JP2013244994A - Indicator structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an indicator structure enabling a person to visually recognize whether two medicines are already mixed and used or are after use when two different medicines are mixed for use.SOLUTION: An indicator structure has a transparent, flexible and hollow vessel, and an ampule housed in the hollow part of the vessel. The first liquid capable of decomposing pigment is charged in the ampule. A space is formed between the ampule and the hollow inner surface of the vessel, and the second liquid colored by the pigment is charged in the space. When the vessel and the ampule are bent or broken, the ampule is destructed to discharge the first liquid in the vessel, and the first liquid is mixed so as to decompose the coloring pigment of the second liquid.

Description

  The present invention relates to an indicator structure that can be used to know whether a drug has already been mixed and used when two different drugs are used, and particularly suitable for chlorine dioxide. It is.

  Formulations that release volatile drugs such as insect repellents and fungicides have been commercialized so that the point in time when the release of the volatile drugs can be confirmed visually. If the volatile chemical is a sublimable solid, it can be confirmed by the disappearance of the solid. In the case where the volatile drug is a liquid, a substance that has a function of changing its color at the end of volatilization of the volatile drug and can visually confirm the end of the release is generally used.

As a method of discoloration when using a liquid volatile chemical, for example, the following methods have been studied.
An example is a method of adding an electron-donating colored organic compound as described in Patent Document 1 or a chemically changing indicator such as a pH indicator and changing the color of the indicator along with volatilization. In addition, as disclosed in Patent Document 2, a method in which a non-volatile pigment is dissolved in a volatile organic compound, and the color is changed by causing the pigment to condense and disappear when the volatile organic compound is volatilized. is there.

  In Patent Document 3, a coating layer made of a transparent powder made of a transparent material is provided on the surface of a colored porous granular base material, and the coating layer is colored by transmitting light when impregnated with a drug. A method is described in which a color is exhibited and the coating layer reflects light to exhibit a white color after volatilization of the drug.

By the way, among such volatile chemicals, there is chlorine dioxide having a deodorizing and bactericidal effect.
For example, as disclosed in Patent Document 4, chlorite that releases chlorine dioxide is stored in a container and gradually released, or dissolved in water as disclosed in Patent Document 5. A composition containing aggregate containing chlorine dioxide in a water-absorbing polymer can be mentioned.
And in pharmaceutical preparations such as bactericides and deodorants using chlorine dioxide, in order to be able to confirm the final stage of volatilization by visual observation, as in Patent Document 6, on the surface of a sheet such as paper, a dye and Provide a mixed layer composed of a chlorine dioxide permeable resin, so that the dye does not come into direct contact with chlorine dioxide, the timing of fading the type and amount of the dye, the type of chlorine dioxide permeable resin and the thickness of the mixed layer It adjusts by the combination of these, and what was made to attach to the predetermined position of the chlorine dioxide volatilization preparation which match | combined the end of volatilization and timing is mention | raise | lifted.

JP-A-2-290592 JP-A-6-116544 JP 2004-346283 A JP 2002-370910 A JP 2003-012424 A JP 2012-29770 A

  However, since chlorine dioxide has a strong oxidizing power, even if an attempt is made to indicate the end in the system as in Patent Documents 1 to 3 using an aqueous solution containing dissolved chlorine dioxide, the contact organic compound or pH indicator by chlorine dioxide during storage In addition, other dyes are decomposed, and there is a problem that the color is lost without waiting for the end of volatilization.

  In addition, since the residue of chlorite remains even after chlorine dioxide is released, the end of the chlorite could not be known by the disappearance of the solid, like a sublimable solid.

  For this reason, the indicator which displays appropriately the end of volatilization of chlorine dioxide is logically difficult to manufacture, and has not been realized.

In order to generate chlorine dioxide, sodium chlorite is enclosed in chemical-resistant glass ampules or polyethylene (PE) or polypropylene (PP) containers, while acidic solution is sealed in PE or PP containers. There is a case. In this case, since the container itself is milky white and the solution after use is transparent, the color of the appearance is very similar, and it is difficult to determine whether it is before use or after use.
For this reason, after using the product after using it by mistake, start using it as it is, or try to use the product after using it by mistake, bend the container, etc. There was a problem that liquids could scatter and cause injury.
Also, if you try to use a used item again by mistake, the container will not change its color during reaction, so it will be incorrectly judged as a defective product. If the reaction progresses without your knowledge, if you leave it unattended, the solution will eventually finish and become transparent, and it will look the same as before use, and it will be mistaken for the appearance before use. There was a problem of doing.

  The present invention has been made to solve the above-mentioned problems. When two different drugs are mixed and used, whether the drugs are already mixed and used is visually checked. The present invention relates to an understandable indicator structure, and particularly aims to provide an indicator structure suitable for chlorine dioxide.

  An indicator structure according to the present invention includes a hollow container having translucency and flexibility, and an ampule accommodated in a hollow portion of the container, and the dye is decomposed in the ampule. A possible first liquid is filled, a space is formed between the ampoule and the hollow inner surface of the container, and a second liquid colored with a pigment is filled in the space; The amp is broken by bending or breaking the container and the ampule, and the first liquid is discharged into the container so that the first liquid decomposes the coloring pigment of the second liquid. It is characterized by being mixed.

  The ampoule may be made of glass or hard resin.

The stick may be made of a resin that is permeable to chlorine dioxide.

The first solution is an aqueous sodium chlorite solution, the second solution is an acidic aqueous solution, and the stick may be made of polyethylene or polypropylene. Or the sheet-like thing which divided the inside into the some division with the soft film may be used.

Sectional drawing of one Embodiment which concerns on the indicator structure concerning this invention. The figure which showed the example of the base sequence of the pigment | dye which concerns on this embodiment. The figure which showed another example of the base sequence of the pigment | dye which concerns on this embodiment. The figure which showed another example of the base sequence of the pigment | dye which concerns on this embodiment. The figure which showed another example of the base sequence of the pigment | dye which concerns on this embodiment. The figure which showed another example of the base sequence of the pigment | dye which concerns on this embodiment. The perspective view which showed the example of the indicator structure which concerns on another embodiment.

Embodiments according to the present invention will be described with reference to the drawings.
FIG. 1 shows an example of an indicator structure according to this embodiment.
In FIG. 1, the indicator structure according to the present embodiment includes a stick 1 having a hollow bar shape and a glass ampoule 2 disposed in a hollow portion of the stick 1.

The stick 1 is formed in a vertically long bar shape, and a hollow portion extending in the vertical direction is formed.
The stick 1 is made of a resin and has flexibility, and a resin capable of transmitting chlorine dioxide generated in the stick 1 and releasing it into the atmosphere is used. As this resin, for example, polyethylene (PE) or polypropylene (PP) is suitable.
The hollow portion of the stick 1 has such a size that a gap is formed between the inner surface of the hollow portion and the ampoule 2 when the ampoule 2 is accommodated. This gap is configured to be filled with the second solution.

The ampoule 2 is for containing the medicine 4 for generating chlorine dioxide. The ampoule 2 is formed in the shape of a hollow vertically long bar, and is configured to be smaller than the inner diameter of the hollow portion of the stick 1. In the ampoule 2, a sodium chlorite (NaClO ₂ ) solution is accommodated as the drug 4.
In addition, the ampoule 2 is made of a hard material such as a thin plate-like glass, and has a structure in which it is damaged by bending stress and the contained sodium chlorite solution is discharged into the stick.

In addition, a gap is formed between the hollow portion of the stick 1 and the ampoule 2, and an acidic solution 3 is accommodated as another medicine for generating chlorine dioxide in the gap.
Examples of the acidic solution 3 include aqueous solutions of organic acids such as citric acid, tartaric acid, malic acid, aconitic acid, adipic acid, maleic acid, fumaric acid, succinic acid, succinic anhydride, and acetic acid, and inorganic acids such as hydrochloric acid and amidosulfuric acid. And an ethanol solution that changes to an acid by reaction with sodium chlorite.
This acidic solution is colored with a colorant that is acid-resistant and discolorable with chlorine dioxide, and as this colorant, for example, a food additive synthetic colorant can be used. As a preferable example, as shown in FIGS. 2 to 6, Kiriya Chemical Co., Ltd., Red No. 2 (FIG. 2), Red No. 102 (FIG. 3), Red No. 106 (FIG. 4), Blue No. 1 (FIG. 5). ) And Blue No. 2 (FIG. 6).

Next, how to use the chlorine dioxide generating material to which the above indicator structure is applied will be described.
First, in an unused state, an ampoule 2 contains a sodium chlorite solution, and an acid solution (citric acid) colored in red or blue between the ampoule 2 and the hollow portion of the stick 1. Solution).
In this state, since the stick 1 is made of a translucent resin such as polyethylene, the color (red, blue, etc.) of the acidic solution colored with the pigment is visible when viewed from the outside.
In this state, the sodium chlorite solution in the ampoule 2 is transparent and filled with the colored acidic solution around the ampoule 2, so that the color of the acidic solution (pigment) Only the color colored by (1) can be seen.
In this state, since the sodium chlorite solution and the acidic solution are separated, chlorine dioxide is not generated (unused state).

  In order to generate chlorine dioxide from this state, the user folds the stick 1 with his / her hand to break the ampoule 2 made of glass. As a result, the ampoule 2 is made of glass, so that the ampoule 2 is broken due to bending stress, and the sodium chlorite solution filled in the ampoule 2 is discharged into the stick 1. On the other hand, since the stick 1 itself is made of a flexible resin such as polyethylene, it is bent flexibly and does not break.

Thereby, sodium chlorite in the ampoule 2 reacts with citric acid in the gap between the stick 1 and the ampoule 2 to generate chlorine dioxide.
Since chlorine dioxide is a gas at room temperature, the inside of the stick 1 is filled with chlorine dioxide. When the concentration exceeds a predetermined level, it passes through the polyethylene on the outer wall of the stick 1 and is released into the atmosphere. An odor effect can be obtained.

Moreover, the pigment | dye in an acidic solution is decomposed | disassembled by a chlorine dioxide or a sodium chlorite solution, and coloring with a pigment | dye lose | disappears as time passes.
As a result, the generated chlorine dioxide itself exhibits a yellow or brown color, so that the color colored by the pigment gradually falls within the stick 1 and changes to the yellow or brown color of the chlorine dioxide itself. It turns transparent when chlorine is gone.
Thereby, it can be determined that the color of the stick 1 has changed and becomes transparent when it has become transparent.

As described above, according to the above-described embodiment, the stick 1 has the color of the pigment of the acidic solution (red, blue, etc.) before use, and the chemical inside reacts to generate chlorine dioxide. When it is yellow or brown, it becomes transparent after use, so that each use state can be clearly distinguished.
As a result, the stick 1 after use is mistakenly used before use, or the post-use sticker is bent incorrectly, and the stick 1 is broken and the solution inside or the glass splashes. Can be prevented.

  In the above-described embodiment, the example in which sodium chlorite is placed in the ampoule 2 and the citric acid solution is placed in the stick 1 has been described. However, the medicine is not limited to this, and chlorine dioxide is generated. There is no particular limitation as long as it is a drug.

  In the above-described embodiment, the generation of chlorine dioxide has been described, but other cases are also applicable. For example, the present invention can be similarly applied to a case where two drugs are mixed and the dye is decomposed and bleached by a solution in an ampoule.

As another example, a soft film may be filled with the solution.
In this case, in order to generate chlorine dioxide, in the case shown in FIG. 7, an acidic solution colored with a pigment is contained in the gas permeable outer bag 11, and chlorous acid is contained in the inner bag 12 that does not transmit the gas liquid. Sodium solution is enclosed.
In this state, pressure is applied to the gas permeable outer bag 11 with a palm or a finger to break the inner bag 12 accommodated therein, and the sodium chlorite solution in the inner bag 12 and the gas permeable outer bag 11 Chlorine dioxide can be generated by reacting with an acidic solution.
This bag structure can also be applied to structures such as Japanese Patent Application Laid-Open Nos. 2006-335448 and 2006-335447 as conventional techniques.

  As yet another structure, as a stick-type structure disclosed in Japanese Patent Application Laid-Open No. 2011-230956, this acidic substance (liquid or solid) may be colored with the above-described colorant.

About selection of coloring agent.
(1) Select light-resistant and acid-resistant dyes, adjust the dye concentration to 0.2% and citric acid concentration to 3.9%, fill a 4.8-6mm x L50mm polypropylene resin tube and seal The light resistance was investigated by installing it on a south-facing exposure stand about 1 meter high outdoors for 35 days. As a result, the light resistance of natural pigments was very small and not practical. The above-mentioned Red No. 102, Red No. 106, and Blue No. 1 were relatively high in light resistance and practical.
(2) Put 15 mL of 8% sodium chlorite solution in a 100 mL pigment glass beaker, add 15 mL of 4.9% anhydrous citric acid mixed with 0.1 g of pigment, mix and then seal the resin and leave it in the dark at room temperature. did. As a result, for Sinroihi's Sinrohi colors FZ-SB (skyblue) and FZ-6013 (Red), the degree of bleaching is slight after 31 days at room temperature in the dark and cannot be used as an indicator. Generally, inorganic pigments have low fading and are not easily bleached by chlorine dioxide.
(3) Heat resistant red No. 102 0.028mg / L, red No. 106 0.008mg / L, blue No. 1 0.016mg / L dye concentration adjusted to 3.9% citric acid solution, φ4.8-6mm × An L50 mm polypropylene resin tube was filled and sealed. This was immersed in 80 ° C. water bath and treated for up to 104 hours to confirm the fading.
For Blue No. 1, a polyethylene tube having a diameter of 11 to 14 mm × L 150 mm was also tested. As a result, no discoloration occurred at 80 ° C. until 104 hours. Therefore, Red No. 102, Red No. 106, and Blue No. 1 did not fade significantly upon encountering high temperatures during the inventory period.

Discoloration of pigment caused by defective ampules Glass ampules with very small cracks were filled with 0.25 mL of 5% sodium chlorite solution. When immersed in an acid solution, the acid solution entered the glass ampule and reacted. Colors yellow. A glass resin ampule with a diameter of 4.8-6 mm and a glass ampule colored yellow and 0.25 mL of 3.9% citric acid solution adjusted to 0.028 (mg / L) red No. 102 were filled and sealed. 45 The period until the red color disappeared after standing in a dark place at 0 ° C. was observed. As a result, the red color disappeared from 4 days to 18 days later, and the glass ampoule was yellow.
Therefore, when a micro crack occurs in the glass ampule after manufacturing, the glass ampule exhibits a yellow color, and after a certain period, the red No. 102 is completely discolored by the generated chlorine dioxide.
For this reason, when the ampule was originally yellow and the acid solution was red, the ampule was dissolved by the time when the acid solution entered the glass ampule and reacted to decompose the dye of the acid solution. Is yellow and the acid solution is transparent, or the ampoule and the acid solution are transparent, and in any case not only red, it can be easily determined from the combination of colors that this stick is defective.

Chlorine dioxide consumption rate of each dye If much of the chlorine dioxide is consumed in order to bleach the dye, the amount of chlorine dioxide generated is reduced for a period and the effect as a chlorine dioxide generator is reduced.
(Test A) In a conical flask with a 100 mL glass stopper, put 20 mL of a 4.8% sodium chlorite solution and add 20 mL of a 3.9% citric acid solution adjusted to 0.028 (mg / L) Red No. 102. Sealed with a stopper and stored in a dark place at room temperature. Similarly, the same operation was carried out using 20 mL of 8.5% sodium chlorite solution and 20 mL of 4.9% citric acid solution adjusted to 0.016 (mg / L) blue No. 1.
After 1, 2, 3 and 10 days of mixing the two liquids, 2.5 mL was taken out from the Erlenmeyer flask and the sodium chlorite concentration was measured.
(Test B) In a 100 mL PET transparent container, add 2.5 mL of 4.8% sodium chlorite solution, add 2.5 mL of 3.9% citric acid solution adjusted to 0.028 (mg / L) Red No. 102, and seal tightly. Stored in a dark place at room temperature. Similarly, the same operation was performed using 2.5 mL of 8.5% sodium chlorite solution and 2.5 mL of 4.9% citric acid solution adjusted to be 0.016 (mg / L) blue No. 1. After mixing the two liquids 1, 2, 3 and 10 days, the volume of the liquid in the container was made up to 100 mL, and the sodium chlorite concentration was measured.
(Results) In both test A and test B set to a practical concentration of the dye, chlorine dioxide was not consumed so much that there was a difference due to the fading of the dye. Therefore, the effectiveness of the chlorine dioxide generator prepared with a practical dye concentration is the same as when no dye is added.

Color fading time when using chlorine dioxide generator Make 3.9% citric acid of practical concentration liquid of red No. 102, red No. 106, blue No. 1 and red liquid No. 102 (0.028 mg / L, red 106 No .: 0.008 mg / L, Blue No. 1: 0.016 mg / L). Time from filling 0.25 mL of solution A into a 4.8-6 mm diameter polypropylene resin tube filled with 0.25 mL of 4.6% sodium chlorite, sealing the resin, and the color of each dye disappearing to develop yellow Was observed at room temperature. Furthermore, the same test was conducted with dye concentrations of 2 times, 4 times and 2 mg / L of solution A. As a control, the same test was performed with 3.9% citric acid to which no dye was added.
As a result, in the control to which no dye was added, yellow color was developed in 8 minutes.
In other examples, as shown in Table 1, Red No. 102 is in the range of 0.028 to 0.112 mg / L, 12 minutes later, 2 mg / L is 30 minutes later, Blue No. 1 is 0.016 mg / L, 66 minutes later, and 0.032. After 86 minutes at 0.064 mg / L, it turned almost yellow after 156 minutes at 2 mg / L. In red No. 106, it turned yellow almost in the range of 0.008 to 0.032 mg / L after 68 to 88 minutes, but at 2 mg / L, it remained red and never turned yellow.
Therefore, there is a difference in disappearance of color depending on the pigment, and there is a limit to increasing the concentration. In Red No. 102, since the pigment is bleached and yellowed at an early stage from the start of use, it can be confirmed at an early stage that chlorine dioxide is reliably generated. On the other hand, Blue No. 1 can maintain the color for a long time with a relatively high pigment concentration.

(Effects of dyes on gas emission capacity when using chlorine dioxide generator)
A practical solution of 3.9% red No. 102, Red No. 106, and Blue No. 1 was prepared. Solution A (Red No. 102: 0.028 mg / L, Red No. 106: 0.008 mg / L, Blue No. 1: 0.016 mg / L). A φ4.8-6 mm polypropylene resin tube filled with 0.25 mL of 4.6% sodium chlorite was filled with 0.25 mL of solution A, and the resin was sealed. Three tubes of each dye were sealed in a 180 mL polypropylene container (with a polyethylene sealable lid) and stored at room temperature in a dark place. As a control, the same test was performed with 3.9% citric acid to which no dye was added.
As a result, carefully open the lid of the 180 mL container after 3 days of standing, extract 5 mL of gas with a syringe attached with a thin vinyl chloride tube through the gap, and dilute it appropriately to detect the gas from Gastec. The concentration of chlorine dioxide gas was measured using tubes (23L and 23M). The gas concentrations in the 180 mL containers are all around 15 ppm, and it can be assumed that the presence of the dye does not significantly affect the ability of chlorine dioxide gas to diffuse.

  The present invention relates to an indicator structure that can be used to know whether a drug has already been mixed and used when two different drugs are used, and particularly suitable for chlorine dioxide. It is.

1 stick 2 ampoule 3 acidic solution 4 sodium chlorite solution

Claims (5)

A light-transmitting and flexible hollow container, and an ampoule housed in the hollow portion of the container;
The ampoule is filled with a first liquid capable of decomposing a dye,
A space is formed between the ampoule and the hollow inner surface of the container, and this space is filled with a second liquid colored with a pigment,
The amp is broken by bending or breaking the container and the ampule, and the first liquid is discharged into the container so that the first liquid decomposes the coloring pigment of the second liquid. Mixed,
An indicator structure characterized by that. The ampoule is made of glass or hard resin,
The indicator structure according to claim 1. The stick is made of chlorine dioxide permeable resin,
The indicator structure according to claim 1 or 2. The first solution is an aqueous sodium chlorite solution, the second solution is an acidic aqueous solution,
The stick is made of either polyethylene or polypropylene,
The indicator structure in any one of Claims 1-3. The dye is an acid resistant dye,
The indicator structure according to claim 4.

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