membrane can chemically affect a large amount of liquid outside the membrane. The amount of liquid outside the membrane will change over time.

The principle of [Claim 5] is explained by the terms [0015] to [0017], and the solution A to be dropped is for causing a clock reaction or a vibration reaction or a reaction for generating hydrogen ions or hydroxide ions. One component is contained, and an alginate is contained therein. Alginate has a very strong viscosity with increasing concentration, and the concentration suitable for dropping as a liquid is about 1% by weight, and the limit of dripping at a high concentration is 3% by weight in common sense. 5% by weight is considered the limit.
Solution B to be dripped contains another component for initiating a clock reaction or vibration reaction or a reaction in which hydrogen ions or hydroxide ions are generated, and includes calcium salt, strontium salt, magnesium salt or barium salt. Containing. Although beryllium salts or radium salts are possible, it is impractical to use both elements because they are toxic or rare elements.
Although barium is an element present in relatively large amounts, water-soluble barium salts are not as harmful as beryllium salts, but are harmful to the human body. Not as practical as it is. Since barium sulfate used as an X-ray contrast medium is insoluble in water and very thin hydrochloric acid which is stomach acid, it is not harmful to the human body and can be applied directly to the human body.

Calcium salts or strontium salts are most water-soluble in the form of nitrates and vary greatly with temperature, but they have a water solubility of 50% by weight or more and are easy to handle. Nitrate has oxidizing properties, and it is considered to be admixed with dihydrogen phosphate (primary phosphate) in order to prevent single precipitation of substances such as potassium nitrate by reaction in solution. Calcium dihydrogen phosphate dissolves in water only up to about 1.6% by weight, but can be dissolved in an acid such as about 0.4% by weight phosphoric acid to a high concentration of about 6% by weight.
Calcium and strontium sulfates and carbonates are unsuitable because they are poorly soluble in water, and calcium chloride, strontium chloride, and magnesium chloride are applicable. ) To those that use the iodine starch reaction as defined in (4), this reaction is disturbed and the color at the time of discoloration is deteriorated or the reaction is accelerated. .

When the solution A is dropped into the solution B, a thin film is instantly formed on the outer periphery of the solution A, and the droplet has a spherical shape. Thereafter, substances outside the membrane enter the membrane by osmotic pressure, and a clock reaction or vibration reaction or a reaction in which hydrogen ions or hydroxide ions are generated is started.
The discoloration suddenly occurs at the completion of the clock reaction or vibration reaction, and the formed spherical droplet suddenly changes its color from the outside after a certain period of reaction introduction period. This state of change can be enjoyed as an effect such as interior. At the same time, calcium ions penetrate into the membrane, and the spherical droplets gradually solidify to the inside.
As described in the paragraph [0010], even in the reaction in which hydrogen ions or hydroxide ions are generated, if the alkalinity or acidity of the solution A is made stronger than the area where the indicator changes color, the pH range where the indicator changes color. The film formed by the solution A can develop a phenomenon according to the clock reaction, in which there is no color change until the pH reaches, and the chemical reaction progresses and suddenly changes color when the pH of the indicator changes. It can be seen that the solution inside gradually changes color in layers.
However, the fact that the substance existing inside the membrane also diffuses outside is as described in the section [0017], and the indicator inside the membrane also diffuses outside the membrane, and the solution outside the membrane gradually changes color. This is not very attractive and can be avoided by using a highly dyeable pH indicator and preventing it from diffusing outside by staining with alginate. This is embodied in [Claim 23] and will be described later.

The spherical droplets generated from the solution A (8 in FIG. 2) gradually change color when falling in the solution B (9 in FIG. 2), but only a chemical reaction proceeds to the inside of the droplet. In reality, the depth of the solution B cannot be taken so as to be dropped in the solution B for a long period of time. Further, when the reaction rate is increased so as to change the color while simply falling in the solution B, the reaction is too early and the presentation effect is low.
Therefore, in order to reduce the falling speed of the spherical droplets generated from the liquid A in the solution B and extend the path, a sloping path as shown in (10 in FIG. The solution may be to roll or slide the droplets to create a state of moving in the B liquid for a long time.
Therefore, the problem is a small droplet (11 in FIG. 2) having a diameter of about 0.1 mm or less of the A liquid that may be generated by impact on the liquid surface when the A liquid is dropped onto the B liquid. . The droplet when A liquid is dropped into B liquid is somewhat dependent on the diameter of the tube used for dropping, but is roughly determined by the surface tension of the solution, and is as large as about 3 mm in diameter. However, if no countermeasures are taken here, a small droplet having a diameter of about 0.1 mm generated by impact on the liquid surface at the time of dropping enters under this large droplet (12 in FIG. 2). There is a possibility that large droplets are prevented from rolling or sliding along a sloping path and stop moving.
According to the tests of the inventors, when a small droplet enters into a large droplet and stops moving with a certain probability, the effect of a stopped droplet is Then you can use the following, and the problem that the whole movement gets worse occurs.

Therefore, it is best to screen out small droplets as described in [0021] immediately after they are generated.
[Claim 6] embodies this measure. As shown in (13 in FIG. 2), a "squirrel-like" plate is placed in the B liquid, gently inclined, and the A liquid is placed thereon. When a drop of 1 mm is dropped, a small drop (11 in FIG. 2) having a diameter of about 0.1 mm generated by impact falls through the gap between the “slatted” plates (14 in FIG. 2). Another path as shown in FIG. 2 can be removed from the path followed by a large droplet. For example, in FIG. 2, the liquid B drops directly toward the bottom of the container for solution B (15 in FIG. 2). Thus, it is possible to remove small droplets and prevent the movement of large droplets from stopping due to this.

Now, the spherical matter generated from the droplet of the liquid A described above falls in the solution B. As a necessary condition, the specific gravity of the solution A is heavier than the specific gravity of the solution B. As the specific gravity of the solution A is heavier than that of the B solution, the solution A is surely dropped.
The purpose of [Claim 8] is to surely drop the spherical matter generated from the droplets of the solution A into the solution B as described above. For this purpose, the solute having a specific gravity higher than that of water is applied to the solution A. Is added at least 1% by weight. That is, in order to increase the specific gravity of the solution A, a method in which a solid substance is dissolved in the solution A is used. As the substance used for this solute, any substance that does not interfere with the intended chemical reaction serves its purpose. be able to. In this case, substances that are easily soluble in water without affecting the clock reaction, vibration reaction, reaction of generating hydrogen ion or hydroxide ion, and solidification reaction of alginate are suitable. For example, sucrose, fructose, Potassium monophosphate, potassium sulfate, sodium sulfate, sodium nitrate, potassium nitrate, sodium chloride, potassium chloride, ammonium chloride, monobasic ammonium phosphate, ammonium sulfate, etc. are present as far as possible.
On the other hand, as an unsuitable substance, for example, calcium salt, strontium salt, magnesium salt, barium salt, which has an effect of binding alginate to, for example, calcium ions and the like to produce a highly viscous solid, When the reactions shown in (1) to (4) of the item [0011] are applied, examples of substances that interfere with this reaction include chloride, bromide, iodide and the like. Further, when carrageenan is applied to the solution A, a potassium salt having an effect of similarly producing a highly viscous solid is not suitable.

Here, in [Claim 9], it is defined that sulfite or hydrogen sulfite such as sodium sulfite and an aqueous starch solution are used as one of the substances causing a clock reaction, and urea is added to this solution. The meaning is in the following two points.
(1) In order to prevent deterioration of the aqueous starch solution at room temperature, a weak but bactericidal and reducing urea is mixed with the aqueous starch solution to decompose the bacteria and dissolve starch in the solution or oxygen dissolved in the solution. Prevents oxidative degradation. Prevention of oxidative alteration of sulfite or bisulfite by oxygen.
(2) Use urea as a solute for increasing the specific gravity of the solution A as described in the section [0023].
In particular, it has been experimentally found that it is effective to contain about 10% by weight of urea in the liquid A for the purpose of increasing the specific gravity described in the section [0023]. If the specific gravity is not large enough with respect to the B liquid, a small bubble may adhere to the A liquid droplet due to the impact when the A liquid is dropped. This bubble is generated from the A liquid droplet. The falling of the spherical object in the B liquid may be prevented, and the operation may be stopped.
In addition, as for the use of urea for preventing starch degradation, a test on the minimum limit value has not been conducted, but it is considered that there is an effect of clearly preventing degradation at a concentration of about 1% by weight, and that it is also effective at a lower concentration.

Another effective measure for preventing the decomposition of the aqueous starch solution is that the aqueous starch solution contains an alkali hydroxide such as sodium hydroxide or potassium hydroxide, sodium methoxide, sodium ethoxy as defined in [Claim 10]. That is, a substance exhibiting strong alkalinity is dissolved in water such as potassium, methoxide, potassium ethoxide, potassium carbonate, sodium carbonate.
In alkaline, bacteria that degrade starch cannot propagate, and because hydrolysis of starch occurs in weak acidity, alkaline results in hindering the hydrolysis. When the effective reactions shown in (1) to (4) of the item [0011] are used, it is more effective to apply [Claim 9] together.

As a measure to prevent starch degradation, it is also effective to contain about 0.001% by weight or more of thymol, which is a fungicide and has a unique scent of herb "Thyme" and a main component that brings about its bactericidal action. It is also effective to use alcohol as a bactericidal agent. Further, the sulfite or bisulfite added at the same time itself reacts and removes oxygen dissolved in the aqueous solution, and serves to prevent oxidative degradation of starch.
In addition, based on the above, if an aqueous starch solution is stored as follows, it can be used stably for a long time.
(1) Use this starch aqueous solution at a high concentration and dilute it immediately before use.
(2) This starch aqueous solution is heat-sterilized and thymol is added. As thyme is used as food, there is no problem with the safety of thymol to the human body when used in small amounts.
(3) The starch aqueous solution having a high concentration is stored in a full container so that air does not remain in the container as much as possible so that oxygen is not easily mixed.
(4) Add alcohol to the starch aqueous solution with high concentration. It has been confirmed that if it is about 5% or more, an effective effect is exhibited.
(5) Similarly, sulfite or bisulfite is mixed at a high concentration.
(6) The urea and alkaline substance shown in [Claim 9] and [Claim 10] are mixed. However, the concentration of urea may be increased according to the increase in concentration of aqueous starch solution, but the concentration of alkaline substances does not need to be increased so much. Use without raising. This limit is considered to be about 0.4% by weight in terms of sodium hydroxide in the inventors' experience.
(7) Add a trace amount of a chelating agent such as EDTA to mask and inactivate a metal salt contained in a trace amount in tap water or the like, which acts as a catalyst for oxidative decomposition of aqueous starch solution, sulfite or bisulfite.

One solution C uses a sulfite or bisulfite such as sodium sulfite and an aqueous starch solution, and the other solution D uses an iodate such as potassium iodate and an acid such as phosphoric acid or sulfuric acid. In order to shorten the reaction time until the clock reaction is completed in the combination of the solutions to be generated, an intermediate product in the clock reaction is added to the solution C or the solution D, or sulfite or bisulfite and iodate. A reducing agent having a faster reaction rate than the first-stage oxidation-reduction reaction rate that occurs between the first and second components may be added to Solution C.
This clock reaction consists of the following three reaction stages. The first stage reaction is rapidly advanced or the product from the first stage reaction is added in advance to accelerate the time until the entire reaction is completed. be able to.
In the first stage reaction, first, in an acidic aqueous solution, sulfite slowly reduces the iodate, converts itself into sulfate, and generates iodide ions from the reduced iodate.
IO3- + 3.HSO3- = I- + 3.SO4 (2-) + 3.H +
Subsequently, in the second stage reaction, a reaction in which triiodide ions are generated by the slow reaction of iodide ions generated from the reduced iodate and iodate,
IO3- + 8 ・ I- + 6 ・ H + = 3 ・ I3- + 3 ・ H2O
As the third stage reaction, a rapid reduction reaction of triiodide ions to iodide ions by sulfite in an acidic aqueous solution that occurs simultaneously with the second stage occurs. I3- + HSO3- + H2O = 3 · I- + SO4 (2-) + 3.H +
Due to the rapid reaction in the third stage, the color change to blue-purple due to the iodine starch reaction does not appear until all the sulfite or bisulfite is consumed, and all the sulfite or bisulfite is When it is reduced, a color change appears.
Here, IO3- means iodate ion, HSO3- means bisulfite ion, I- means iodine ion, H2O means water, SO4 (2-) means sulfate ion, H + means hydrogen ion, and I3- means triiodide ion. For example, the symbols 3 ·, 8 ·, 6 · indicate that the ion is involved in the reaction of 3 equivalents, 8 equivalents, and 6 equivalents, respectively, and the = symbol points to the right indicating the progress of the reaction. This symbol is used in place of the arrow symbol and represents that the reaction proceeds from the left side to the right side.
Bisulfite ions (HSO3-) are generated from directly added bisulfite or generated from sulfite in an acidic aqueous solution.

[Claim 11] defines a method of adding an intermediate product in the clock reaction to the solution C in order to shorten the reaction time until the clock reaction is completed. That is, the intermediate product in this clock reaction is iodide (I−), and adding a small amount of this is equivalent to the fact that the reaction of the first stage of this clock reaction progressed quickly, and thus The reaction time until the reaction is completed can be shortened.
By applying this method to the method of [Claim 1] or [Claim 5] or [Claim 7], it can be used when it is desired to adjust the time until the completion of the clock reaction. The addition of iodide can accelerate the completion of the reaction, and the time to completion of the reaction can be lengthened by lowering the iodate concentration or acid concentration of the mixed solution.
Although the reaction time can be shortened by increasing the iodate concentration or acid concentration of the mixed solution, there is a drawback that the color at the completion of the reaction becomes too dark if the iodate concentration is increased, and the acid concentration is reduced. If it is too high, the iodide of [Claim 11] has an adverse effect such as a decrease in the strength of the solid matter on a chemical reaction that binds through the calcium ions of the alginate and the like to produce a highly viscous solid matter. The method of adding is particularly effective when used in combination with the method of [Claim 5].

[Claim 12] In order to shorten the reaction time until the clock reaction is completed, the reduction of iodate, which is the first stage clock reaction, is rapidly performed by ascorbic acid (vitamin C), Defines how to rapidly produce intermediate products in the reaction. As a result, it is possible to shorten the time until the first stage reaction, which is a relatively slow rate-determining stage of the clock reaction, is completed, and to shorten the completion time of the entire clock reaction. This is used when it is desired to adjust the time until the completion of the clock reaction by applying to the method of [Claim 1] or [Claim 5] or [Claim 7] as in [0028]. it can.
In addition, in order to rapidly reduce the iodate, a reducing agent such as hydrosulfite is also effective in addition to the above vitamin C.
However, the purpose of speeding up the reaction by adding vitamin C is not to control the shortening of the reaction time, but to the solution defined in [Claim 1] or [Claim 5] depending on the speed of the clock reaction completion time. The amount of the vitamin C added can be quantified by moving the discoloration position upward and visually measuring the amount of movement.
That is, the source of vitamin C to be added is, for example, fruit juice or juice, and the reaction time is added by adding about 10% to the sulfite or bisulfite-containing side of the reaction shown in (1) of the item [0011]. And the reaction position of the reaction described in [Claim 1] moves. This movement amount is converted into a shortened time, and in addition to the reaction time shortening shown in the paragraphs [0031] to [0036] of the patent application “Japanese Patent Application No. 2004-77964” filed earlier by the present inventors. If converted, the amount of added vitamin C is quantified.
To convert the reaction position to reaction time, it is easy to measure the number of seconds after dropping the solution in advance and shake the scale. Conversion from shortened time to vitamin C concentration As described in the specification of “Japanese Patent Application No. 2004-77964”, it is to perform a reverse calculation from a table in which the relationship between vitamin C concentration and the shortened reaction time is measured in advance. Omitted because of the description.

  Now, in the interior etc. defined in [Claim 5] and summarizing the effects in the [0015] to [0020], particularly in the [0020] section of the specification, the [0011] As for those using the iodine starch reaction as defined in (1) to (4) of (1) to (4), when the liquid A droplet is continuously dropped into the B liquid, The triiodide ions (iodine) generated in the droplets permeate through the film formed on the outer periphery of the liquid A and elute into the liquid B little by little as described in the section [0017]. After a long period of time, if the B solution is reddish brown or starch is also eluted a little by this triiodide ion (iodine), it becomes colored purple.

  Invented in order to prevent this, as defined in [Claim 13], is a method of adding hydrogen peroxide to this B liquid. In the time order of 1 to 2 days, this hydrogen peroxide oxidizes triiodide ions (iodine) eluted from droplets of liquid A to iodate ions, and liquid B is triiodide ions (iodine). This prevents the reddish brown or reddish purple color that has reacted with starch.

  However, in the long time order of 2 days or more, the reverse reactivity of hydrogen peroxide reduction also appears, which reduces the iodate ions present in large quantities in the B liquid to iodine, On the contrary, the B liquid is made reddish brown by the generated iodine or triiodide ions generated from it, which is oxidized to gaseous oxygen and water. At this time, the hydrogen peroxide concentration is lowered, the reaction described in the item [0031] does not occur, and the reddish brown color is fixed. Therefore, the procedure for adding hydrogen peroxide to the liquid B is preferably mixed with the liquid B within one day before the performance, or just before the performance if desired.

As described above, the chemical reaction applied to the interior of [Claim 1], [Claim 2] or [Claim 5] is a vibration reaction, a clock reaction, a reaction in which hydrogen ions or hydroxide ions are generated. The clock reaction that suddenly obtains a deep reddish or dark blue-violet color of the iodine starch reaction from iodate, sulfite and starch has been described in detail from (2) of item [0011]. A similar demonstration effect can be obtained for reactions such as (11).
For example, when the Belousov-Zhabotinsky reaction as in (8) of item [0011] is used, repeated discoloration in which the color changes from green, blue, purple, red and back to green is seen in the interior. be able to.

  In addition, in the case of using the (clock) reaction in which hydroxide ion (OH-) is generated by mixing (6) thiosulfate and periodate in [0011], the pH indicating the pH change of this mixed solution is used. If a pH indicator with several different discoloration points is mixed and applied as an indicator, it is possible to construct an interior whose color changes one after another, for example, red, orange, yellow, green, blue, indigo, and purple. is there. This relates to [Claim 14] to [Claim 23], which will be described in detail later.

  Now, as means for initiating the vibration reaction, the clock reaction, and the reaction in which hydrogen ions or hydroxide ions are generated as described above, as described in [Claim 1], [Claim 2], and [Claim 5]. Although the case of using such a method has been described, as a method of mixing the solution at a constant time interval, a method using so-called “shishidoshi” transmitted from ancient times in Japan can be considered.

[Claim 7] describes a method of starting a vibration reaction, a clock reaction, and a reaction in which hydrogen ions or hydroxide ions are generated by using this “shishio doshi”, and the reaction is started by mixing. Two or more kinds of solutions are introduced little by little into a “shishio doshi” shape, and the solution is sufficiently accumulated. When this “shishio doshi” is activated, the solution flows into the container all at once and the two or more kinds of solutions are mixed.
This “shishio doshi” that receives two or more kinds of solutions may take a method in which two or more of them operate separately and the solution in them flows into one container, or the connection shown in (16 in FIG. 3). As in the case of “Shishidoshi”, two or more “Shishidoshi” may be connected, and when the inflow operation is activated, the solution may be poured into one container (17 in FIG. 3) and mixed at the same time.
If the container is provided with an outlet (18 in FIG. 3) through which the solution is discharged little by little, the solution after the completion of the reaction is slowly discharged, and then the container is emptied until “Shishidoshi” is activated. Thus, the reaction by the next solution mixing can be awaited.
The container may be as shown in (17 in FIG. 3), or a tubular container as shown in FIG. 4 of [Example 4] described later.

There is a phenomenon in which two or more kinds of solutions are mixed and an acidic or alkaline substance is slowly generated by a chemical reaction.
For example, in the reaction (5) of item [0011], hydrogen ions (hydrochloric acid) are slowly generated by hydrolysis and become acidic. In reactions (6) and (7), hydroxide ions are generated by chemical reaction. The solution slowly becomes alkaline.

  At this time, if a pH indicator whose color changes depending on pH is added to one or more of two or more types of solutions, there is no change up to the discoloration point at which the indicator changes color, and the amount of hydrogen ions or hydroxide ions generated This is a phenomenon similar to a clock reaction, in which the color of the solution suddenly changes as it passes through the discoloration point.

  What applies this phenomenon to interiors and the like is defined in [Claim 2], [Claim 5] and [Claim 7], but what is considered to be excellent in the composition of the reaction component [Claim 14]. ]. This reaction component is not listed in [0011] (1) to (11).

[Claim 14] In the color development of the indicator, the thiosulfate is oxidized by the reaction of thiosulfate such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate with hydrogen peroxide to produce tetrathionate, At this time, hydrogen ions are consumed and the solution becomes alkaline.
This chemical reaction is described as follows.
2 · S2O3 (2-) + H2O2 + 2 · H + = S4O6 (2-) + 2 · H2O
Here, S2O3 (2-) is a thiosulfate ion, H2O2 is hydrogen peroxide, H + is a hydrogen ion, S4O6 (2-) is a tetrathionate ion, and H2O is water. It shows that ions are involved in 2 equivalents of the reaction, and the symbol of = is a symbol used in place of the right arrow symbol indicating the progress of the reaction, and indicates that the reaction proceeds from the left side to the right side.
This means that two thiosulfate ions are oxidized by one molecule of hydrogen peroxide, consuming two hydrogen ions, resulting in one tetrathionate ion and two molecules of water. Therefore, the acidity of the acidic solution slowly decreases due to the consumption of hydrogen ions, and the reaction proceeds even in neutral or alkaline aqueous solution, and the hydroxide ions increase due to the consumption of hydrogen ions. The alkalinity of becomes stronger.

Now, if a pH indicator is mixed in the mixed solution that causes this reaction, an interior or the like that changes color can be formed. [Claim 2], [Claim 5] and [Claim 7] The effect can be brought out when applied to the interior or the like defined in (1) or “toy or interior” defined in Japanese Patent Application No. 2004-177997.
The advantage of applying the reaction shown in [Claim 14] to these interiors and the like is that the material is generally safe and inexpensive, and that a sufficient reaction can be caused by using a small amount of these materials. It is a point that can be done. [0011] The reactions shown in items (6) and (7) can be used for such interiors, but the materials are not common and relatively expensive materials such as periodate are used. It is necessary to use those which are harmful to human bodies such as formaldehyde, and the reaction of [Claim 14] is excellent in this respect.

As defined in [Claim 15], for the purpose of applying to the interior defined in [Claim 2], [Claim 5] and [Claim 7], in the coloration of the indicator constituting it, periodate Reaction of periodate such as potassium acid, sodium periodate, and ammonium periodate with thiosulfate such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate results in oxidation of thiosulfate to tetrathionate A phenomenon can be used in which a salt is formed, hydrogen ions are consumed and the solution becomes alkaline.
[0041] As mentioned in [0041], this reaction requires the use of a relatively expensive periodate, which is a disadvantage, while the advantage is that the reaction is relatively fast and the color on the alkaline side is It is easy to come out.

This chemical reaction is described as follows.
2 · S2O3 (2-) + IO4- + 2 · H + = S4O6 (2-) + IO3- + H2O
Here, S2O3 (2-) means thiosulfate ion, IO4- means periodate ion, H + means hydrogen ion, S4O6 (2-) means tetrathionate ion, IO3- means iodate ion, and H2O means water. The symbol 2 · indicates that the ion is involved in 2 equivalents of the reaction, and the symbol = is a symbol used in place of the right arrow symbol indicating the progress of the reaction, and the reaction from the left side to the right side is performed. It shall represent progress.
This formula means that two thiosulfate ions are oxidized by one molecule of periodate ion, consuming two hydrogen ions, one tetrathionate ion and one iodate. Because of the generation of ions and one molecule of water, the acidity of the acidic solution slowly decreases due to the consumption of hydrogen ions, and the reaction proceeds even in neutral and alkaline aqueous solutions. Hydroxyl ions increase and the alkalinity of the solution increases.

In the description of items [0037] to [0043], a pH indicator obtained by mixing methyl red and bromthymol blue and phenolphthalein or cresolphthalein as shown in [16] as a pH indicator. Is applied, seven colors of rainbow can appear depending on its pH.
Methyl red has a discoloration point near pH 5, showing red on the acid side, orange near pH 5, yellow on the alkali side, and bromthymol blue having a discoloration point near pH 7, on the acid side. Yellow, green near pH 7, blue on the alkali side, phenolphthalein or cresolphthalein has a discoloration point near pH 9, colorless on the acidic side, pale red near pH 9, more alkaline on this side Shows red.
Accordingly, a pH indicator in which these pH indicators are mixed at an appropriate ratio is red on the acidic side of pH 5, orange near pH 5, yellow near pH 6, green near pH 7, blue near pH 8, indigo near pH 9, pH 9 It shows a purple color change on the alkali side.
Furthermore, when a little thymol blue having a discoloration point near pH 9, yellow on the acid side, green on pH 9 and blue on the alkali side is added a little, the indigo color near pH 9 comes out well. .

  Here, for example, according to the configuration of [Claim 2] or [Claim 5] or [Claim 7], the solution defined in [Claim 14] or [Claim 15] is mixed, and one or both of the mixed are mixed. When an acid such as phosphoric acid or hydrochloric acid is mixed with the aqueous solution so that the pH of the mixed solution is 4 or less, the mixed solution first shows an acidic red color, and the pH of the solution changes. In the course of development, various color changes such as red, orange, yellow, green, blue, indigo, and purple can be caused, and an interesting interior with color change can be constructed.

Thus, in claim 16, a pH indicator that changes into seven colors of red, orange, yellow, green, blue, indigo and purple is defined. The advantage of this composition indicator is that the relationship between color and pH is simple and easy to understand, as described above, so that the color of the current solution can be determined by this color.
However, a disadvantage is that, when making alkaline by mixing the solutions defined in [Claim 14] and [Claim 15], it takes a long time until indigo and purple are generated. That is, although the hydroxide ion due to the reaction simply increases with time, the pH index is log, the pH 9 hydroxyl ion concentration is 10 times the pH 8 hydroxide ion concentration, from pH 8 blue to pH 9 indigo. The time taken to move to pH is about 10 times the time taken to move from green at pH 7 to blue at pH 8. It takes 10 times as long as the indigo color to develop until the purple color near pH 10 develops beautifully.
In addition, the time to shift from acidic red to orange can be controlled by adjusting the acidity, and it remains red for a certain period of time, and then suddenly shifts to orange, and then yellow, green, blue, indigo one after another. It is necessary and acceptable to make the transition of purple and color interesting.

The composition of the pH indicator defined in [Claim 17] is considered in order to solve the problem caused by the composition of the indicator defined in [Claim 16] described in [0046] above, It defines a pH indicator obtained by mixing methyl red and bromthymol blue and cresol red (o-cresol sulfophthalein).
Since the pH indicator of this composition appears indigo or purple with a relatively low alkalinity, this pH indicator can be used, for example, according to [Claim 2], [Claim 5], [Claim 7] and [Claims] of the present invention. 14] and [Claim 15], and when applied to "toys or interiors" defined in Japanese Patent Application No. 2004-177997, it takes a long time for the indigo and purple to develop color. Problems can be avoided, and more effective interiors or “toys or interiors” can be configured.
Moreover, the composition of the pH indicator defined in [Claim 17] can also be applied as the pH indicator defined in [Claim 1] of Japanese Patent Application No. 2004-61319.

Of the above components, methyl red has a discoloration point near pH 5, showing red on the acid side, orange near pH 5, yellow on the alkali side, and bromthymol blue discoloring point near pH 7. Yellow on the acidic side, green on the pH side near blue, blue on the alkali side, and cresol red (o-cresol sulfophthalein) has a discoloration point near pH 8, yellow on the acidic side, pH 5 Orange in the vicinity, red on the alkali side.
Therefore, a pH indicator in which these pH indicators are mixed in an appropriate ratio is red on the acidic side of pH 5, orange near pH 5, yellow near pH 6, green near pH 7, blue near pH 7.5, indigo near pH 8. , It shows a purple color change on the alkali side from pH8.
Further, when phenolphthalein or cresolphthalein, which has a discoloration point near pH 9, is colorless on the acidic side, pale red near pH 9, and red on the alkali side, is added, and a purple color of pH 9 or more is further added. It comes out well. Moreover, when phenolphthalein or cresolphthalein is added excessively, it becomes possible to develop reddish purple in a range where the alkalinity is higher after purple of pH 9 or higher.

  As shown in [Claim 19], the pH indicator defined in [Claim 17] or [Claim 18] is applied and mixed as the indicator defined in [Claim 14] or [Claim 15]. Alternatively, if an acid such as phosphoric acid, hydrochloric acid or sulfuric acid is mixed in both aqueous solutions and the pH of the mixed solution is adjusted to 4 or less, the mixed solution first shows acidic red, As the pH of the solution changes, it can cause various color changes such as red, orange, yellow, green, blue, indigo, and purple, and constitute an interesting interior etc. Can do. In this case, indigo and purple are colored with a lower alkalinity than that defined in [Claim 16], so that a more effective interior or "toy or interior" can be constructed.

In addition, when an acid is added to one of the solutions to be mixed in advance in [Claim 14] or [Claim 15], when the acid is added to the thiosulfate side, the thiosulfate is decomposed by the acid and sulfur and sulfurous acid gas are added. Therefore, it should be added to the hydrogen peroxide side in [Claim 14] and to the periodate side in [Claim 15]. Since hydrogen peroxide increases its stability against self-decomposition under weak acidity, it is important to add an acid to the hydrogen peroxide side of [Claim 14] in order to increase its storage stability. .
In general, a small amount of acid such as phosphoric acid is added to the hydrogen peroxide solution of about 3% marketed as oxidol to ensure its stability.

Next, [claim 20] will be described in terms of items [0052] to [0056].
As shown in [0040], a combination of the solutions shown in [Claim 14], that is, an aqueous thiosulfate solution such as sodium thiosulfate in solution C and an aqueous hydrogen peroxide solution in other solution D When these solutions are used and mixed, the solution slowly becomes alkaline, but this reaction is promoted by a trace amount of copper ions or iron ions to the order of several ppm, and particularly copper ions show good results.
In addition, the characteristics of iron ions until the solution becomes neutral are not significantly different from those of copper ions. Yes.

This is because copper ions or iron ions catalyze the reaction in which thiosulfate is oxidized by hydrogen peroxide. This will be described using copper ions as an example.
In an aqueous solution, copper ions can take the form of divalent copper ions (Cu2 +) and monovalent copper ions (Cu +). Ions (Cu2 +) act as oxidizing agents, and substances that are easily reduced are oxidized, and themselves are reduced to monovalent copper ions (Cu +). Here, monovalent copper ions (Cu +) are oxidized by hydrogen peroxide present in the surroundings, and are returned to divalent copper ions (Cu2 +) again, and the oxidation and reduction reaction circulates. At this time, the copper ions act as a catalyst when the entire reaction is viewed from the outside.

The same can be said for the catalytic phenomenon of the above [0052] even with iron ions.
Although iron ions can be in a divalent or trivalent state in an aqueous solution, trivalent iron ions (Fe3 +) have a strong oxidizing action, and divalent iron ions (Fe2 +) have a strong reducing property.
If trivalent iron ions (Fe3 +) are contained in the aqueous solution and at the same time a substance that is easily oxidized is included, the trivalent iron ions (Fe3 +) act as an oxidizing agent, and the substances that are easily reduced are oxidized. Is reduced to divalent iron ions (Fe2 +). Here, the divalent iron ion (Fe2 +) is oxidized by hydrogen peroxide present in the surroundings, and returns to the trivalent iron ion (Fe3 +) again, and the oxidation and reduction reaction circulates. At this time, the iron ions act as a catalyst when the entire reaction is viewed from the outside.

When a divalent iron ion (Fe2 +) is contained in the aqueous solution, the divalent iron ion (Fe2 +) is oxidized to a trivalent iron ion (Fe3 +) by hydrogen peroxide present in the surrounding area. In the same manner as in the item [0053], a reaction in which trivalent iron ions (Fe 3+) are easily oxidized is followed.
In addition, in [0051], it was described that iron ions are inferior to copper ions because of the characteristics when the solution goes from neutral to alkaline, but this is because the iron ions are very neutral or alkaline. This is probably because iron hydroxide having a low water solubility is likely to be produced, and if it is too neutral, iron ions are reduced due to the generation of this substance and the catalytic action is lowered. There is no problem because copper ions have a lower tendency than iron ions, and copper ions show good results in this respect.

Therefore, when a pH indicator as shown in, for example, [Claim 16] to [Claim 18] is added to either or both of the solution C and the solution D and these are mixed, Discoloration can be accelerated. This is the object of [claim 20].
In order to speed up the reaction, a method of increasing the concentration of the reactants can be considered, but it can be said that it is a better choice to use a catalytic substance that works in a very small amount considering the economy or the amount of the substance to be discharged increases.
In order to slow down the reaction, the concentration of the reactant can be lowered, and this can be done easily.

When many copper ions or iron ions are used, they are harmful to the environment. However, as will be described later in the examples, a concentration of several ppm has a sufficient effect and does not significantly affect the environment. For example, the allowable amount of copper ions or iron ions in tap water is set in consideration of the fact that it does not affect the taste, and the allowable amount is 1 ppm for copper ions and 0.3 ppm for iron ions. It has become. Further, the amount of copper necessary for a human day is said to be 2 to 5 mg. From this, it can be seen that the amount of copper applied in the present invention is at a level causing no safety problem.
It should be noted that the amount of iron required per day for humans is larger than copper, and is said to be 7 to 48 mg per day. It is said that red blood cells in blood are also fixed to hemoglobin hemoglobin with a role of carrying oxygen, and it is said that adult human body contains 3 to 4 g of iron.
However, it goes without saying that both elements are harmful if taken in excess of the daily requirement.

Next, a simple quantitative measurement method for copper ions or iron ions in [Claim 21] will be described below.
In the paragraphs [0051] to [0056], the method of increasing the reaction rate shown in [Claim 14] by adding copper ions or iron ions was described, but conversely, it is contained in the solution from this reaction time. The amount of copper ions or iron ions can be measured.

  Generally, iron ions are insoluble as iron hydroxide even if neutral, and are easily removed from water, and tap water contains only a very small amount, as can be seen from the standard value of tap water of 0.3 ppm. Also, the maximum copper ion is about 1 ppm. This is 4.08 mg / l in terms of the concentration of the aqueous solution of copper sulfate pentahydrate.

Here, as shown in [Claim 14], an aqueous thiosulfate solution is prepared as one solution C, and an aqueous hydrogen peroxide solution is prepared as the other solution D. The aqueous hydrogen peroxide solution is prepared, for example, by dissolving oxidol, which is a commercially available 3% aqueous hydrogen peroxide solution, in water. As shown in the examples, the hydrogen peroxide concentration of the solution D may be very dilute, about 0.15%.
At this time, for example, a pH indicator as shown in [Claim 16] to [Claim 18] is added to either or both of them.
When preparing these solutions, prepare solutions C and D using water that does not contain copper ions and iron ions, such as distilled water or ion exchange water, mix them, and measure the time when discoloration occurs. deep. In the case of a pH indicator as shown in [Claim 16] to [Claim 18], seven colors appear. Therefore, the color change can be clearly understood, and yellow or the like where the color appears for a short time is selected. The time when the color appears may be measured.
Further, when preparing the solution C or the solution D, for example, copper sulfate pentahydrate (CuSO4 · 5H2O) or iron (III) sulfate (Fe2 (SO4) 3) In the form of an aqueous solution containing a small amount of copper ions or iron ions. When the solution C and the solution D to which copper ions or iron ions are added are mixed, discoloration to each color occurs in a time earlier than that using water containing no copper ions and iron ions. Similarly, it is good to know the color change most clearly, select yellow or the like whose color appears for a short time, and measure the time when the color appears. Here, by changing the amount of copper ions or iron ions, the time for the color change to occur is measured in advance, and a correspondence table between the concentration of each ion and the color change time is prepared.

By using the time measured in [0059] as a reference and comparing the result of measuring the time until each color changes with water containing copper ions or iron ions to be measured, The concentration of trace amounts of copper ions or iron ions contained can be determined. As described in [0059], when a pH indicator that appears in seven colors as shown in [Claim 16] to [Claim 18] is used as the indicator, the most discoloration can be clearly seen, and the color is It is preferable to select yellow or the like having a short appearance time, and measure the appearance time of the color as a comparison target.
In addition, when both copper ions and iron ions are contained in the measurement target aqueous solution, it is difficult to quantitatively determine each of them.
Further, as described in [Claim 21], when copper ions or iron ions are simply quantitatively measured in an interior or the like using the tubular container of [Claim 2], the influence of copper ions or iron ions is affected. The phenomenon that the time until the appearance of each color is shortened and the reaction position of the reaction described in [Claim 2] moves is used. If this amount of movement is converted into a shortened time, the amount of copper ions or iron ions can be easily quantitatively measured.
In order to convert the reaction position into the reaction time, it is easy to measure the number of seconds after the solution is dropped and shake the scale.

Tetrathione produced by oxidation of thiosulfate in a mixture of thiosulfate and hydrogen peroxide as defined in [Claim 14] or in a mixture of thiosulfate and periodate as defined in [Claim 15] Acid salts are easily decomposed, and sulfur compounds such as sulfur and bisulfite are generated. This is generally felt as “sulfur smell”, and this is somewhat felt in the solution after the reaction.
In order to suppress this, it is effective to mix sulfites such as sodium sulfite, potassium sulfite and ammonium sulfite with the solution after the reaction, as shown in [Claim 22]. This should be added to the solution after the reaction is completed, since it will interfere with the reaction if added before the reaction in which the alkaline substance is generated.
In addition, the same effect can be obtained by applying a weakly alkaline substance by adding an alkaline substance to bisulfite instead of the above sulfite, but this is equivalent to adding sulfite, [ It does not depart from claim 22].
In addition, the method of adding the copper salt shown in [Claim 21] is also effective for suppressing the “sulfur odor”.
If the thiosulfate used in [Claim 14] or [Claim 15] is acidified during storage, sulfur or sulfite is easily generated and decomposed. Since it decomposes slowly even by acidification by absorption of carbon dioxide in the air, in order to prevent this, a small amount of hydrogen carbonate or carbonate such as sodium hydrogen carbonate or potassium carbonate is added to prevent acidic decomposition It is effective to do. This is to prevent acidification by bicarbonate or carbonate. Also, chelating agents such as disodium ethylenediaminetetraacetate (EDTA2Na) are used to mask and inactivate metal salts that are contained in tap water and catalyze this oxidation in order to prevent oxidation due to oxygen dissolved in the solution. It is also effective to add However, as described in [Claim 20] and [Claim 21], when positively adding copper ions or iron ions or using them for quantitative detection of both ions, mask these. A chelating agent such as disodium ethylenediaminetetraacetate (EDTA2Na), which has the effect of depriving the catalytic action, should not be added.

Finally, as defined in [Claim 5], the granular droplets produced by the reaction of alginate and calcium salt, etc., are sealed inside by changing the internal acidity or alkalinity. The characteristics when using Congo red as the pH indicator will be described.
By applying a chemical reaction such as [Claim 14] or [Claim 15] or [0011] (5) or (7) of the specification, the granular droplets are formed inside the granular droplets. Acidity or alkalinity can be changed. Further, the acidity or alkalinity inside the droplet can be changed by a method in which an acidic or alkaline solution outside the membrane is permeated into the inside of the membrane using the osmotic pressure between the solution and the membrane. At this time, if a pH indicator is contained inside the droplet, the color inside the droplet can be changed. Needless to say, those defined in [Claim 16] to [Claim 18] can be applied as pH indicators.

However, as a phenomenon of osmotic pressure between the solution and the membrane, the substance inside the membrane also diffuses outside the membrane, and the pH indicator contained inside the membrane is diffused outside. For this reason, if the operation for generating the droplets is continued, the solution outside the film gradually becomes colored with the color of the pH indicator, and the coloring of the droplets as a presentation becomes inconspicuous, resulting in a decrease in the presentation effect. .
Therefore, in this case, this problem can be avoided by using a strong pH indicator as the applied pH indicator, and as defined in [Claim 23], Congo Red is preferred in this case. Congo red is a pH indicator that has a color change point near pH 4.3 and is acidic and bluish purple, red near pH 4.3, and red-orange on the alkaline side. Congo red is also used as a dye, a substance that appeared in the early days of the development of chemical dyes, and as it is used for cell staining in the fields of medicine and the like, it is highly dyeable and dyed. After that, it has the feature that it is hard to lose color.
Congo red applied here is strongly dyed to a high-viscosity solid substance of high molecular weight, such as alginate or alginic acid, which is mediated by calcium ions, etc. It will not spread to you. This can prevent the solution outside the film from being colored.

  According to the present invention, it is possible to provide an interior or the like that brings about the mysteriousness that suddenly a dark reddish purple or bluish purple occurs without doing anything, the colored color changes one after another, or various colors appear repeatedly. . With this interior, children are interested in the principle of this phenomenon, and by explaining and explaining this scientific phenomenon, the concept of three primary colors, acid and alkali, Teaching children about the concept of pH, which is the strength of alkalis, precipitation of iodide ions and triiodide ions by redox and color development by iodine starch reaction, the nature of vitamin C, vibrational reaction and clock reaction This is effective for educational aspects.

In addition, according to the present invention, the above phenomenon can be generated one after another without human intervention,
An interior that emphasizes the mystery of the phenomenon that occurs can be given.
A solid sphere-shaped object can be created from the solution, and the effect of changing the color of the sphere-shaped object can be produced, and an interior that emphasizes the mystery of the phenomenon that has occurred can be provided.

  Furthermore, according to the present invention, it is possible to constitute an interior or the like that can be used stably for a long period of time by preventing alteration or decomposition of reagents used in the interior or the like.

  According to the present invention, the conventional reagent for detecting vitamin C using reductive decolorization with vitamin C using an indophenol reagent such as dichloroindophenol, the reagent is expensive, and an aqueous solution of this reagent. It is easy to disassemble, it can not withstand long-term storage, it takes time and effort to create detection reagents, it is very difficult to handle except for specialists in analytical chemistry, it is cheap, easy to handle, long-term storage, easy to handle A method for measuring vitamin C content can be provided. In the same way, we provide a method for detecting extremely small amounts of copper ions, and quantitatively measure vitamin C, which is a familiar and important substance, and inform children about the fun of science. It has an effect on the educational aspect, which is an opportunity to teach.

  The best mode for carrying out the present invention is best for interiors, displays, toys, and accessories that produce scientific effects using scientific phenomena. In addition, it is best suited as a learning device that can detect vitamin C easily at home and teach it to children and the like, and a demonstration device with the character of magic performed at exhibitions and parties.

  Moreover, as an embodiment for carrying out the present invention, a “toy or interior that changes color” as defined in Japanese Patent Application No. 2004-177997 is also suitable.

  A series of procedures shown in [Claim 1], [Claim 3], [Claim 4], [Claim 9], and [Claim 10] will be described using an embodiment.

As shown in FIG. 1, a solution having the following formulation is prepared as one solution C (5 in FIG. 1), which is defined in [Claim 1] and in which a clock reaction is started by mixing.
1000cc water
Soluble starch 2.0g (0.2% aqueous solution)
Sodium sulfite 0.88g (0.088% aqueous solution)
20 g of urea (2% aqueous solution)
Thymol 0.02g (0.002% aqueous solution)
EDTA2Na 0.04 g (0.004% aqueous solution)
Sodium hydroxide 0.16g (0.016% aqueous solution)
However, EDTA2Na is ethylenediaminetetraacetic acid disodium.
In addition, as described in [0026] (1), the solution of the above preparation is, for example, soluble starch 5%, sodium sulfite 2.2%, thymol 0.05%, sodium hydroxide 0.4%, If 40 cc of a high concentration of 25% urea and 5% ethyl alcohol is prepared and diluted 25 times with 960 cc of water just before use, it can withstand long-term storage. As a result of diluting this, urea becomes 1%. Even at this level, the effect of preventing starch degradation can be expected.

In addition, a solution having the following composition is prepared as the other solution D (6 in FIG. 1), which is defined in [Claim 1] and starts a clock reaction by mixing.
1000cc water
Potassium iodate 2g (0.2% aqueous solution)
Phosphoric acid 8g (0.8% aqueous solution)

  Each of these is stored in a separate tank container, the flow rate is adjusted with a pinch cock, and each is set to a flow rate of 0.05 cc (1 drop per second), and this is shown in (7 in FIG. 1). The solution received in B and mixed in this funnel B is added dropwise to the outlet of funnel A indicated by (3 in FIG. 1). A wire (4 in FIG. 1) for securing a clearance between the tip of the funnel A and the tubular container (1 in FIG. 1) is wound around the tip of the funnel A.

  Now, the solution C (5 in FIG. 1) and the solution D (6 in FIG. 1) dropped onto the funnel B are mixed on the funnel B, dropped near the outlet of the funnel A, and passed through the funnel A. Then, when it flows through the tubular container, it becomes a lump of a colorless and transparent solution as indicated by (2 in FIG. 1), and is further sufficiently mixed while flowing. In the case of the formulation shown in the paragraphs [0071] and [0072], the solution mass suddenly becomes a very dark red at the position of the tubular container at the time when about 8 seconds have passed in the case of the formulation shown in the paragraphs [0071] and [0072]. A clear purple solution was obtained.

  As shown in the paragraph [0071], the solution C contains urea as defined in [Claim 9] and sodium hydroxide as defined in [Claim 10], but there is no such mixture. Solution C and Solution D mixed after 2 weeks did not develop a reddish purple color, but only a light reddish brown triiodide ion (iodine). After a further two weeks with a lot of air in the tank, the light reddish brown triiodide ion (iodine) also disappeared, but this was because the sodium sulfite added to the C solution was oxidized by oxygen This is thought to be because it changed to sodium sulfate and the reduction reaction of potassium iodate to the triiodide ion (iodine) no longer occurred. This is defined in [Claim 9] and [Claim 10], and can be avoided by the method described in detail in (1) to (7) of [0026] in the specification. Even when C is stored as it is, oxidation of sodium sulfite can be avoided by the methods (2), (3), (6), and (7) in the item [0026].

  [Claim 2], [Claim 3], [Claim 4], [Claim 14], [Claim 17], [Claim 18], [Claim 19], [Claim 22] A series of procedures will be described using an embodiment.

As shown in FIG. 1, a solution having the following formulation is prepared as one solution C (5 in FIG. 1) in which generation of hydroxide ions is started by mixing, as defined in [Claim 2].
1000cc water
Sodium thiosulfate 33g (3.3% aqueous solution)
Methyl red 5.5mg (0.00055% aqueous solution)
Cresol red 26.7mg (0.0027% aqueous solution)
Bromthymol blue 26.7mg (0.0027% aqueous solution)
Phenolphthalein 40.0mg (0.004% aqueous solution)
Sodium bicarbonate 100mg (0.01% aqueous solution)
In addition, methyl red, cresol red (o-cresol sulfophthalein), bromthymol blue, and phenolphthalein actually made an alkaline solution dissolved at a concentration 60 times higher than this, and dissolved this to obtain solution C. Thereafter, the excess alkali contained in the indicator was neutralized with dilute hydrochloric acid to neutralize, and then sodium bicarbonate was added. This solution C is a greenish liquid.

Moreover, the solution of the following preparation is created as the other solution D (6 of FIG. 1) which starts generation | occurrence | production of a hydroxide ion by mixing defined in [Claim 2].
1000cc water
Hydrogen peroxide 1.5g (0.15% aqueous solution)
Hydrogen chloride 0.063g (0.0063% aqueous solution)
Actually, hydrogen peroxide was prepared by diluting 20% of oxidol, which is a 3% hydrogen peroxide aqueous solution, with water, and dilute hydrogen chloride aqueous solution (very dilute hydrochloric acid) And diluted 20 times.

  Each of these is stored in a separate tank container, the flow rate is adjusted with a pinch cock, and each is set to a flow rate of 0.05 cc (1 drop per second), and this is shown in (7 in FIG. 1). The solution received in B and mixed in this funnel B is added dropwise to the outlet of funnel A indicated by (3 in FIG. 1). A wire (4 in FIG. 1) for securing a clearance between the tip of the funnel A and the tubular container (1 in FIG. 1) is wound around the tip of the funnel A.

Now, the solution C (5 in FIG. 1) and the solution D (6 in FIG. 1) dropped onto the funnel B are mixed on the funnel B, dropped near the outlet of the funnel A, and passed through the funnel A. Then, when it flows through the tubular container, it becomes a lump of a red transparent solution as shown by (2 in FIG. 1), and further mixed well while flowing. In the case of the formulation shown in the paragraphs [0077] and [0078], the solution mass suddenly becomes an orange-colored transparent solution at the position of the tubular container at the time when 10 seconds have elapsed in the case of the preparation shown in items [0077] and [0078]. The color gradually changes, yellow after 12 seconds, green after 14 seconds, blue after 25 seconds, indigo after 32 seconds, purple after 40 seconds, and deep red-purple after 120 seconds. became.
In this embodiment, it takes about 10 seconds for the color to change from red to orange, and after that, the color changes sequentially and changes to purple within a relatively quick time of about 40 seconds. For effective production, it is better to take some time until the color changes from red to orange, and the color change to purple is not too long. It is considered that the mixing ratios of solution C and solution D as in the example are suitable.
If you try to change the color to purple more quickly, the transition from orange to yellow and green will be too early, and the effect will be inferior, and if you adjust the solution thinly so that you can see this transition slowly, the color will transition to purple easily. The result is not. The above is a preparation example of a solution suitable for production. The present invention is not limited to this adjustment value, and various adjustments are made in consideration of the container shape and production.

  The mixed solution has a slight “sulfur smell”, but when discharged to a waste tank containing 100 cc of 3% aqueous sodium sulfite solution as shown in [Claim 22], this “sulfur” The “smell” disappeared.

  A series of procedures shown in [Claim 5], [Claim 6], [Claim 9], [Claim 10], [Claim 11], and [Claim 13] will be described using an embodiment. .

As shown in FIG. 2, a solution having the following formulation is prepared as one solution A (8 in FIG. 2), which is defined in [Claim 5] and in which a clock reaction is started by mixing.
1000cc water
Soluble starch 2.0g (0.2% aqueous solution)
Sodium sulfite 0.88g (0.088% aqueous solution)
Sodium alginate 10g (1% aqueous solution)
Urea 100g (10% aqueous solution)
Thymol 0.02g (0.002% aqueous solution)
EDTA2Na 0.04 g (0.004% aqueous solution)
Sodium hydroxide 0.16g (0.016% aqueous solution)
Potassium iodide 0.1g (0.01% aqueous solution)
Potassium sorbate 1.33g (0.133% aqueous solution)
However, EDTA2Na is ethylenediaminetetraacetic acid disodium.
Solution A becomes a colorless, transparent, slightly viscous liquid.

In addition, a solution having the following composition is prepared as the other solution B (9 in FIG. 2) which is defined in [Claim 5] and starts a clock reaction by mixing.
1000cc water
Potassium iodate 2.5g (0.25% aqueous solution)
Phosphoric acid 4g (0.4% aqueous solution)
Calcium hydrogen phosphate monohydrate 15g (1.5% aqueous solution)
Calcium nitrate tetrahydrate 15g (1.5% aqueous solution)
Hydrogen peroxide 0.3g (0.03% aqueous solution)
However, in practice, hydrogen peroxide is prepared by diluting 100% of oxidol, which is a 3% aqueous hydrogen peroxide solution with water (10 cc of oxidol in 990 cc of water). Added just before.
Solution B becomes a colorless and transparent liquid.

  Among these, the solution A is stored in a tank container, the solution B is put in the container of the solution B indicated by (15 in FIG. 2), and the “slatted” plate indicated by (13 in FIG. 2) (see FIG. 2). Set the sloped path shown in 10) and another path shown in (14 in FIG. 2), adjust the flow rate of Solution A with a pinch cock, and give a flow rate of 0.005 cc (1 drop per 10 seconds) And drop it into a container indicated by (14 in FIG. 1).

  Now, the colorless and transparent solution A dropped in the container of the solution B (15 in FIG. 2) becomes a round shape at the moment when it is dropped into the solution B, and the periphery of the solution B is solidified and is colorless and transparent. Large droplets (12 in FIG. 2) are formed. At this time, small droplets (11 in FIG. 2) may be generated at the same time.

The generated small droplet (11 in FIG. 2) falls from the clearance of the “snow-like” plate shown by (13 in FIG. 2) and passes through another path shown by (14 in FIG. 2) (FIG. 2). It does not enter the sloped path shown in 9) of 2 and is excluded at the lower part of the container for solution B (15 in FIG. 2).
The colorless and transparent large droplet (12 in FIG. 2) slowly passes through the “sink-like” plate shown in (13 in FIG. 2) and the inclined path shown in (10 in FIG. 2). It moves toward the bottom of the container of B (15 in FIG. 2), and after about 20 seconds, it can be seen that the very thin film portion on the outer side turns reddish purple, and after 40 seconds, a clearly large droplet (FIG. 2). A purple-red ring surrounding 12) was seen, and after 300 seconds it had fallen to the bottom of the solution B container (15 in FIG. 2), and became a large liquid-dyed droplet.

  In addition, when urea is not added to the solution A, a large droplet (12 in FIG. 2) does not easily fall along the inclined path shown by (10 in FIG. 2), and some of the liquid stops and stops in the middle. When the liquid dropped into the solution B, a minute bubble generated by the impact was attached, and a state of floating above the solution B appeared.

  In addition, when potassium iodide is not added to solution A, the above-mentioned discoloration time is long, and after 72 seconds, it can be seen that the outer thin film portion finally turns reddish purple. It was in a state where it dropped to the bottom of the solution B container (15 in FIG. 2) before being recognized.

  Further, when hydrogen peroxide is not added to the solution B, when the dropping of the liquid A is continued for about 1 hour, a large droplet (12 in FIG. 2) accumulated at the bottom of the container of the solution B (15 in FIG. 2) When the reddish purple color diffuses and the solution B near the bottom of the solution B container (15 in FIG. 2) becomes reddish purple or reddish brown over time, but hydrogen peroxide has been added No such discoloration was observed, and no such discoloration was observed as a result of continuing dropping for 12 hours. However, it was confirmed that the time for starting discoloration extended from 20 seconds to about 30 seconds by dropping for 12 hours.

  Soluble starch, sodium sulfite, thymol, potassium iodide and sodium hydroxide were not added as components in Solution A, but 0.0027% of Congo Red was dissolved instead. However, after about 10 seconds, the outside of the film starts to turn blue-purple, and the inside becomes large red-orange droplets (3 in FIG. 2). After about 40 seconds, this is a blue-purple state and falls. In this example, the droplets using Congo Red are discolored by phosphoric acid existing outside the membrane, but are defined in [Claim 23] and described in [0063] of the specification. Like the effect described in detail, the external solution did not stain blue-violet.

  A series of procedures shown in [Claim 2], [Claim 7], [Claim 15], [Claim 16], and [Claim 22] will be described using an embodiment.

As shown in FIG. 4, a solution having the following formulation is prepared as one solution C (5 in FIG. 4) in which generation of hydroxide ions is started by mixing, as defined in [Claim 2].
1000cc water
Sodium thiosulfate 33g (3.3% aqueous solution)
Methyl red 5.5mg (0.00055% aqueous solution)
Bromthymol blue 26.7mg (0.0027% aqueous solution)
Thymol blue 2.3mg (0.00023% aqueous solution)
Phenolphthalein 110.0mg (0.011% aqueous solution)
Sodium bicarbonate 100mg (0.01% aqueous solution)
In addition, methyl red, bromothymol blue, thymol blue, and phenolphthalein actually make an alkaline solution dissolved at a concentration 60 times higher than this, and dissolve this to make solution C, and then the excess contained in the indicator The alkali was neutralized with dilute hydrochloric acid to neutral, and then sodium bicarbonate was added. This solution C is a greenish liquid.

Further, a solution having the following composition is prepared as the other solution D (6 in FIG. 4) in which generation of hydroxide ions is started by mixing, as defined in claim 2.
1000cc water
Potassium periodate 3.1 g (0.31% aqueous solution)
Hydrogen chloride 0.036g (0.036% aqueous solution)
In practice, a dilute hydrogen chloride aqueous solution (very dilute hydrochloric acid) was prepared by diluting 0.126% hydrochloric acid 3.5 times with water.

  Each of these is stored in a separate tank container, the flow rate is adjusted with a pinch cock, and each is set to a flow rate of 0.05 cc (1 drop per second), which is indicated by (16 in FIG. 4). Drip into the “Shishiodo”. When “Shishidoshi” is activated, the discharged solution is guided to the tubular container (1 in FIG. 4) and mixed there. This container has a shape in which a funnel-shaped receiving port and a tubular container part are combined. The tip of the funnel-shaped receiving port has a clearance between the tip of the funnel-shaped receiving port and the tubular container as shown in (4 of FIG. 4). Wire to secure is wound.

Now, the greenish solution C (5 in FIG. 4) and the colorless transparent solution D (6 in FIG. 4) dropped onto the funnel A (3 in FIG. 4) are mixed on the funnel A, resulting in a red color. The solution becomes a transparent solution of red and becomes a lump of red transparent solution as shown in (2) of FIG. 4 while flowing through the tubular container, and is further sufficiently mixed while flowing. In the case of the preparation shown in the paragraphs [0093] and [0094], the solution mass turns into an orange transparent solution at the position of the tubular container at the time when 1 second has elapsed in the case of the preparation shown in the paragraphs [0093] and [0094]. The color changes one after another, yellow after 2 seconds, green after 3 seconds, blue after 5 seconds, indigo after 10 seconds, purple after 100 seconds, and from the exit (18 in FIG. 4) It was slowly discharged.
In [Embodiment 4], the funnel B defined in [Claim 4] and shown in (7 in FIG. 1) is not used, but in this case, it is shown in (16 in FIG. 4). Since a large amount of solution is guided from the funnel A to the tubular container (1 in FIG. 4) at a time by the action of the connected “Shishidoshi”, the solution lump is easy to form, and the funnel B is omitted. Needless to say, the funnel B is better for the purpose of facilitating the formation of a lump of solution.
When the solution C and the solution D are poured into a container such as the container (17 in FIG. 3) instead of the tubular container, the entire mixed solution changes color as described above.

  The mixed solution has a slight “sulfur smell”, but when discharged to a waste tank containing 100 cc of 3% aqueous sodium sulfite solution as shown in [Claim 22], this “sulfur” The “smell” disappeared.

In the mixing of the solution combining [Claim 14] and [Claim 18], the time until each color is generated varies depending on the concentration of an acid such as thiosulfate, hydrogen peroxide, phosphoric acid or hydrochloric acid.
Since the concentration of thiosulfate and hydrogen peroxide affects the rate at which hydroxide ions are generated, it affects the time it takes to transition to yellow, green, blue, indigo, and purple after it turns orange. When it is dark, the transition time is fast, and when it is light, the transition time is long.
The concentration of acids such as phosphoric acid and hydrochloric acid simply affects the time until the color changes from red to orange, that is, the time when the color change is felt to start, and when the acid concentration is high, the time is long and low. In that case, the time is shortened. This is because the acid concentration affects the amount of hydrogen ions that must be consumed before reaching the discoloration point of the pH indicator.
These matters will be described using examples.

As shown in FIG. 1, a solution having the following formulation is prepared as one solution C (5 in FIG. 1) in which generation of hydroxide ions is started by mixing, as defined in [Claim 2].
1000cc water
Sodium thiosulfate 32g (3.2% aqueous solution)
Methyl red 5.5mg (0.00055% aqueous solution)
Cresol red 26.7mg (0.0027% aqueous solution)
Bromthymol blue 26.7mg (0.0027% aqueous solution)
Phenolphthalein 40.0mg (0.004% aqueous solution)
Sodium bicarbonate 100mg (0.01% aqueous solution)
However, the sodium thiosulfate concentration is variable as described in [0100] below, and the effect of this concentration on the color change time is examined.
This solution C is a greenish liquid.

A solution having the following composition is prepared as the other solution D (6 in FIG. 1) in which generation of hydroxide ions is started by mixing, as defined in [Claim 2].
1000cc water
Hydrogen peroxide 1.42g (0.142% aqueous solution)
Hydrogen chloride 0.06g (0.006% aqueous solution)
However, the hydrogen peroxide and hydrogen chloride concentrations are variable as described in [0101] below, and the influence of these concentrations on the color change time is investigated.

Here, the concentrations of sodium thiosulfate (abbreviated as Na2S2O3 in the table), hydrogen peroxide (abbreviated as H2O2 in the table) and hydrogen chloride (abbreviated as HCl in the table) were changed, and red, orange, yellow, green, blue, respectively. The results of measuring the time ([s]) until indigo and purple appear are shown below. The concentration of each reagent is shown after mixing. When 3 cc of solution C and 3 cc of solution D are mixed according to the prescriptions of the above [0098] and [0099] items, sodium thiosulfate 1.6% Hydrogen peroxide 0.071% and hydrogen chloride 0.0030%.
Concentration of each reagent after mixing [%] Time until each color is generated [s]
HCl H2O2 Na2S2O3 Red Orange Yellow Green Blue Indigo Purple 0.0030 0.071 1.60 0 10 12 14 25 32 40
0.0030 0.071 1.00 0 15 17 19 60 70 100
0.0030 0.071 0.80 0 22 25 27 75 80 95
0.0044 0.071 2.40 0 12 13 14 25 30 35
0.0044 0.071 4.70 0 12 13 14 15 19 30

0.0030 0.048 1.60 0 13 15 17 35 40 45
0.0030 0.048 3.20 0 7 8 9 13 15 25

0.0030 0.071 1.60 0 10 12 14 25 32 40
0.0030 0.048 1.60 0 13 15 17 35 40 45
0.0030 0.0242 1.60 0 21 24 25 58 64 70
0.0030 0.0945 1.60 0 8 9 10 22 27 40

0.0030 0.048 1.60 0 13 15 17 35 40 45
0.0020 0.048 1.60 0 1 3 5 18 25 30
From the above data, the characteristics of the mixed solution of [Claim 14] and [Claim 18] described in item [0098] can be read well, but color determination at the time of measurement is human eye and subjective It is necessary to consider that there are a lot of errors.
The relationship between each color and the approximate pH of the aqueous solution is judged based on the description in [0048]. Approximately, red is acidic side of pH5 and H4.5 or less, orange is around pH5, yellow is In the vicinity of pH 6, green is in the vicinity of pH 7, blue is in the vicinity of pH 7.5, indigo is in the vicinity of pH 8, purple is in the alkaline side of pH 8, and the standard is pH 8.5 or more.
FIG. 5 to FIG. 8 show the above data plotted on a logarithmic scale with the pH of the solution on the horizontal axis and the time until the color change on the vertical axis.
Here, FIG. 5 shows a state of change in discoloration time when the hydrogen peroxide concentration is made constant and the sodium thiosulfate concentration is changed, and FIG. 6 similarly shows a state where the hydrogen peroxide concentration is made lower than that in FIG. Change in discoloration time when changing sodium thiosulfate concentration, FIG. 7 shows change in discoloration time when changing hydrogen peroxide concentration with constant hydrogen chloride concentration and sodium thiosulfate concentration, 8 shows how the color change time changes when the hydrogen chloride concentration is changed with the hydrogen peroxide concentration and the sodium thiosulfate concentration kept constant.
From these figures, it can be seen that the reaction of generating hydroxyl ions proceeds rapidly until the mixed solution is weakly acidic, and that the reaction is delayed when it exceeds neutrality. As described in the paragraph [0040], hydrogen ions H + are present in this reaction, and the reaction rate is increased because the concentration of hydrogen ions rapidly decreases when neutrality is reached or when neutrality is exceeded. It is thought that it is decreasing. The concentration of hydrogen chloride affects the time until a series of color changes starting from orange starts, and does not significantly affect the time required for the subsequent color change. The higher the hydrogen peroxide concentration or sodium thiosulfate concentration is, the shorter the time required for the start of color change or the time required for the change of color change to be reduced.
As the alkalinity increases, the degree of color change, that is, the rate of generation of hydroxide ions (OH-) appears to increase again, but this is because hydrogen peroxide is alkaline and is easily decomposed, and oxidation of sodium thiosulfate causes hydroxyl acid. The inventors consider that this is because the reaction of generating ions easily occurs.

In [Claim 9] and [Claim 10], it is defined that urea and an alkaline substance are added, and this effect is described in [0024] to [0026] of the specification.
This effect is shown below as an example.

The following table shows the results of tests conducted by the inventors from September 15 to October 13, 2004 to confirm the effects of [Claim 1], [Claim 9] and [Claim 10]. is there.
The test results are based on the composition shown in [Example 1], and those containing or not containing substances related to the present invention or those whose concentration was changed when the number of days passed. It includes the results of measuring the degree of color development (degree of deterioration) when mixed and the time until discoloration.

A solution having the following composition is prepared as one solution C (5 in FIG. 1) in which a clock reaction is started by mixing.
1000cc water
Soluble starch 2.0g (0.2% aqueous solution)
Sodium sulfite 0.88g (0.088% aqueous solution)
20 g of urea (2% aqueous solution)
Thymol 0.02g (0.002% aqueous solution)
Sodium hydroxide 0.16g (0.016% aqueous solution)

  Based on this, the time [s] until the color change when changing the concentration and composition component and the deterioration degree of the color change were determined in four stages of excellent, good, good, good / no good every day. 0107].

At this time, a solution having the following composition was prepared as the other solution D (6 in FIG. 1) that started the clock reaction by mixing, and mixed with the solution C at a ratio of 1: 1 to show the color development. Observed.
1000cc water
Potassium iodate 2g (0.2% aqueous solution)
Phosphoric acid 8g (0.8% aqueous solution)

Hereinafter, as the composition of the solution C shown in the item [0104], the tested components are shown by weight% of each component in the aqueous solution.
Solution number [%]
Ai Uo starch 0.2 0.2 0.2 0.2 0.2
Sodium sulfite 0 0.088 0.088 0.088 0
Sodium bisulfite 0.073 0 0 0 0.073
Thymol 0.001 0.001 0.001 0.001 0.001
Potassium sorbate 0.133 0.133 0 0 0
Sodium hydroxide 0 0.016 0 0.016 0
Urea 0 10 0 0 0
Solution number [%]
Oyster
Starch 0.2 0.2 0.2 0.2
Sodium sulfite 0.088 0.088 0.088 0.088
Sodium bisulfite 0 0 0 0
Thymol 0.002 0.002 0.002 0.002
Potassium sorbate 0 0 0 0
Sodium hydroxide 0.016 0.016 0.016 0.016
Urea 0 10 2 5
The solution A was mixed with the solution D having the composition shown in the item [0106] at a ratio of 1: 1, and the time until the color change [s], the color depth of the color change, and the result of judging the color tone were determined. It is shown below.
Immediately after preparation of the solution 8 days 12 days 16 days 22 days 30 days 41 days later A Excellent 8s No 10s No No No No Excellent Excellent 8s Excellent 8s Excellent 11s Excellent 12s Good 2s Good U Excellent 2s Allowed 2s Allowed Excellent 6s Excellent 6s Excellent 6s Good 5s Good 2s Good O Excellent 5s Excellent 5s Excellent 6s Good 4s Good 2s Immediately after creation 4 days 8 days 13 days 21 days 32 days later 8s Excellent 5s Excellent 5s Excellent 5s Excellent 5s Excellent 5s Excellent 5s Excellent 8s Excellent 8s Excellent 10s Excellent 10s Excellent 13s Acceptable 10s Negative 8s Excellent 6s Excellent 7s Excellent 7s Excellent 6s Excellent 2s Excellent 8s Excellent 6s Excellent 7s Excellent 9s Excellent 8s Excellent 2s Excellent In the above results, the color changes over time If the container is shortened, the container is opened and closed repeatedly, fresh air is introduced into the container, oxygen is supplied, and the sulfite contained therein is oxidized and consumed. The main cause is believed to be. A mark with excellent or good discoloration indicates that the reddish purple color is good and means that the degree of deterioration of the starch is small.
Some of the urea 10% showed poor discoloration over time, but with regard to this result, hydroxide ions and ammonium ions are generated by the decomposition of urea in a long-term aqueous solution. Therefore, it is considered that the reaction of triiodide ions generated in the clock reaction has become weak.
In this test, sodium hydroxide was added and urea was added in an amount of 2 to 5% by weight.
In addition, this measurement confirmed the time-dependent change of the solution C in the case where it must be stored in a diluted state. When actually storing, as described in the item [0026], at a high concentration, Because it is stored so that almost no air enters the container, it is much better stored.

  In [Example 1], the relationship between the acid concentration and the time until color change when the type of acid to be applied is changed is described in Japanese Patent Application No. 2004-77964, and the concentration of iodate ions Since the quantitative relational expression is described in the paragraph [0008] of the specification of Japanese Patent Application No. 2004-77964, the relationship with the hydrogen ion concentration is described in the paragraph [0008]. The explanation was omitted.

In [Example 7], without using a tubular container or “Shioshidoshi”, the “coloring method of 7-colored aqueous solution that looks like a magic trick” using very concentrated thiosulfate, and this discoloration by copper ions. An example in which time can be controlled is shown. Moreover, it shows that the amount of copper ions contained in the water to be measured can be quantified by this discoloration time measurement.
[Embodiment 7] is an example in which [Claim 14] and [Claim 17] to [Claim 19] and [Claim 20] are combined.

A solution having the following formulation is prepared as one solution C in which generation of hydroxide ions is started by mixing as defined in [Claim 14].
Sodium thiosulfate pentahydrate 16g
Add water to the sodium thiosulfate to make 20 cc. (80% aqueous solution)

A solution having the following formulation is prepared as the other solution D as defined in [Claim 14] in which generation of hydroxide ions is started by mixing.
1000cc water
Hydrogen peroxide 0.48g (0.048% aqueous solution)
Hydrogen chloride 0.042g (0.0042% aqueous solution)
Methyl red 5.5mg (0.00055% aqueous solution)
Cresol red 26.7mg (0.0027% aqueous solution)
Bromthymol blue 26.7mg (0.0027% aqueous solution)
Phenolphthalein 40.0mg (0.004% aqueous solution)
The 0.048% aqueous hydrogen peroxide solution was prepared by dissolving 16 cc of 3% aqueous hydrogen peroxide commercially available as oxidol in 984 cc of water, and adding 0.15 cc of 3.5% hydrochloric acid to this. Equivalent to adding 0.042 g of hydrogen chloride.
This solution D is a reddish liquid.

For the purpose of producing like magic tricks, the following procedure is implemented.
(1) 0.1 cc of the solution C shown in the item [0110] is dropped into the container A. Although depending slightly on the diameter of the dropper or the like, one drop is about 0.05 cc. In this case, two drops were dropped. At this volume of solution, the solution may be clear and appear to contain nothing in the container.
(2) 4.9 cc of the solution D prepared in the item [0111] is mixed in the container A in which the solution C is dropped in (1), and mixed well. Immediately after mixing, the mixed solution in the container A is a reddish liquid.
(3) Time measurement is started immediately after mixing.
(4) When a certain period of time (24 s in the case of this preparation) has elapsed, the mixed solution that has entered the container A suddenly starts to change color from the original red to orange, yellow, and green. Measure and record time.
(5) The color changes to blue, indigo, and purple following (4), but the time required for the color change after blue is longer than the color change time until green. It is difficult to determine at which point it is blue, and the determination error increases. However, considering the large error, the time when each color is reached is determined and recorded.
By the effects (1) to (5) above, the red liquid is poured into the container A that looks empty, and after a while, the liquid in the container A changes from red to orange, yellow, The color changes from green, blue, indigo, and purple, and can produce a magic effect.

Here, the concentrations of sodium thiosulfate (abbreviated as Na2S2O3 in the table), hydrogen peroxide (abbreviated as H2O2 in the table) and hydrogen chloride (abbreviated as HCl in the table) were kept constant, and copper sulfate pentahydrate was added to the solution D. The results of measuring the time ([s]) until red, orange, yellow, green, blue, indigo and purple appear when added are shown below. The concentration of each reagent is shown after mixing. In the above, when 0.1 cc of solution C and 4.9 cc of solution D are mixed, 1.6% sodium thiosulfate, 0.048 hydrogen peroxide %, Hydrogen chloride 0.0042%.
The copper sulfate pentahydrate (CuSO4 · 5H2O) contains 24.5% of copper ions in terms of weight, and the following is shown by the concentration of copper sulfate pentahydrate. In the case of%, it is necessary to multiply this value by 0.245.
Concentration of copper sulfate pentahydrate after mixing [%] Time until each color is generated [s]
Red Orange Yellow Green Blue Indigo Purple 0.000 (0 ppm) 0 24 26 28 55 70 100
0.001 (10 ppm) 0 18 20 24 40 50 70
0.002 (20 ppm) 0 17 19 22 27 40 60
0.004 (40 ppm) 0 9 11 13 23 28 34
0.006 (60 ppm) 0 8 10 12 22 26 30
0.008 (80 ppm) 0 7 8 9 11 13 18
0.012 (120 ppm) 0 5 6 7 9 11 16
0.014 (140 ppm) 0 4 5 6 8 10 15
0.020 (200 ppm) 0 3 4 5 6 7 9
0.028 (280 ppm) 0 3 4 5 6 7 8
0.036 (360 ppm) 0 2 3 4 5 6 7
0.040 (400 ppm) 0 1 2 3 4 5 6
0.060 (600 ppm) 0 1 1.5 2 3 4 5
0.080 (800 ppm) 0 0 0.5 1 2 2.5 3
0.100 (1000 ppm) 0 0 0.5 1 2 2.5 3
0.200 (2000 ppm) 0 0 0 0.5 1 1.5 2
0.400 (4000 ppm) 0 0 0 0.5 0.6. 7 1
It should be noted that, after the mixing, the concentration of copper sulfate pentahydrate exceeds 0.1%, and after 3 s after mixing, the solution once turns purple, then returns to green after 7 s, and after a while, becomes purple again. A pH oscillation phenomenon was observed. 0.2% returned from purple to green after 4 s, and 0.4% returned from purple to green after 2 s, but it took a longer time to return to purple again. This results in different changes in the production of the interior. In the appearance of the pH oscillation phenomenon, it was difficult to control the time until the color change, and the range of the oscillating pH was somewhat narrow, but in this application, the fact that the pH oscillation phenomenon appeared in the combination of the above concentrations is described. deep. Usually, in order to make the pH oscillation phenomenon appear, it is difficult to select the concentration of the solution. Under the combined conditions of this substance and its concentration, the pH oscillation phenomenon was observed after stirring immediately after mixing and leaving it to stand. Such a pH vibration phenomenon is a vibration phenomenon as in [Claim 1] and a phenomenon in which hydroxide ions and the like are generated as in [Claim 2].
In the vicinity of the concentration of copper sulfate pentahydrate after mixing exceeding 0.08% by weight, the effect of reducing “sulfur odor” after the reaction is clearly seen, and as defined in [Claim 22]. At the same time, the effect of the copper salt described in the [0051] section of the specification was also confirmed.

The test results described in the above [0113] are shown in FIG.
The relationship between each color and the approximate pH of the aqueous solution is the same as in item [0101], where approximately red is acidic side of pH 5 and H4.5 or less, orange is near pH 5, yellow is near pH 6, green PH is around 7, blue is around pH 7.5, indigo is around pH 8, purple is more alkaline than pH 8, and the pH is 8.5 or more.
From the data, the effect of [claim 20] described in items [0051] to [0056] can be read well. That is, as the copper ion concentration increases, the rate at which hydroxide ions are generated increases, and this is because the rate at which thiosulfate is oxidized is increased due to the influence of the copper ion catalyst.
As for the test results, it is necessary to consider that there are a lot of errors because color determination at the time of measurement is performed by human eyes and subjectivity. The time to change to purple when the concentration of copper sulfate pentahydrate is 0.001% and the time to change to purple at 0.002% are opposite to the overall trend. This is considered to be due to an error in color determination by human eyes.

In the measurement results shown in [0113], paying attention to the time when yellow and green are passed, the copper ion concentration in terms of copper sulfate pentahydrate and the state of time until each color changes are shown in this figure. 10 shows.
From this figure, it can be seen that as the copper ion concentration increases, the time until discoloration is shortened, and this can be used in reverse to determine the copper ion concentration of a solution with an unknown copper ion concentration. This is the method of [Claim 0021].
That is, when there is an aqueous solution with an unknown copper ion concentration, the solution C and the solution D are prepared in the same manner as the items [0110] and [0111], and a pH indicator is added to the solution. These are mixed in the ratio specified above, and the time of passing yellow or green at this time is measured, and if applied to FIG. 10, the copper ion concentration of the unknown aqueous solution is calculated.

In the color change time measurement from [0109] to [0114] in [Example 7], the effect of copper ions contained in tap water in advance is not taken into account, but in practice it is described as 0.000%. It is necessary to consider the possibility that a small amount of copper ions (in terms of tap water standards, 0.0004%, 4 ppm copper sulfate pentahydrate equivalent) is affecting.
In the test of the inventors, the addition of ethylenediaminetetraacetic acid disodium (EDTA2Na) is used to mask copper ions in tap water, and the effect is observed. Even when EDTA2Na considered to be present was added, an effect of extending the time until discoloration was still observed. The inventors considered that the cause was that the main reaction was hindered by oxidation of EDTA2Na, and as a result, the trace amount of copper ions originally contained in the tap water used this time was Thus, it could not be determined by the method of masking with EDTA2Na.
Therefore, when copper ions are quantified in the test results, an error of a maximum of 1 ppm of copper ions contained in tap water occurs, but this is considered to be negligible here. In order to perform quantitative measurement with higher accuracy, it is necessary to use water from which copper or iron ions have been removed with high purity. However, in this measurement, there are judgment errors, etc., and it is considered meaningless to increase the accuracy to that level, and no more accurate calibration reference value was obtained here. However, if the pH is strictly measured by an electrical method or the like and a highly accurate calibration value is obtained, it is possible to quantitatively measure a very small amount of copper ions with high accuracy.
Here, the test results using EDTA2Na are described below with reference.
However, 1.6% sodium thiosulfate, 0.048% hydrogen peroxide, and 0.0042% hydrogen chloride are used, and these concentrations are the same as those when measuring the effect of copper ions.
EDTA2Na concentration after mixing [%] Time until each color is generated [s]
Red Orange Yellow Green Blue Indigo Purple 0.000 (0 ppm) 0 24 26 28 55 70 100
0.002 (20 ppm) 0 28 32 40 70 90 110
0.004 (40 ppm) 0 30 35 40 70 90 110
0.008 (80 ppm) 0 36 38 45 70 85 120
0.012 (120 ppm) 0 40 42 57 90 110 125
0.016 (160 ppm) 0 42 45 62 90 105 140
0.020 (200 ppm) 0 60 65 80 120 150 200
0.040 (400 ppm) 0 60 65 105 140 160 210
0.080 (800 ppm) 0 60 65 135 185 200 240
In addition, when converting the effect of EDTANa to the effect of copper ion masking, it is necessary to use the following difference in molecular weight or equivalent amount as a coefficient.
Molecular weight of EDTA2Na = 338.3
Equivalent amount of copper sulfate pentahydrate = 249.6
That is, for example, 0.002% of EDTA2Na masks 0.00148% of copper ions in terms of copper sulfate pentahydrate. This is equivalent to 0.00036% (3.6 ppm) of copper ions in terms of copper ions.

In addition, a test was conducted in which iron ions were added in the form of iron (III) chloride (FeCl3) and iron (III) sulfate (Fe2 (SO4) 3). It took a very long time to migrate, and it was not appropriate to use iron ions for the purpose of controlling the discoloration time.
An example of the test results performed is shown below.
However, 1.6% sodium thiosulfate, 0.048% hydrogen peroxide, and 0.0042% hydrogen chloride are used, and these concentrations are the same as those when measuring the effect of copper ions.
Concentration of iron (III) chloride after mixing [%] Time until each color is generated [s]
Red Orange Yellow Green Blue Indigo Purple 0.000 (0 ppm) 0 24 26 28 55 70 100
0.002 (20 ppm) 0 5 7 8 47 60 80
Concentration of iron (III) sulfate after mixing [%] Time until each color is generated [s]
Red Orange Yellow Green Blue Indigo Purple 0.000 (0 ppm) 0 24 26 28 55 70 100
0.002 (20 ppm) 0 12 14 16 50 70 120
The reason why it is not appropriate to use iron ions is that the test result at a copper sulfate pentahydrate concentration of 0.002% shortens the time until the color changes to blue, indigo and purple. In the case of iron ions, it can be read from the fact that there is almost no change in the discoloration after blue.

  In addition, although manganese ions (Mn2 +) and cobalt ions (Co2 +) were added instead of iron ions and copper ions, they did not show a catalytic effect, and there was no significant difference in the discoloration time compared with the case where they were not added. It was. These were tested in the form of manganese chloride tetrahydrate (MnCl 2 .4H 2 O) and cobalt chloride hexahydrate (CoCl 2 .6H 2 O) with 0.002% added to the solution.

In this [Embodiment 7], the solution C having a high concentration and the solution D are mixed by hand. As an embodiment different from [Embodiment 4] in [Claim 7], one “Shishidoshi” The solution C of [0110] is introduced into the container A, and the solution D of the item [0111] is directly dropped into the container A at a rate of 1/49 of that of the solution C. And the solution D are mixed at a ratio of 49: 1, it is possible to have an effect of automatically producing a similar procedure without the intervention of a human hand. The container A can be continuously operated if it has a mechanism for slowly discharging excess solution.
In this example, the mixing ratio and concentration of the solution are specifically shown. However, the concentration and mixing ratio should be changed depending on the situation of the container used, and used at different concentrations and ratios. However, it does not depart from the present invention.

  In addition, although copper ion is forcibly added in this example, as shown in [claim 21], conversely, from this result, it is known that copper ion is contained in the measurement target water. The quantity can be calculated back by measuring the time until each color appears.

It is effective to use the above embodiments in combination as a single demonstration device. For example, as of November 2, 2004, when the present inventors plan to submit the present invention, the inventors are producing a presentation device that combines [Example 1] and [Example 3]. This work will be submitted in mid-November for the 19th Hands Grand Prix sponsored by Tokyu Hands, which will be closed in late November 2004.
This is because by mixing two colorless liquids, a dark reddish purple liquid of iodine starch reaction suddenly generated by a clock reaction is considered to be wine, and a granular solid generated by alginate and calcium ions Iodine starch reaction using clock reaction, gradually changed into reddish-purple granular material, which was likened to colored grape grains. It is an exhibit that tries to express the gist of "cultivating vineyards and growing good grapes. Nature is circulating and will return again as much as given."
In addition, a “demonstration device in which seven colors of rainbow appear” combining [Example 2] and [Example 4] is currently being produced as another exhibit, and from [Example 1] to [Implementation] Even if all of [Example 4] is applied to one work, it is possible to produce an interesting one, and it is effective to perform [Example 7] as an assisting production.

Finally, as a supplement, in the description of the above [0010] to [0121], sulfite, bisulfite, acid, calcium salt, strontium salt, magnesium salt, iodate, thiosulfate, iodide, peroxo Sulfates, divalent manganese salts, potassium salts, copper salts, and iron salts are defined as general salts or acids with some examples of specific substance names, but more specific compound names are specified. If so, it is added that the following compounds can be listed for each general substance name.
Sulphite: Sodium sulfite, potassium sulfite, ammonium bisulfite Bisulfite: sodium bisulfite, potassium bisulfite, bisulfite ammonium acid: phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, bromic acid, iodic acid, acetic acid, lactic acid, citric acid, Calcium tartrate: calcium hydrogen phosphate, calcium nitrate, calcium lactate, calcium chloride, calcium bromide, calcium iodide Strontium salt: strontium nitrate, strontium chloride magnesium salt: magnesium sulfate, magnesium nitrate, magnesium chloride iodate: iodic acid Potassium, sodium iodate, ammonium iodate thiosulfate: sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate iodide: potassium iodide, sodium iodide, ammonium iodide, iodide Lead, aluminum iodide, hydroiodic acid, manganese iodide, lithium iodide peroxodisulfate: potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate divalent manganese salt: manganese sulfate, manganese chloride, manganese nitrate Potassium salts: potassium sulfate, potassium nitrate, potassium chloride, potassium dihydrogen phosphate (primary potassium phosphate), dibasic potassium phosphate, tribasic potassium phosphate, potassium diphosphate, potassium sorbate, potassium thiosulfate, sulfurous acid Potassium, potassium bromide, potassium iodide, potassium benzoate, potassium carbonate, potassium bicarbonate, potassium iodate, potassium hydrogen iodate, potassium acetate, potassium tartrate, potassium hydrogen tartrate, monopotassium citrate, tripotassium citrate, Dihydrogen citrate , Potassium ethoxide, potassium hydroxide, potassium formate, potassium gluconate, potassium hydrogen oxalate, potassium borate, potassium pyrophosphate, potassium pyrosulfate, potassium pyruvate copper salt: copper sulfate, copper nitrate, copper chloride, ammonium chloride Copper, copper bromide, copper iodide, copper iodate, copper formate, copper acetate, copper phosphate, copper pyrophosphate, copper carbonate, copper citrate, copper phthalate, copper tartrate: iron sulfate, iron nitrate , Iron chloride, ammonium chloride, iron bromide, iron iodide, iron iodate, iron formate, iron acetate, iron phosphate, iron pyrophosphate, iron citrate, iron phthalate, iron tartrate

  [Claim 1], [Claim 2], [Claim 5], [Claim 7] The present invention appeals visual beauty to children and the like, and is interested in science from the mystery of the phenomenon. The applicability to toys and interiors with the elements of magic to be held was shown, and the applicability to home interiors and in-store interiors that visually enjoy sudden changes in hue was shown.

[Claim 3], [Claim 6], and [Claim 9] to [Claim 23] are methods for assisting these in order to improve the state of the interior or the like described in [0123]. Yes, when used in combination with [Claim 1], [Claim 2], [Claim 5] and [Claim 7], the visual beauty and the mystery of the phenomenon are increased to make it more beautiful or more interesting. This makes it possible to produce toys and interiors.
[Claim 14] is applied to interiors and the like centering on [Claim 2] and [Claim 7], the reaction time is a numerical value suitable for presentation, the reaction time can be easily adjusted, and the cost is low. It is considered to be particularly suitable because it is composed of a safe material and the amount of material used is small, and a good demonstration effect can be obtained when used in combination with the indicator shown in [Claim 17] or [Claim 18]. have.

[Claim 12] provides a method for measuring the content of vitamin C by a simple method and an inexpensive raw material, and easily measures vitamin C at home, so that it is an important ingredient as a nutrient for children and the like. It is possible to apply it as an educational material that gives interest in and educates the vitamin C.
Similarly, [Claim 21] provides a method of measuring the content of copper ions or iron ions contained in water by a simple method and an inexpensive raw material.

  In addition, as shown in specific examples of solution formulation in [Example 1] to [Example 4] and [Claim 7], the amount of chemicals used in these reactions is compared with the amount of the solution to be prepared. Therefore, it is very few, and there are many substances that are often used in daily life, and consideration is also given to economic efficiency and environmental load at the time of disposal.

The inventors have a hobby of devising, for example, “slightly interesting things” as described above and “things that attract interest in natural science and chemistry”, and the present invention was also carried out as part of such hobby activities. It is.
In particular, the sudden change of color when nothing is done or the rainbow 7 colors appear one after another seems to be very interesting for children interested in science, chemistry or magic. If you show it, you will cheer, and the person who produces it will be very rewarding.
In this patent application, the detailed composition of this production, the formulation of the solution, the applied ideas, the principle of discoloration, etc., the detailed examples are described, and I remembered myself, but the record of this idea is other I would be happy if it would be useful information for those who are making "something interesting".

The figure which shows one Example of this invention and this invention. The figure which shows one Example of this invention and this invention. The figure which shows one Example of this invention and this invention. The figure which shows one Example of this invention. Change in discoloration time when the hydrogen peroxide concentration is kept constant and the sodium thiosulfate concentration is changed. Change in discoloration time when the hydrogen peroxide concentration is kept constant and the sodium thiosulfate concentration is changed. Change in discoloration time when the hydrogen peroxide concentration is changed with the hydrogen chloride concentration and sodium thiosulfate concentration kept constant. Change in discoloration time when the concentration of hydrogen chloride and the concentration of sodium thiosulfate are kept constant and the concentration of hydrogen chloride is changed. Relationship between concentration of copper sulfate pentahydrate after mixing [%] and time until each color occurs Relationship between the concentration of copper sulfate pentahydrate and the change in time to pass yellow or green

Explanation of symbols

1 Tubular container 2 Lump of solution 3 Funnel A
4 Wire 5 Solution C
6 Solution D
7 Funnel B
8 Solution A
9 Solution B
10 Inclined Path 11 Small Droplet 12 Large Droplet 13 “Snow-Shaped” Plate 14 Another Path 15 Solution B Container 16 Connected “Shishiodoshi”
17 Container 18 Exit

Claims (23)

  It is composed of two or more kinds of solutions in which a clock reaction or vibration reaction is started by mixing and a tubular container, these solutions are mixed and introduced into the tubular container, and while the mixed solution flows through the tubular container, An interior, display, toy, and accessory characterized by causing a sudden change in the state of a solution at a certain position of a tubular container by a clock reaction or a vibration reaction. (Hereinafter, the generic term for interior, display, toy and accessories is called "interior etc.")   It is composed of two or more kinds of solutions in which a reaction in which hydrogen ions or hydroxide ions are generated by mixing, a pH indicator and a tubular container, and these solutions and the pH indicator are mixed and introduced into the tubular container, An interior or the like characterized by causing a sudden color change of a solution at a certain position of the tubular container by a reaction in which hydrogen ions or hydroxide ions are generated while the mixed solution flows through the tubular container. In an interior or the like composed of a solution, a container having a wide inlet and a narrow outlet (hereinafter referred to as a funnel when using abbreviations) and a tubular container, the solution is received by the funnel, and the solution is introduced from the funnel into the tubular container. In order to create a state where the outer peripheral wall of the funnel tip and the inner peripheral wall of the tubular container are not in direct contact with each other, the outer peripheral wall of the funnel tip and the inner peripheral wall of the tubular container are not directly in contact with each other. In addition,
(1) Wrap a thread-like object such as a wire, a thread, or a rubber string around the tip of the funnel, and insert it into a tubular container.
(2) Make a protrusion on the outer periphery except near the tip of the funnel and insert it into the tubular container.
(3) Make a protrusion on the inner wall side of the tubular container and insert a funnel into it.
(4) An interior or the like characterized by applying any one or a plurality of concave inner walls of a tubular container and inserting a funnel therein.   [Addition of two or more types of solutions in which a clock reaction or a vibration reaction or a reaction in which hydrogen ions or hydroxide ions are generated by mixing] is added to the funnel A shown in [Claim 3]. In a featured interior, etc., another two or more funnels B receive the two or more solutions, and the funnel B is positioned so that the mixed solution is dropped on the outlet of the funnel A. Interiors characterized by that.   By mixing, for example, an alginate or carrageenan such as sodium alginate, potassium alginate or ammonium alginate is added to one of the two solutions in which a clock reaction or vibration reaction or a reaction in which hydrogen ions or hydroxide ions are generated is initiated. For example, a solution B obtained by adding one or more of calcium salt, magnesium salt, strontium salt, barium salt, or potassium salt such as calcium hydrogen phosphate, calcium nitrate, and calcium lactate to the other solution A and the other solution An interior or the like characterized in that the solution A is dropped into the solution B.   The interior or the like shown in [Claim 5] composed of an aqueous solution A containing at least alginate or carrageenan and an aqueous solution B containing one or more of calcium salt, magnesium salt, strontium salt, barium salt or potassium salt In which the colorless transparent granular solid generated by dripping the aqueous solution A into the aqueous solution B is received by a “snow-like” plate having a gap of 0.1 mm to 2.5 mm in width, etc. .   It is composed of two or more kinds of solutions in which a clock reaction or a vibration reaction or a reaction in which hydrogen ions or hydroxide ions are generated by mixing, and a so-called “Shishidoshi” container. Alternatively, both are introduced separately into a “Shishidoshi” container, and after a certain period of time, “Shishidoshi” discharges these solutions into one container and mixes them. An interior or the like characterized by performing an operation of mixing a solution at regular intervals. As defined in [Claim 5], “two kinds of solutions in which a clock reaction is started by mixing” is used as one solution C using, for example, a sulfite or bisulfite such as sodium sulfite and an aqueous starch solution. In one solution D, for example, a combination of a solution that causes a clock reaction using an iodate such as potassium iodate and an acid such as phosphoric acid or sulfuric acid, 1% by weight of a solute having a specific gravity higher than that of water is added to the solution C. Interiors characterized by the addition of the above.   As defined in [Claim 1] or [Claim 5] or [Claim 7], “two kinds of solutions in which a clock reaction is started by mixing” is added to one solution C, for example, sulfite such as sodium sulfite. Alternatively, in a combination of a solution in which bisulfite and an aqueous starch solution are combined with another solution D to cause a clock reaction using an iodate such as potassium iodate and an acid such as phosphoric acid or sulfuric acid, Interiors characterized by adding urea.   As defined in [Claim 1] or [Claim 5] or [Claim 7], “two kinds of solutions in which a clock reaction is started by mixing” is added to one solution C, for example, sulfite such as sodium sulfite. Or a combination of a solution of hydrogen sulfite and an aqueous starch solution, and the other solution D that causes a clock reaction using an iodate such as potassium iodate and an acid such as phosphoric acid or sulfuric acid. An interior or the like characterized by adding an alkaline substance that dissolves in water, such as sodium hydroxide or potassium hydroxide, to C.   As defined in [Claim 1] or [Claim 5] or [Claim 7], “two kinds of solutions in which a clock reaction is started by mixing” is added to one solution C, for example, sulfite such as sodium sulfite. Alternatively, in a combination of a solution containing hydrogen sulfite and an aqueous starch solution and causing the other solution D to cause a clock reaction using an iodate such as potassium iodate and an acid such as phosphoric acid, For example, interiors characterized by the addition of iodides such as sodium iodide, potassium iodide, ammonium iodide, zinc iodide, aluminum iodide, hydroiodic acid, manganese iodide, and lithium iodide.   As defined in [Claim 1] or [Claim 5] or [Claim 7], “two kinds of solutions in which a clock reaction is started by mixing” is added to one solution C, for example, sulfite such as sodium sulfite. Alternatively, in a combination of a solution containing hydrogen sulfite and an aqueous starch solution and causing the other solution D to cause a clock reaction using an iodate such as potassium iodate and an acid such as phosphoric acid, Interiors characterized by the addition of ascorbic acid (vitamin C).   As defined in [Claim 5], as “two kinds of solutions in which a clock reaction is started by mixing”, sulfite or bisulfite such as sodium sulfite, an aqueous starch solution and an alginate are added to one solution A. Used in the other solution B in which a clock reaction is caused using an iodate such as potassium iodate and an acid such as phosphoric acid and a calcium salt, magnesium salt, strontium salt or barium salt. Interior etc. characterized by adding hydrogen peroxide to solution B.   As “two or more solutions in which a reaction in which hydrogen ions or hydroxide ions are generated by mixing” is started, an aqueous thiosulfate solution such as sodium thiosulfate is added to one solution C, and an aqueous solution D is added to the other solution D. Using an aqueous hydrogen peroxide solution, a pH indicator is added to one or both of these, and these solutions are mixed, or the other is dropped into one solution by the method shown in [Claim 5], and the chemical is added. An interior or the like characterized by causing color change of the mixed pH indicator by generation of hydroxide ions by reaction.   [Claim 2] or [Claim 5] or [Claim 7] As defined in "two or more kinds of solutions in which a reaction in which hydrogen ions or hydroxide ions are generated by mixing" is defined as one solution A thiosulfate salt such as sodium thiosulfate is used as C, an aqueous periodate solution such as potassium periodate is used as the other solution D, and a pH indicator is added to either or both of these solutions. Or the other is dropped into one solution by the method shown in [Claim 5], and the color change of the mixed pH indicator is caused by generation of hydroxyl ions by a chemical reaction. And interior.   As a pH indicator defined in [Claim 14] or [Claim 15], a pH indicator obtained by mixing at least methyl red and bromthymol blue and phenolphthalein or cresolphthalein is applied and mixed, or Acids such as phosphoric acid and hydrochloric acid are mixed in both aqueous solutions, and a variety of colors such as red, orange, yellow, green, blue, indigo and purple are used as the pH of the solution changes. Interiors characterized by color changes.   At least methyl red, bromthymol blue, and cresol red (o-cresol sulfophthalein) are added to one or more of the “two or more solutions in which a reaction in which hydrogen ions or hydroxide ions are generated by mixing” is initiated. Mixing pH indicators obtained by mixing, and causing various color changes such as red, orange, yellow, green, blue, indigo and purple at the stage where the pH of the solution changes Characteristic interior etc.   An interior using a pH indicator characterized by adding phenolphthalein or cresolphthalein to the pH indicator defined in claim 17.   The pH indicator defined in [Claim 17] or [Claim 18] is applied as the indicator defined in [Claim 14] or [Claim 15] and mixed with one or both aqueous solutions, for example, phosphoric acid or It is characterized by mixing various acids such as hydrochloric acid and causing various color changes such as red, orange, yellow, green, blue, indigo and purple when the pH of the solution changes. And interior.   As “two types of solutions in which a clock reaction is started by mixing”, an aqueous thiosulfate solution is used for one solution C and an aqueous hydrogen peroxide solution is used for the other solution D as shown in [Claim 14]. In an interior or the like constituted by adding a pH indicator to one or both of these, for example, a copper salt (copper compound) such as copper sulfate, copper nitrate or copper chloride, or iron sulfate or iron nitrate is added to the solution C. Interiors characterized by the addition of iron salts (iron compounds) such as iron chloride.   As “two types of solutions in which a clock reaction is started by mixing”, an aqueous thiosulfate solution is used for one solution C and an aqueous hydrogen peroxide solution is used for the other solution D as shown in [Claim 14]. Or by adding a pH indicator to either or both of them, measuring the time until the color change of the pH indicator occurs after a certain time after mixing these solutions, or as defined in [Claim 2] A method of easily quantitatively measuring the concentration of copper ions or iron ions contained in the solution C or the solution D or both of the solutions C and D by measuring the position where the discoloration occurs when applied to an interior or the like.   In the interior or the like defined in [Claim 14] or [Claim 15], “two or more solutions in which a reaction that generates hydrogen ions or hydroxide ions is started by mixing” is mixed and the reaction is completed. After the discoloration is completed, the interior or the like characterized by mixing, for example, either or both of a sulfite such as sodium sulfite, potassium sulfite, and ammonium sulfite, or a copper salt such as copper sulfate. One solution A contains either or both of an alginate such as sodium alginate or carrageenan, and the other solution B contains a calcium or magnesium salt such as calcium hydrogen phosphate or calcium nitrate or a strontium salt or barium. An interior or the like characterized in that Congo red is dissolved in the solution A in an interior or the like in which one or a plurality of salts or potassium salts is mixed and the solution A is dropped into the solution B.

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