JP4906749B2 - Ozone detection sheet - Google Patents

Description

  The present invention relates to an ozone detection sheet that detects ozone present in a gas such as the atmosphere by a fading reaction.

At present, air pollution caused by NO _x , SPM (Suspended Particulate Matter), and photochemical oxidant occurs, and the influence on the environment is a problem. For example photochemical oxidants, a strong oxidizing a with a substance such as ozone as a main component, pollutants such as NO _x and hydrocarbons discharged from factories and offices and automobiles upon exposure to sunlight by photochemical reaction It is produced and causes photochemical smog.

  In Japan, environmental standards are set for these substances, and they are measured by general environmental atmospheric measurement stations in various regions. For example, an environmental standard is set for this concentration of photochemical oxidant, and gas concentration measurement is performed by an automatic measurement method such as an ultraviolet absorption method at general atmospheric environment observation stations in various places. In addition, about the photochemical oxidant, the average value measured per hour is 0.06 ppm or less as an environmental standard.

  In the ozone gas concentration measurement by the automatic measurement method described above, as a measurement of ozone present in the atmosphere, a gas to be measured is bubbled into a neutral potassium iodide solution, and a method of detecting using the color reaction of the generated iodine, A detection method using absorption of ozone in the ultraviolet region is used. However, these measurement methods can measure a very small amount of gas of several ppb, but have the disadvantage that the apparatus becomes large in size and has a complicated configuration, so that simple measurement cannot be performed. In addition, these devices are expensive and always require maintenance for maintaining accuracy. In addition, automatic measurement using these devices always requires electric power, and requires regular calibration (maintenance) work. Therefore, it requires a huge amount of money to maintain, and the installation environment is controlled by power and temperature. , And standard gas must be secured, and there are many restrictions.

  By the way, in order to accurately investigate the distribution of gas concentrations in the environment, evaluate the impact on the local environment, and assess the impact of human exposure, the environment should be monitored using a measurement method that can be easily carried by individuals. There is a need. For this purpose, development of a measuring device such as a gas sensor and a simple measuring method that are not compatible with the above-described large-scale measuring device and that can be easily used at low cost and in small size is desired.

  In recent years, ozone has been attracting attention for its strong bactericidal power (oxidizing power) and the advantage that it does not generate harmful substances after being decomposed into oxygen, and is used in various industrial fields such as water treatment, food sterilization, and paper bleaching. Usage is expanding. For this reason, a standard value of 100 ppb for 8 hours is set as the working environment standard for the ozone concentration. In factories that use ozone, as well as installing ozone alarms, it is necessary for each worker to manage the working conditions within the scope of labor standards. A portable measuring instrument is required.

  Under such circumstances, the development of ozone gas measurement technology is currently progressing widely, such as semiconductor gas sensors, solid electrolyte gas sensors, electrochemical gas sensors, and quartz oscillation gas sensors. However, these were developed to evaluate the response in a short time, and few were developed for monitoring that requires accumulation of measurement data. Therefore, when it is necessary to accumulate measurement data, it is necessary to keep it operating at all times. Further, for example, in the case of a semiconductor sensor, it is necessary to keep the detection unit at several hundred degrees Celsius, and a lot of electric power is always required to always operate.

  Further, since the above-described sensor has a detection sensitivity of about sub ppm, it cannot cope with the concentration in the real environment such as measurement of ozone of 10 ppb. Some semiconductor sensors respond to 10 ppb of ozone, but the detection output is non-linear with respect to the concentration. Furthermore, the output value differs greatly from sensor to sensor, and a comparison using different sensors is possible. It's not easy. In many cases, the influence of other gases cannot be ignored.

  In addition, there is a method using a detector tube type gas measuring device, but this method was also developed for the purpose of locally measuring the concentration at a measurement location for a very short time. Use is difficult.

  In contrast to the ozone gas analysis technique described above, ozone detection paper carrying starch and potassium iodide has been proposed as a simple and highly sensitive ozone analysis technique (see Patent Document 1). However, the technique according to Patent Document 1 requires a pump for forcibly sucking the gas to be detected, a light source for measurement, and a power for driving a detector composed of these. In addition, a special sheet-like carrier is required, and the sheet needs to be updated for each measurement, so that accumulative measurement is not easy. In addition, in the measurement using the detection paper, there is a problem that all photochemical oxidants are detected, not ozone. In addition, when this method is used, the produced iodine gradually evaporates, which causes a problem in accuracy and reproducibility.

  As a simple and highly sensitive method for analyzing ozone gas, a technique using ozone detection paper carrying indigo carmine has been proposed (see Non-Patent Document 1). However, in the case of this ozone detection paper, there is a problem that the sensitivity is not sufficient and the accumulated amount of 100 ppb × 8 hours, which is the working environment standard, cannot be measured sufficiently. In addition, a technique for adjusting the sensitivity by installing a membrane filter on the surface of an ozone detection sheet carrying a blue indigo dye and adjusting the thickness of the membrane filter has been proposed (see Non-Patent Document 2).

  In addition, the inventors have proposed an ozone detection element using a porous glass provided with a dye that changes its light absorption in the visible region by reacting with ozone as a simple and advanced ozone detection element. (See Patent Document 2). According to this technique, ozone gas can be measured with high accuracy without requiring a large-scale apparatus. However, even in this technique, power for driving the light source and the detector is required for measurement, and an expensive carrier such as porous glass is required.

  In addition, the inventors have proposed a detection paper provided with an indigo dye that reacts with ozone and changes light absorption in the visible region on a cellulose sheet as a simple and highly sensitive ozone detection paper (see Non-Patent Document 3). ). According to this technique, it is possible to measure ozone with high sensitivity without requiring a large-scale apparatus.

Japanese Patent No. 3257622 JP 2004-144729 A Anna C. Franklin, et al., "Ozone Measurement in South Carolina Using Passive Sampler", Journal of the Air & Waste Measurement Association, Vol.54, pp.1312-1320, 2004. "Operating Instructions for Ozone Monitor", Part # 380010-10, http://www.kandmenvironmental.com/PDFs/ozone.pdf Maruko Yoko et al., "Development of ozone detection paper", 17th Annual Meeting of the Japan Ozone Association, p167, June 14, 2007.

  As described above, in the past, if ozone gas is to be detected accurately in the ppb order in accordance with environmental standards, an expensive and large-scale device configuration is required, which is troublesome and cannot be easily detected. there were. In addition, with the conventional technology, it is difficult to measure the amount of accumulation when trying to measure easily, and there are problems such as requiring electric power and requiring a special carrier. There was nothing.

  The present invention has been made in order to solve the above-described problems, and it is easy to carry out the integrated amount of ozone in the gas to be measured by the accumulation effect without using power and being easily portable. It is an object of the present invention to provide an ozone detection sheet that can be easily detected and carried by an individual.

  The ozone detection sheet according to the present invention comprises a sheet-like carrier composed of fibers, an azo dye having a sulfite group supported on the carrier and bonded to a position not adjacent to a hydroxy group and an azo group, and the carrier. And an alkaline substance that makes the aqueous solution alkaline (for example, sodium hydroxide). The azo dye may be selected from among orange I, orange II, crocein orange G, tropeoline O, acid alizarin violet N, modern blue 13, and chalcone.

  In the ozone detection sheet, the azo dye may include two hydroxy groups bonded adjacent to the azo group on different sides with respect to the azo group. The azo dye in this case is selected from Acid Alizarin Violet N, Modern Blue 13, and Chalcone.

  In the ozone detection sheet, the azo dye may have a hydroxy group bonded to the p-position with respect to the azo group. The azo dye in this case is either orange I or tropeoline O.

  The ozone detection sheet is formed by immersing a carrier in a detection solution made alkaline by dissolving a pigment and dissolving an alkaline substance, impregnating the carrier with the detection solution, and drying. It is sufficient that the carrier is provided with a humectant supported together with the dye. The humectant may be at least one of glycerin, ethylene glycol, and propylene glycol.

  As described above, according to the present invention, an azo dye having a sulfite group bonded to a position not adjacent to a hydroxy group and an azo group and an alkaline substance in which an aqueous solution is alkaline are formed on a sheet-like carrier composed of fibers. Since the ozone detection sheet is supported, the integrated amount of ozone in the gas to be measured can be easily detected by the accumulation effect without using electric power and easily portable. A portable ozone detection sheet can be provided.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[Embodiment 1]
FIG. 1 is a process diagram illustrating an example of a method for manufacturing an ozone detection sheet according to Embodiment 1 of the present invention. First, as shown in FIG. 1A, a container 102 in which a detection solution 101 is stored is prepared. The detection solution 101 includes an azo dye (detection component) composed of orange I (p- (4-Hydroxy-1-naphthylazo) benzenesulfonic acid, sodium salt: C ₁₆ H ₁₁ N ₂ NaO ₄ S), and glycerin (C ₃ H It is an aqueous solution in which the humectant comprising ₈ O ₃ ) is dissolved and made alkaline by dissolving the base, and the weight percentage of the humectant is about 20%.

  The detection solution 101 is prepared by, for example, dissolving 0.034 g of orange I in 25 ml of an aqueous solution in which sodium hydroxide is dissolved as a base which is an alkaline substance to have a concentration of 0.1 mol / liter, and 10 g of glycerin and Water is added to make the total amount 50 g. Orange I is an azo dye (dye), and a detection solution 101 prepared by dissolving orange I in an alkaline solution is an aqueous solution exhibiting rose pink. The color of the detection solution 101 can be visually confirmed.

  Next, as shown in FIG. 1B, a sheet-like carrier 103 having a predetermined size is prepared. The sheet-like carrier 103 is a sheet composed of fibers such as cellulose, and is, for example, cellulose filter paper (No. 2) manufactured by Advantech (Toyo Filter Paper Co., Ltd.). The sheet-like carrier 103 may be white, for example. Next, the prepared sheet-like carrier 103 is dipped in the detection solution 101, for example, dipped for 30 seconds to impregnate (infiltrate) the detection solution 101 into the sheet-like carrier 103, and as shown in FIG. The impregnated sheet 104 impregnated with is formed. This state can be said to be a state in which the impregnated sheet 104 is dyed with orange I which is a dye.

  Thereafter, the impregnated sheet 104 is pulled up from the detection solution 101 and dried in dry nitrogen to evaporate and dry a solvent (medium) such as moisture impregnated in the impregnated sheet 104, as shown in FIG. Thus, it is set as the state in which the ozone detection sheet | seat (ozone detection element) 105 was formed. As shown in FIG. 1 (e), orange I, which is an azo dye having a hydroxy group as the dye 111, is carried on the ozone detection sheet 105 formed in this way together with sodium hydroxide as the alkaline substance 112. Will be. The ozone detection sheet 105 also carries glycerin as the moisturizing agent 113. The obtained ozone detection sheet 105 is in a state of exhibiting rose pink (stained in rose pink), and this color can be visually confirmed.

  As described above, the ozone detection sheet is prepared by drying, but due to the presence of moisture in the atmosphere (air), the surface of the fiber constituting the sheet-like carrier, together with the dye and the alkaline substance, It is considered that moisture (a thin film of water) is formed (supported). In addition, it is considered that the above-described moisture is held (supported) more by the presence of the humectant. This state can also be considered that an extremely thin film of an aqueous solution in which a pigment and an alkaline substance are dissolved is formed on the surface of the fibers constituting the sheet-like carrier.

  Note that the above-described support indicates a state in which substances such as a dye, an alkaline substance, and a humectant are chemically or physically or electrically bonded or adsorbed to a carrier (base material). A sheet composed of fibers such as cellulose has a hydrophilic surface, and water, an aqueous solution, and a water-soluble substance are easily adsorbed. Therefore, the detection solution that is an aqueous solution and the water-soluble pigment or alkaline substance adhere (adsorb) to the surface of the fibers constituting the sheet. As described above, a state in which a pigment or the like is coated and / or impregnated on a sheet made of fibers is supported.

  The ozone detection sheet 105 manufactured in this manner is exposed to an environment in which ozone is present, so that the density of rose pink gradually decreases with the exposure time, and finally changes to a white state. For example, when the ozone detection sheet 105 is exposed to an environment having an ozone concentration of 0.1 ppm for 5 hours, a white state (original filter paper color) is obtained. Thus, according to the ozone detection sheet 105, it is possible to detect ozone by a change in color, and it is possible to perform cumulative detection. This color change is considered to be due to fading according to the decomposition of the azo dye Orange I by ozone.

Here, the pigment that can be used is not limited to orange I, but orange II (p- (2-Hydroxy-1-naphthylazo) benzenesulfonic acid, sodium salt: C ₁₆ H ₁₁ N ₂ NaO ₄ S), crocein. Orange G (6-Hydroxy-5-phenylazo-2-naphthalenesulfonic acid, sodium salt: C ₁₆ H ₁₁ N ₂ O ₄ NaS), Troperion O (4- (2,4-Dihydroxyphenylazo) benzenesulfonic acid, sodium salt: C ₁₂ An azo dye (dye) having a hydroxy (—OH) group bonded to the benzene ring or naphthalene ring adjacent to the azo group, such as H ₉ N ₂ NaO ₅ S), can be used.

Acid Alizarin Violet N (4-Hydroxy-3- (2-hydroxy-1-naphthylazo) benzenesulfonic acid, sodium salt: C ₁₆ H ₁₁ N ₂ NaO ₅ S) and Modern Blue 13 (4- (5-Chloro) -2-hydroxyphenylazo) -3,5-dihydroxy-1,7-naphthalene disulfonic acid, disodium salt: C ₁₆ H ₉ ClN ₂ Na ₂ O ₉ S ₂ ), etc. An azo dye having two hydroxy groups bonded adjacent to each other can be used. These are configured to include two hydroxy groups bonded adjacent to the azo group on different sides with respect to the azo group.

In addition, both naphthalene rings such as chalcone (3-Hydroxy-4- (2-hydroxy-1-naphthylazo) -1-naphthalenesulfonic acid, sodium salt: C ₂₀ H ₁₃ N ₂ NaO ₅ S) have azo An azo dye with a hydroxy group bonded adjacent to the group can be used. This is also provided with two hydroxy groups bonded adjacent to the azo group on different sides with respect to the azo group.

  All of the azo dyes described above have a sulfite group bonded to a position not adjacent to the hydroxy group and the azo group. In other words, each of the above-described azo dyes includes a sulfite group and a hydroxy group that are bonded to positions not adjacent to the azo group.

In addition, azo dyes are produced by diazo coupling occurring between diazonium and an aromatic ring, and nitrite ions are used in the production process. For this reason, the azo dye hardly reacts with NO _x or the like, and ozone gas can be selectively detected in the environmental measurement.

  Further, according to the ozone detection sheet 105 by the manufacturing method shown in FIG. 1, it is formed by impregnating the detection solution 101 containing the humectant whose weight% is about 20, so that The color change (ozone detection capability) due to the presence of ozone is more effectively expressed. It is considered that the reaction between the pigment and ozone in the ozone detection sheet 105 is promoted by including (supporting) the humectant. However, if the concentration of the humectant in the detection solution is too high, for example, exceeding 50%, the time required for drying becomes enormous, making it difficult to produce a reproducible detection sheet.

  The relationship between the amount of the humectant and the change in the color of the ozone detection sheet due to the presence of ozone will be described below. Below, the comparison by the several sample (ozone detection sheet) produced by changing the quantity (content) of the moisturizer in the detection solution 101 is demonstrated. In addition, below, it demonstrates including the conditions made into states (acidic and neutral state) other than alkalinity.

  First, 0.034 g of Orange I is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to make the total amount 50 g to prepare (produce) the detection solution A-1. Prepared without glycerin as a moisturizer. Using this detection solution A-1, an ozone detection sheet A-1 is prepared in the same manner as described above. Ozone detection sheet A-1 is formed in the state which exhibited rose pink. Note that Orange I has spectral characteristics as shown in FIG. 2 and is different between an alkaline case and an acidic case.

  Further, 0.034 g of Orange I is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to 5 g of glycerin as a humectant to make 50 g, thereby producing a detection solution B-1. Using this detection solution B-1, an ozone detection sheet B-1 is prepared in the same manner as described above. The ozone detection sheet B-1 is formed in a state exhibiting rose pink.

  Further, 0.034 g of Orange I was dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water was added to 10 g of glycerin as a humectant to prepare 50 g of detection solution C-1, and this detection The ozone detection sheet C-1 is produced with the solution C-1 in the same manner as described above. The ozone detection sheet C-1 is formed in a state exhibiting rose pink.

  Further, 0.034 g of Orange I was dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water was added to 15 g of glycerin as a moisturizing agent to prepare a detection solution D-1 having a total amount of 50 g. Using the detection solution D-1, an ozone detection sheet D-1 is prepared in the same manner as described above. The ozone detection sheet D-1 is formed in a state exhibiting rose pink.

  Further, 0.034 g of Orange I was dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water was added to 20 g of glycerin as a moisturizer to prepare a detection solution E-1 having a total amount of 50 g. Using the detection solution E-1, an ozone detection sheet E-1 is prepared in the same manner as described above. The ozone detection sheet E-1 is formed in a state exhibiting rose pink.

  Further, 0.034 g of Orange I, 3.0 g of citric acid and 10 g of glycerin as a humectant were added with water to prepare a detection solution F-1 having a total amount of 50 g. Similarly, the ozone detection sheet F-1 is produced. The ozone detection sheet F-1 is formed in an orange color. The ozone detection sheet F-1 is a sample made acidic by adding citric acid.

  In addition, 0.034 g of Orange I and 10 g of glycerin as a humectant were added with water to prepare a detection solution G-1 having a total amount of 50 g, and this detection solution G-1 was used to detect the ozone detection sheet G- as described above. 1 is produced. The ozone detection sheet G-1 is formed in an orange color. In this case, citric acid, sodium hydroxide (base) or the like is not added, and pH adjustment such as alkalinity is not performed.

  For each of the above-described samples (ozone detection sheets A-1, B-1, C-1, D-1, E-1, F-1, and G-1), the ozone concentration was set to 0.1 ppm, respectively. A test was conducted by exposing to ozone gas by leaving it in a box filled with air at a temperature of 60 ° C and humidity of 60%, and the reflectance of the ozone detection sheet at a wavelength of 525 nm was measured for the discolored state of the result of this test. It was measured. Orange I showed a different color when acidified, and the detection sheet F-1 was measured for reflectance at a wavelength of 480 nm. The volume of the box is 200 liters, and internal air is sucked at 2 liters / minute for analysis of the internal ozone concentration, and air containing a predetermined concentration of ozone is supplied at 2 liters / minute. Thus, it exposes to the to-be-detected air and measures the color change of each ozone detection sheet. In addition, the color change is also observed visually. The test results are shown in Table 1 below.

  From the results shown in Table 1, it can be seen that the detection sheet B-1 to the detection sheet E-1 containing the moisturizing agent can be reliably detected by integrating the exposure for 5 hours even if the ozone concentration is as low as 0.1 ppm. It can also be seen that the amount of change in color per unit time in the produced detection sheet differs depending on the amount (ratio) of the humectant in the detection solution used when producing the ozone detection sheet. When glycerin is used as a humectant, if the content in the detection solution is in the range of ˜20%, the amount of color change per unit time increases as the amount of glycerin increases. Further, from the result that the detection sheet A-1 cannot be detected, it can be understood that the detection cannot be performed so much if the moisturizing agent is not used. From the results of Table 1, in the case of Orange I, the concentration of glycerin in the detection solution may be 10% to 40%, and the case of 20% is optimal.

  Further, even when a humectant is used, as shown in the detection sheet F-1, when a detection sheet is produced with an acidic detection solution, no color change is detected, and ozone is almost impossible to detect. . Further, even when a humectant is used, as shown in the detection sheet G-1, when the pH is not adjusted without adding a base or an acid, and it is not alkaline, the change in the detected color is small, and visually It cannot be confirmed.

[Embodiment 2]
Next, the ozone detection sheet in Embodiment 2 of this invention is demonstrated. Hereinafter, a case where Orange II is used as the azo dye instead of Orange I described above will be described. First, 0.034 g of Orange II is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to make a total amount of 50 g to prepare a detection solution A-2. Prepared without glycerin as a moisturizer. Using this detection solution A-2, an ozone detection sheet A-2 is prepared as described above. The ozone detection sheet A-2 is formed in an orange color state. Note that Orange II has spectral characteristics as shown in FIG. 3, and the peak position does not change much between the alkaline and acidic cases, but is slightly different.

  Further, 0.034 g of Orange II is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 5 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution B-2. Using this detection solution B-2, an ozone detection sheet B-2 is prepared in the same manner as described above. The ozone detection sheet B-2 is formed in an orange color.

  Further, 0.034 g of Orange II is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 10 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution C-2. Using this detection solution C-2, an ozone detection sheet C-2 is prepared in the same manner as described above. The ozone detection sheet C-2 is formed in an orange color.

  Further, 0.034 g of Orange II is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 15 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution D-2. Using this detection solution D-2, an ozone detection sheet D-2 is prepared in the same manner as described above. The ozone detection sheet D-2 is formed in an orange color.

  Further, 0.034 g of Orange II is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 20 g of glycerin as a humectant and water are added to make 50 g, thereby producing a detection solution E-2. Using this detection solution E-2, an ozone detection sheet E-2 is prepared in the same manner as described above. The ozone detection sheet E-2 is formed in an orange color state.

  Further, 0.034 g of Orange II, 3.0 g of citric acid and 10 g of glycerin as a humectant were added with water to prepare a detection solution F-2 with a total amount of 50 g. Similarly, an ozone detection sheet F-2 is produced. The ozone detection sheet F-2 is formed in an orange color. The ozone detection sheet F-2 is a sample made acidic by adding citric acid.

  Further, 0.034 g of Orange II and 10 g of glycerin as a humectant were added with water to prepare a detection solution G-2 having a total amount of 50 g, and this detection solution G-2 was used to detect ozone detection sheet G- 2 is produced. The ozone detection sheet G-2 is formed in an orange color. In this case, citric acid, sodium hydroxide (base) or the like is not added, and pH adjustment such as alkalinity is not performed.

  About each sample mentioned above (ozone detection sheet | seat A-2, B-2, C-2, D-2, E-2, F-2, G-2), respectively, ozone concentration shall be 0.1 ppm and 25 A test of exposure to ozone gas by leaving it in a box filled with air at 60 ° C. and humidity of 5% for 5 hours, and the discoloration state of the result of this test, the reflectance of the ozone detection sheet at a wavelength of 500 nm It was measured. Since Orange II has a maximum portion of the spectrum including 500 nm even in an acidic state, the reflectance at a wavelength of 500 nm was also measured for the ozone detection sheet F-2. The volume of the box is 200 liters, and internal air is sucked at 2 liters / minute for analysis of the internal ozone concentration, and air containing a predetermined concentration of ozone is supplied at 2 liters / minute. Thus, it exposes to the to-be-detected air and measures the color change of each ozone detection sheet. In addition, the color change is also observed visually. The test results are shown in Table 2 below.

  From the results shown in Table 2, it can be seen that the detection sheet C-2 and the detection sheet D-2 containing a humectant can be reliably detected by integrating exposure for 5 hours even if the ozone concentration is as low as 0.1 ppm. It can also be seen that the amount of change in color per unit time in the produced detection sheet differs depending on the amount (ratio) of the humectant in the detection solution used when producing the ozone detection sheet. When glycerin is used as a humectant, if the content in the detection solution is in the range of ˜20%, the amount of color change per unit time increases as the amount of glycerin increases. Further, from the result that the detection sheet A-2 is not detected, it can be seen that the detection cannot be performed so much if the moisturizing agent is not used. From the results of Table 2, in the case of Orange II, the concentration of glycerin in the detection solution may be 20% to 30%, and the case of 20% is optimal.

  Further, even when a humectant is used at the same concentration as that of the detection sheet C-2, as shown in the detection sheet F-2, when the detection sheet is prepared with the detection solution in the acidic state, no color change is detected. It is almost impossible to detect ozone. Moreover, even if a humectant is used, as shown in the detection sheet G-2, when the pH is not adjusted without adding a base or an acid, and it is not alkaline, the change in the detected color is small, and visually It cannot be confirmed.

[Embodiment 3]
Next, the ozone detection sheet in Embodiment 3 of this invention is demonstrated. Hereinafter, a case where crocein orange G is used as the azo dye instead of the above-described orange I and orange II will be described. First, 0.034 g of crocein orange G is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to make a total amount of 50 g to prepare a detection solution A-3. Prepared without glycerin as a moisturizer. Using this detection solution A-3, an ozone detection sheet A-3 is prepared in the same manner as described above. The ozone detection sheet A-3 is formed in an orange color. Note that crocein orange G has spectral characteristics as shown in FIG. 4, and has similar characteristics in an alkaline case and an acidic case.

  Further, 0.034 g of crocein orange G is dissolved in 25 ml of a 0.1 mol / liter sodium hydroxide aqueous solution, and 5 g of glycerin as a humectant and water are added to make 50 g, thereby producing a detection solution B-3. . Using this detection solution B-3, an ozone detection sheet B-3 is prepared in the same manner as described above. The ozone detection sheet B-3 is formed in an orange color.

  Further, 0.034 g of crocein orange G is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 10 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution C-3. . Using this detection solution C-3, an ozone detection sheet C-3 is prepared in the same manner as described above. The ozone detection sheet C-3 is formed in an orange color.

  Further, 0.034 g of crocein orange G is dissolved in 25 ml of a 0.1 mol / liter sodium hydroxide aqueous solution, and 15 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution D-3. . Using this detection solution D-3, an ozone detection sheet D-3 is prepared in the same manner as described above. The ozone detection sheet D-3 is formed in an orange color.

  Further, 0.034 g of crocein orange G is dissolved in 25 ml of a 0.1 mol / liter sodium hydroxide aqueous solution, and 20 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution E-3. . Using this detection solution E-3, an ozone detection sheet E-3 is prepared in the same manner as described above. The ozone detection sheet E-3 is formed in an orange color.

  Further, detection solution F-3 was prepared by adding water to 0.034 g of crocein orange G, 3.0 g of citric acid and 10 g of glycerin as a humectant to make the total amount 50 g, and this detection solution F-3 As described above, an ozone detection sheet F-3 is prepared. The ozone detection sheet F-3 is formed in an orange color. The ozone detection sheet F-3 is a sample made acidic by adding citric acid.

  Further, 0.034 g of crocein orange G and 10 g of glycerin as a humectant were added with water to prepare a detection solution G-3 having a total amount of 50 g, and this detection solution G-3 was used to detect ozone as described above. G-3 is produced. The ozone detection sheet G-3 is formed in an orange color. In this case, citric acid, sodium hydroxide (base) or the like is not added, and pH adjustment such as alkalinity is not performed.

  About each sample mentioned above (ozone detection sheet | seat A-3, B-3, C-3, D-3, E-3, F-3, G-3), respectively, ozone concentration shall be 0.1 ppm and 25 A test of exposure to ozone gas by leaving it in a box filled with air at 60 ° C. and humidity of 5% for 5 hours, and the discoloration state of the result of this test, the reflectance of the ozone detection sheet at a wavelength of 500 nm It was measured. Since the maximum part of the spectrum of the crocein orange G includes 500 nm even in an acidic state, the reflectance at a wavelength of 500 nm was also measured for the ozone detection sheet F-3. The volume of the box is 200 liters, and internal air is sucked at 2 liters / minute for analysis of the internal ozone concentration, and air containing a predetermined concentration of ozone is supplied at 2 liters / minute. Thus, it exposes to the to-be-detected air and measures the color change of each ozone detection sheet. In addition, the color change is also observed visually. The test results are shown in Table 3 below.

  From the results shown in Table 3, the detection sheet B-3, the detection sheet D-3, and the detection sheet D-3 containing the moisturizing agent are reliably detected by integrating the exposure for 5 hours even if the ozone concentration is as low as 0.1 ppm. I understand that I can do it. It can also be seen that the amount of change in color per unit time in the produced detection sheet differs depending on the amount (ratio) of the humectant in the detection solution used when producing the ozone detection sheet. When glycerin is used as a humectant, if the content in the detection solution is in the range of ˜20%, the amount of color change per unit time increases as the amount of glycerin increases. Further, from the result that the detection sheet A-3 is not detected, it can be understood that the detection cannot be performed so much if the humectant is not used. From the results of Table 3, in the case of crocein orange G, the concentration of glycerin in the detection solution may be 10% to 30%, and the case of 20% is optimal.

  Further, even when a humectant is used at the same concentration as that of the detection sheet C-3, as shown in the detection sheet F-3, when the detection sheet is prepared with the detection solution in the acidic state, no color change is detected. It is almost impossible to detect ozone. Further, even when a humectant is used, as shown in the detection sheet G-3, when the pH is not adjusted without adding a base or an acid, and it is not alkaline, the change in the detected color is small, and visually It cannot be confirmed.

[Embodiment 4]
Next, the ozone detection sheet in Embodiment 4 of this invention is demonstrated. Below, the case where tropeoline O is used as an azo dye is demonstrated. First, 0.03 g of tropeoline O is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to make a total amount of 50 g to prepare a detection solution A-4. Prepared without glycerin as a moisturizer. Using this detection solution A-4, an ozone detection sheet A-4 is prepared in the same manner as described above. The ozone detection sheet A-4 is formed in a yellow state. Note that tropeoline O has spectral characteristics as shown in FIG. 5 and is slightly different between an alkaline case and an acidic case.

  Further, 0.03 g of tropeoline O is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 5 g of glycerin as a moisturizer and water are added to make 50 g to prepare a detection solution B-4. Using this detection solution B-4, an ozone detection sheet B-4 is prepared in the same manner as described above. The ozone detection sheet B-4 is formed in a yellow state.

  Further, 0.03 g of tropeoline O is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 10 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution C-4. Using this detection solution C-4, an ozone detection sheet C-4 is prepared as described above. The ozone detection sheet C-4 is formed in a yellow state.

  Further, 0.03 g of tropeoline O is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 15 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution D-4. Using this detection solution D-4, an ozone detection sheet D-4 is prepared in the same manner as described above. The ozone detection sheet D-4 is formed in a yellow state.

  Further, 0.03 g of tropeoline O is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 20 g of glycerin as a humectant and water are added to make 50 g, thereby producing a detection solution E-4. Using this detection solution E-4, an ozone detection sheet E-4 is prepared in the same manner as described above. The ozone detection sheet E-4 is formed in a yellow state.

  Further, 0.03 g of tropeoline O, 3.0 g of citric acid and 10 g of glycerin as a humectant were added with water to prepare a detection solution F-4 with a total amount of 50 g. Similarly, an ozone detection sheet F-4 is produced. The ozone detection sheet F-4 is formed in a yellow state. The ozone detection sheet F-4 is a sample made acidic by adding citric acid.

  Further, 0.03 g of tropeoline O and 10 g of glycerin as a humectant were added with water to prepare a detection solution G-4 having a total amount of 50 g, and this detection solution G-4 was used to detect the ozone detection sheet G- 4 is produced. The ozone detection sheet G-4 is formed in a yellow state. In this case, citric acid, sodium hydroxide (base) or the like is not added, and pH adjustment such as alkalinity is not performed.

  For each of the samples (ozone detection sheets A-4, B-4, C-4, D-4, E-4, F-4, G-4), the ozone concentration was set to 0.1 ppm. A test of exposure to ozone gas by leaving it in a box filled with air at 60 ° C. and humidity of 5% for 5 hours, and for the discoloration state of the result of this test, reflectivity of the ozone detection sheet at a wavelength of 440 nm It was measured. Tropeolin O exhibited a different color when acidified, and the detection sheet F-4 was measured for reflectance at a wavelength of 400 nm. The volume of the box is 200 liters, and internal air is sucked at 2 liters / minute for analysis of the internal ozone concentration, and air containing a predetermined concentration of ozone is supplied at 2 liters / minute. Thus, it exposes to the to-be-detected air and measures the color change of each ozone detection sheet. In addition, the color change is also observed visually. The test results are shown in Table 4 below.

  From the results shown in Table 4, the detection sheet C-4, the detection sheet D-4, and the detection sheet E-4 containing the moisturizing agent are reliably detected by integrating the exposure for 5 hours even if the ozone concentration is as low as 0.1 ppm. I understand that I can do it. It can also be seen that the amount of change in color per unit time in the produced detection sheet differs depending on the amount (ratio) of the humectant in the detection solution used when producing the ozone detection sheet. When glycerin is used as the humectant, if the content in the detection solution is in the range of ˜30%, the amount of color change per unit time increases as the amount of glycerin increases. Further, from the result that the detection sheet A-4 cannot detect, it can be understood that the detection cannot be performed so much if the moisturizing agent is not used. From the results in Table 4, in the case of tropeoline O, the concentration of glycerin in the detection solution may be 20% to 40%, and the case of 30% is optimal.

  Further, even when a humectant is used at the same concentration as that of the detection sheet C-4, as shown in the detection sheet F-4, when the detection sheet is prepared with the detection solution in the acidic state, no color change is detected. It is almost impossible to detect ozone. Further, even when a moisturizing agent is used, as shown in the detection sheet G-4, when the pH is not adjusted without adding a base or acid, and it is not alkaline, the change in the detected color is small, and visually It cannot be confirmed.

Note that Orange I, Orange II, Crocein Orange G, and Tropeolin O shown above have at least one hydroxy group in the benzene ring or naphthalene ring, and also have a sulfite group (SO ₃ group adjacent to the azo group). ) Among these, tropeoline O has two hydroxy groups bonded to the o-position and the p-position, and has no sulfite group (SO ₃ ) adjacent to the azo group. In other words, the dye is an azo dye that has at least one hydroxy group and the SO ₃ group is bonded to the azo group other than in the o-position. The hydroxy group is bonded to the o-position or p-position with respect to the azo group.

[Embodiment 5]
Next, the ozone detection sheet in Embodiment 5 of this invention is demonstrated. Below, the case where acid alizarin violet N is used as an azo dye is demonstrated. First, 0.035 g of acid alizarin violet N is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to make the total amount 50 g, thereby producing a detection solution A-5. Prepared without glycerin as a moisturizer. Using this detection solution A-5, an ozone detection sheet A-5 is prepared as described above. The ozone detection sheet A-5 is formed in a purple state. Acid Alizarin Violet N has spectral characteristics as shown in FIG. 6 and is different between alkaline (pH 9 or more) and acidic.

  Further, 0.035 g of acid alizarin violet N is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 5 g of glycerin as a humectant and water are added to make 50 g to prepare a detection solution B-5. . Using this detection solution B-5, an ozone detection sheet B-5 is prepared in the same manner as described above. The ozone detection sheet B-5 is formed in a purple state.

  Further, 0.035 g of acid alizarin violet N is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 10 g of glycerin as a humectant and water are added to make 50 g to prepare a detection solution C-5. . Using this detection solution C-5, an ozone detection sheet C-5 is prepared as described above. The ozone detection sheet C-5 is formed in a purple state.

  Further, 0.035 g of acid alizarin violet N is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 15 g of glycerin as a humectant and water are added to make 50 g, thereby producing a detection solution D-5. . Using this detection solution D-5, an ozone detection sheet D-5 is prepared as described above. The ozone detection sheet D-5 is formed in a purple state.

  Further, 0.035 g of acid alizarin violet N is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 20 g of glycerin as a humectant and water are added to make 50 g to prepare a detection solution E-5. . Using this detection solution E-5, an ozone detection sheet E-5 is prepared as described above. The ozone detection sheet E-5 is formed in a purple state.

  In addition, 0.035 g of acid alizarin violet N, 3.0 g of citric acid and 10 g of glycerin as a moisturizer were added with water to prepare a detection solution F-5 with a total amount of 50 g, and this detection solution F-5 As described above, an ozone detection sheet F-5 is prepared. The ozone detection sheet F-5 is formed in an orange color. The ozone detection sheet F-5 is a sample made acidic by adding citric acid.

  Further, 0.035 g of Acid Alizarin Violet N and 10 g of glycerin as a humectant were added with water to prepare a detection solution G-5 having a total amount of 50 g, and this detection solution G-5 was used to detect ozone as described above. G-5 is produced. The ozone detection sheet G-5 is formed in a purple state. In this case, citric acid, sodium hydroxide (base) or the like is not added, and pH adjustment such as alkalinity is not performed.

  About each sample mentioned above (ozone detection sheet A-5, B-5, C-5, D-5, E-5, F-5, G-5), respectively, ozone concentration shall be 0.1 ppm and 25 A test of exposure to ozone gas by leaving it in a box filled with air at a temperature of 60 ° C and humidity of 60% for 5 hours was conducted. The discoloration state of the result of this test was the reflectance of the ozone detection sheet at a wavelength of 530 nm. It was measured. Acid Alizarin Violet N showed a different color when acidified, and the detection sheet F-5 was measured for reflectance at a wavelength of 510 nm. The volume of the box is 200 liters, and internal air is sucked at 2 liters / minute for analysis of the internal ozone concentration, and air containing a predetermined concentration of ozone is supplied at 2 liters / minute. Thus, it exposes to the to-be-detected air and measures the color change of each ozone detection sheet. In addition, the color change is also observed visually. The test results are shown in Table 5 below.

  From the results shown in Table 5, the detection sheet B-5, the detection sheet C-5, and the detection sheet D-5 containing a moisturizing agent are reliably detected by integrating exposure for 5 hours even if the ozone concentration is as low as 0.1 ppm. I understand that I can do it. It can also be seen that the amount of change in color per unit time in the produced detection sheet differs depending on the amount (ratio) of the humectant in the detection solution used when producing the ozone detection sheet. When glycerin is used as a humectant, if the content in the detection solution is in the range of ˜20%, the amount of color change per unit time increases as the amount of glycerin increases. Further, from the result that the detection sheet A-5 is not detected, it can be understood that the detection cannot be performed so much if the humectant is not used. From the results of Table 5, in the case of Acid Alizarin Violet N, the concentration of glycerin in the detection solution may be 10% to 30%, and 20% is optimal.

  Further, even when a humectant is used at the same concentration as that of the detection sheet C-5, as shown in the detection sheet F-5, when the detection sheet is prepared with an acidic detection solution, no color change is detected. It is almost impossible to detect ozone. On the other hand, as shown in the detection sheet G-5, even if it is not alkaline, if the pH is not adjusted without adding a base or an acid, a humectant is used, and the case of the detection sheet C-5 Similarly, ozone can be detected. This can be said to be a state where the acid is not acidified.

[Embodiment 6]
Next, the ozone detection sheet in Embodiment 6 of this invention is demonstrated. Hereinafter, a case where Modern Blue 13 is used as an azo dye instead of Acid Alizarin Violet N will be described. First, 0.053 g of Modern Blue 13 is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to make a total amount of 50 g to prepare a detection solution A-6. Prepared without glycerin as a moisturizer. Using this detection solution A-6, an ozone detection sheet A-6 is prepared as described above. The ozone detection sheet A-6 is formed in a magenta state. The modern blue 13 has spectral characteristics as shown in FIG. 7, and is different depending on whether it is alkaline or acidic.

  Further, 0.053 g of Modern Blue 13 is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 5 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution B-6. . Using this detection solution B-6, an ozone detection sheet B-6 is prepared as described above. The ozone detection sheet B-6 is formed in a magenta state.

  Further, 0.053 g of Modern Blue 13 is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 10 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution C-6. . Using this detection solution C-6, an ozone detection sheet C-6 is prepared as described above. The ozone detection sheet C-6 is formed in a magenta state.

  Further, 0.053 g of Modern Blue 13 is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 15 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution D-6. . Using this detection solution D-6, an ozone detection sheet D-6 is prepared as described above. The ozone detection sheet D-6 is formed in a magenta state.

  Further, 0.053 g of Modern Blue 13 is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 20 g of glycerin as a humectant and water are added to make 50 g to prepare a detection solution E-6. . Using this detection solution E-6, an ozone detection sheet E-6 is prepared as described above. The ozone detection sheet E-6 is formed in a magenta state.

  Further, 0.053 g of Modern Blue 13, 3.0 g of citric acid and 10 g of glycerin as a humectant were added with water to prepare a detection solution F-6 with a total amount of 50 g, and this detection solution F-6 As described above, an ozone detection sheet F-6 is prepared. The ozone detection sheet F-6 is formed in a reddish purple state. The ozone detection sheet F-6 is a sample made acidic by adding citric acid.

  Also, 0.053 g of Modern Blue 13 and 10 g of glycerin as a moisturizer were added with water to prepare a detection solution G-6 with a total amount of 50 g, and this detection solution G-6 was used to detect ozone as described above. G-6 is produced. The ozone detection sheet G-6 is formed in a magenta state. In this case, citric acid, sodium hydroxide (base) or the like is not added, and pH adjustment such as alkalinity is not performed.

  For each of the above-described samples (ozone detection sheets A-6, B-6, C-6, D-6, E-6, F-6, G-6), the ozone concentration was set to 0.1 ppm. The test was conducted by exposing it to ozone gas by leaving it in a box filled with air at a temperature of 60 ° C and humidity of 60%, and the reflectance of the ozone detection sheet at a wavelength of 550 nm was measured for the discolored state resulting from this test. It was measured. Modern blue 13 showed a different color when acidified, and the detection sheet F-6 was measured for reflectance at a wavelength of 530 nm. The volume of the box is 200 liters, and internal air is sucked at 2 liters / minute for analysis of the internal ozone concentration, and air containing a predetermined concentration of ozone is supplied at 2 liters / minute. Thus, it exposes to the to-be-detected air and measures the color change of each ozone detection sheet. In addition, the color change is also observed visually. The test results are shown in Table 6 below.

  From the results shown in Table 6, it can be seen that the detection sheet B-6 and the detection sheet C-6 containing the moisturizing agent can be detected reliably by integrating the exposure for 5 hours even if the ozone concentration is as low as 0.1 ppm. It can also be seen that the amount of change in color per unit time in the produced detection sheet differs depending on the amount (ratio) of the humectant in the detection solution used when producing the ozone detection sheet. When glycerin is used as a humectant, if the content in the detection solution is in the range of ˜20%, the amount of color change per unit time increases as the amount of glycerin increases. Further, from the result that the detection sheet A-6 is not detected, it can be seen that the detection cannot be performed so much if the moisturizing agent is not used. From the results of Table 6, in the case of Modern Blue 13, the concentration of glycerin in the detection solution may be 10% to 20%, and the case of 20% is optimal.

  Further, even when a humectant is used at the same concentration as that of the detection sheet C-6, as shown in the detection sheet F-6, when the detection sheet is prepared with the detection solution in the acidic state, the color change is not detected much. There is almost no ozone detection. On the other hand, as shown in the detection sheet G-6, even if it is not alkaline, if the pH is not adjusted without adding a base or an acid, by using a moisturizing agent, the case of the detection sheet C-6 Similarly, ozone can be detected. This can be said to be a state where the acid is not acidified.

The acid alizarin violet N and modern blue 13 shown above have two hydroxy groups adjacent to the azo group in the benzene ring or naphthalene ring, and there is no SO ₃ group adjacent to the azo group. In other words, the dye is an azo dye having two hydroxy groups at the o-position with respect to the azo group, and the SO ₃ group bonded to other than the o-position with respect to the azo group.

[Embodiment 7]
Next, the ozone detection sheet in Embodiment 7 of this invention is demonstrated. Below, the case where chalcone is used as an azo dye is demonstrated. First, 0.08 g of chalcone is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to make a total amount of 50 g to prepare a detection solution A-7. Chalcone is an azo dye (azo dye) also called Alizarin Blue Black R, and the detection solution A-7 is an amber-colored aqueous solution. The color of the detection solution A-7 can be visually confirmed. Prepared without glycerin as a moisturizer. Using this detection solution A-7, an ozone detection sheet A-7 is prepared as described above. The ozone detection sheet A-7 is formed in a dark blue state. The chalcone has spectral characteristics as shown in FIG. 8 and is different between an alkaline case and an acidic case.

  Further, 0.08 g of chalcone is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 5 g of glycerin as a humectant and water are added to make 50 g, thereby producing a detection solution B-7. Using this detection solution B-7, an ozone detection sheet B-7 is prepared in the same manner as described above. The ozone detection sheet B-7 is formed in a dark blue state.

  Further, 0.08 g of chalcone is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 10 g of glycerin as a humectant and water are added to make 50 g to prepare a detection solution C-7. Using this detection solution C-7, an ozone detection sheet C-7 is prepared as described above. The ozone detection sheet C-7 is formed in a dark blue state.

  Further, 0.08 g of chalcone is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 15 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution D-7. Using this detection solution D-7, an ozone detection sheet D-7 is prepared as described above. The ozone detection sheet D-7 is formed in a dark blue state.

  Further, 0.08 g of chalcone is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 20 g of glycerin as a humectant and water are added to make 50 g, thereby producing a detection solution E-7. Using this detection solution E-7, an ozone detection sheet E-7 is produced in the same manner as described above. The ozone detection sheet E-7 is formed in a state of having a dark blue color.

  Further, 0.08 g of chalcone is dissolved in 25 ml of ethanol, and 3.0 g of citric acid, 10 g of glycerin and water are added thereto to prepare a detection solution F-7 having a total amount of 50 g. Chalcone is soluble in alkaline water but not very soluble in neutral and acidic water, but using ethanol increases the amount of chalcone dissolved in neutral and acidic water. Can do. In the case of azo dyes having two naphthalene rings, such as chalcone, many of them show water solubility by making them alkaline without showing high water solubility in acidity and neutrality. The ozone detection sheet F-7 is prepared in the same manner as described above using the detection solution F-7 thus prepared. The ozone detection sheet F-7 is formed in a magenta state. The ozone detection sheet F-7 is a sample made acidic by adding citric acid.

  Further, 0.08 g of chalcone was dissolved in 25 ml of ethanol, and 10 g of glycerin and water were added thereto to prepare a detection solution G-7 with a total amount of 50 g. A detection sheet G-7 is prepared. The ozone detection sheet G-7 is formed in a state of exhibiting a violet (purple) color. In this case, citric acid, sodium hydroxide (base) or the like is not added, and pH adjustment such as alkalinity is not performed.

  For each of the above-described samples (ozone detection sheets A-7, B-7, C-7, D-7, E-7, F-7, G-7), the ozone concentration was set to 0.1 ppm and 25 The test was conducted by leaving it exposed to ozone gas for 5 hours inside a box filled with air at 60 ° C and humidity of 60%. For the discolored state of the result of this test, the reflectance of the ozone detection sheet at a wavelength of 650 nm was determined. It was measured. When the chalcone was acidic, it showed a different color, and for the detection sheet F-7, the reflectance at a wavelength of 520 nm was measured. The volume of the box is 200 liters, and internal air is sucked at 2 liters / minute for analysis of the internal ozone concentration, and air containing a predetermined concentration of ozone is supplied at 2 liters / minute. Thus, it exposes to the to-be-detected air and measures the color change of each ozone detection sheet. In addition, the color change is also observed visually. The test results are shown in Table 7 below.

  From the results shown in Table 7, it can be seen that in the detection sheet B-7 to detection sheet E-7 containing a humectant, even if the ozone concentration is as low as 0.1 ppm, the detection can be reliably performed by integrating the exposure for 5 hours. It can also be seen that the amount of change in color per unit time in the produced detection sheet differs depending on the amount (ratio) of the humectant in the detection solution used when producing the ozone detection sheet. When glycerin is used as a humectant, if the content in the detection solution is in the range of ˜20%, the amount of color change per unit time increases as the amount of glycerin increases. Further, from the result that the detection sheet A-7 cannot be detected, it can be understood that the detection cannot be performed so much if the humectant is not used. From the results of Table 7, in the case of chalcone, the concentration of glycerin in the detection solution may be 10% to 40%, and the case of 20% is optimal.

  Further, even when the humectant is used at the same concentration as that of the detection sheet C-7, as shown in the detection sheet F-7, when the detection sheet is prepared with the detection solution in the acidic state, no color change is detected. It is almost impossible to detect ozone. On the other hand, as shown in the detection sheet G-7, even if it is not alkaline, if the pH is not adjusted without adding a base or an acid, by using a moisturizer, the case of the detection sheet C-7 Similarly, ozone can be detected. This can also be said to be a state in which it is not acidified.

The chalcone shown above is an azo dye having two hydroxy groups adjacent to the azo group in the two naphthalene rings and having no SO ₃ group adjacent to the azo group.

  In the above-described embodiment, glycerin is used as the moisturizing agent. However, the present invention is not limited to this, and ethylene glycol, propylene glycol, or the like can be used as described below. Moreover, the other moisturizing agent which the pigment | dye mentioned above melt | dissolves may be sufficient.

  Next, a comparative example will be described. Although the comparative example shown below is an azo dye, it shows a case where ozone cannot be detected even if a detection sheet is prepared as described above.

[Comparative Example 1]
Next, the ozone detection sheet of Comparative Example 1 will be described. Hereinafter, Orange G (7-Hydroxy-8- ( phenylazo) -1,3-naphthalenedisulfonic acid, disodium salt: C 20 H 11 N 2 Na 3 O 10 S 3) as the azo dye for the case of using the explained. First, 0.044 g of orange G is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to make the total amount 50 g to prepare a detection solution H-1. The detection solution H-1 is an aqueous solution having an orange color. The color of the detection solution H-1 can be visually confirmed. Prepared without glycerin as a moisturizer. Using this detection solution H-1, an ozone detection sheet H-1 is prepared in the same manner as described above. The ozone detection sheet H-1 is formed in an orange color.

  Further, 0.044 g of orange G is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 10 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution I-1. Using this detection solution I-1, an ozone detection sheet I-1 is prepared in the same manner as described above. The ozone detection sheet I-1 is formed in an orange color.

  Further, 0.044 g of orange G, 3.0 g of citric acid and 10 g of glycerin as a humectant were added with water to prepare a detection solution J-1 having a total amount of 50 g. Similarly, an ozone detection sheet J-1 is produced. The ozone detection sheet J-1 is formed in an orange color. The ozone detection sheet J-1 is a sample made acidic by adding citric acid.

  For each of the samples (ozone detection sheets H-1, I-1, J-1) described above, each of the boxes filled with air having an ozone concentration of 0.1 ppm, 25 ° C., and 60% humidity. A test for exposure to ozone gas was performed by leaving it inside for 5 hours, and the reflectance of the ozone detection sheet at a wavelength of 500 nm was measured for the discolored state as a result of this test. In the case of Orange G, since the maximum part of the spectrum includes 500 nm even in the acidic state, the reflectance at a wavelength of 500 nm was also measured for the ozone detection sheet J-1. The volume of the box is 200 liters, and internal air is sucked at 2 liters / minute for analysis of the internal ozone concentration, and air containing a predetermined concentration of ozone is supplied at 2 liters / minute. Thus, it exposes to the to-be-detected air and measures the color change of each ozone detection sheet. In addition, the color change is also observed visually. The test results are shown in Table 8 below.

From the results shown in Table 8, discoloration due to ozone is not confirmed in any of the detection sheets. Thus, when orange G is used, ozone is not detected not only in the acidic case but also in the alkaline case. This orange G is an azo dye having a SO ₃ group bonded adjacent to the azo group.

[Comparative Example 2]
Next, the ozone detection sheet of Comparative Example 2 will be described. In the following, neucoccin (7-Hydroxy-8- (4-sulfonato-1-naphthylazo) -1,3-naphthalenedisulfonic acid, trisodium salt: C ₂₀ H ₁₁ N ₂ Na ₃ O ₁₀ S ₃ ) is used as the azo dye. The case where it is used will be described. First, 0.058 g of neucoccin is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to make a total amount of 50 g to prepare a detection solution H-2. The detection solution H-2 is an aqueous solution exhibiting rose pink. The color of the detection solution H-2 can be visually confirmed. Prepared without glycerin as a moisturizer. Using this detection solution H-2, an ozone detection sheet H-2 is prepared in the same manner as described above. The ozone detection sheet H-2 is formed in a state exhibiting rose pink.

  Further, 0.058 g of neucoccin is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and 10 g of glycerin as a moisturizing agent and water are added to make 50 g to prepare a detection solution I-2. Using this detection solution I-2, an ozone detection sheet I-2 is prepared in the same manner as described above. The ozone detection sheet I-2 is formed in a state exhibiting rose pink.

  Further, 0.058 g of neucoccin, 3.0 g of citric acid and 10 g of glycerin as a humectant were added with water to prepare a detection solution J-2 having a total amount of 50 g. The ozone detection sheet J-2 is produced in the same manner as described above. The ozone detection sheet J-2 is formed in a state exhibiting rose pink. The ozone detection sheet J-2 is a sample made acidic by adding citric acid.

  For each of the samples (ozone detection sheets H-2, I-2, J-2) described above, each of the boxes filled with air having an ozone concentration of 0.1 ppm, 25 ° C., and 60% humidity. A test for exposure to ozone gas was performed by leaving it inside for 5 hours, and the reflectance of the ozone detection sheet at a wavelength of 525 nm was measured for the discolored state as a result of this test. In the case of neucoccine, since the maximum part of the spectrum includes 525 nm even in an acidic state, the reflectance at a wavelength of 525 nm was also measured for the ozone detection sheet J-2. The volume of the box is 200 liters, and internal air is sucked at 2 liters / minute for analysis of the internal ozone concentration, and air containing a predetermined concentration of ozone is supplied at 2 liters / minute. Thus, it exposes to the to-be-detected air and measures the color change of each ozone detection sheet. In addition, the color change is also observed visually. The test results are shown in Table 9 below.

From the results shown in Table 9, no fading due to ozone is confirmed in any of the detection sheets. Thus, in the case where neucoccin is used, ozone cannot be detected not only in the acidic case but also in the alkaline case. This new coxin is also an azo dye having an SO ₃ group bonded adjacent to the azo group. Thus, when the SO ₃ group bonded adjacent to the azo group is provided, it is considered that ozone is difficult to react due to steric hindrance.

From the above, it can be seen that an azo dye having an SO ₃ group bonded adjacent to an azo group cannot be used for detection of ozone even if it has a hydroxy group. In addition, for detection of ozone, an SO ₃ group bonded to a position not adjacent to the azo group was provided, and at least one hydroxy group bonded to the p-position relative to the position adjacent to the azo group or the azo group was provided. It must be an azo dye. Among them, an azo dye having two hydroxy groups bonded adjacent to the azo group on the same side with respect to the azo group can be used for ozone detection even if it is not alkaline but not acidic. it can. Moreover, it can use for the detection of ozone by making it alkaline other than this.

Here, the above-described azo dye will be described. The azo dye in the ozone detection sheet of the present invention is considered to be capable of detecting ozone because the reaction with ozone is promoted by making it alkaline as shown below. When each of the azo dyes described above is rendered alkaline using sodium hydroxide or the like, hydrogen of the hydroxy group bonded to the benzene ring or naphthalene ring is eliminated, and -O bonded to the benzene ring or naphthalene ring. ^-The group exists. In such a state, it is considered that ozone is easily taken up (pulled) into the —O 2 ^— group. Further, in an alkaline state, these azo dyes are hydrazone type, and there are -N ^- groups in the azo bond (-N = N-) part, and ozone can be taken into this part. Conceivable.

  In the azo dye in the ozone detection sheet of the present invention, when ozone is taken in as described above, the benzene ring (naphthalene ring) is decomposed by the taken-in ozone, and the structure and electronic state of the dye molecule change, and the visible region. It is considered that the above-mentioned color change (fading) occurs due to the change in the light absorption of the light and the color (hue). For these reasons, it is considered that ozone detection can be performed according to the ozone detection sheet of the present invention using the azo dye.

Note that even an azo dye having a hydroxy group bonded to a benzene ring or a naphthalene ring hardly reacts with ozone when supported in an acidic state. This is probably because the —O 2 ^— group is not present in the acidic state. In order to be able to detect ozone, it is necessary for the azo dye to react with ozone, and the presence of an —O ⁻ group bonded to a benzene ring or a naphthalene ring is important. In some neutral azo dyes, discoloration (fading) is detected by reacting with ozone. This is because a hydrogen bond is formed between the hydrogen of the hydroxy group bonded to the benzene ring or naphthalene ring bonded to the azo group and the nitrogen of the azo group, and the oxygen of the hydroxy group becomes a δ- (minus) state. This is considered to be a state close to the —O 2 ^— group. Even in a neutral state, it is considered that some hydrogen may be eliminated.

  Moreover, according to these azo dyes, as well known, the light resistance is strong, and the light resistance is strong against ultraviolet irradiation. For this reason, even in an environment irradiated with ultraviolet rays, it is possible to expect ozone detection with higher accuracy in a state where the influence is small. Among the aforementioned orange I, orange II, crocein orange G, tropeoline O, acid alizarin violet N, modern blue 13, and chalcone, as described later, orange I and tropeoline O are used as pigments. In the gas detection element in the present embodiment, light resistance was obtained.

  First, the resistance of the ozone detection sheet according to the present invention to sunlight when Orange I is used as a pigment will be described.

  First, 0.034 g of Orange I is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to 10 g of glycerin as a moisturizer to make 50 g, thereby producing a detection solution A-8. The ozone detection sheet A-8 is produced in the same manner as described above, for example, by immersing cellulose filter paper (No. 2) manufactured by Advantech (Toyo Filter Paper Co., Ltd.) in this detection solution A-8 for 30 seconds. The ozone detection sheet A-8 is formed in a state exhibiting rose pink.

  Next, the comparison sheet B-8 shown below is produced as a comparison with the ozone detection sheet A-8. First, 0.045 g of indigo carmine is dissolved in 25 ml of water together with 3.5 g of citric acid, and water is added to 15 g of glycerin as a humectant to make 50 g, thereby preparing a solution B-8. A comparative sheet B-8 is prepared in the same manner as described above by immersing cellulose filter paper (No. 2) manufactured by Advantech (Toyo Filter Paper Co., Ltd.) for 30 seconds in this solution B-8. The comparison sheet B-8 is formed in a blue state.

About ozone detection sheet | seat A-8 and comparative sheet | seat B-8 which were mentioned above, respectively, ozone concentration is set to 0.03 ppm and it exposes to the state irradiated with sunlight, and is left to stand for 4 hours. As for the irradiation of sunlight, the average global solar radiation is 0.45 kW / m ² and the UV-B average amount is 0.25 W / m ² . In addition, each is exposed to a state where the ozone concentration is 0.03 ppm in the absence of sunlight, and is left for 5 hours. Moreover, about the discoloration state of the result of these tests, in ozone detection sheet A-8, the reflectance in wavelength 525nm is measured before and behind exposure, and in comparison sheet B-8, the wavelength in wavelength 620nm is measured before and after exposure. The test results are shown in Table 10 below. Table 10 shows the difference in the wavelength measurement results before and after exposure (reflectance difference).

  As shown in Table 10, in the ozone detection sheet A-8, there is no difference in the reflectance difference before and after the exposure when exposed to sunlight (irradiated) and when not exposed to sunlight. This reflectance difference may be considered to have occurred due to exposure to ozone. On the other hand, in Comparative Sheet B-8, there is a difference in reflectance before and after exposure when sunlight is applied and when sunlight is not exposed. The difference in reflectance is greater when sunlight is applied. large. From this, it is considered that the change (fading) due to exposure to sunlight also occurs in the comparative sheet B-8. In Comparative Sheet B-8 using indigo carmine as a pigment, the change due to sunlight irradiation is about 40% of the change due to ozone.

  Next, resistance to sunlight when tropeoline O is used as a pigment will be described.

  First, 0.034 g of tropeoline O is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to 15 g of glycerin as a humectant to make 50 g, thereby producing a detection solution A-9. The ozone detection sheet A-9 is prepared in the same manner as described above by immersing cellulose filter paper (No. 2) manufactured by Advantech (Toyo Roshi Kaisha, Ltd.) in this detection solution A-9 for 30 seconds. The ozone detection sheet A-9 is formed in an orange color state.

  Next, the comparison sheet B-9 shown below is produced as a comparison with the ozone detection sheet A-9. First, 0.045 g of indigo carmine is dissolved in 25 ml of water together with 3.5 g of citric acid, and water is added to 15 g of glycerin as a humectant to make 50 g to prepare a solution B-9. A comparative sheet B-9 is prepared in the same manner as described above by immersing cellulose filter paper (No. 2) manufactured by Advantech (Toyo Roshi Kaisha, Ltd.) in this solution B-9 for 30 seconds. The comparison sheet B-9 is formed in a blue state.

About the ozone detection sheet | seat A-9 and the comparison sheet | seat B-9 mentioned above, respectively, ozone concentration is set to 0.03 ppm and it exposes to the state irradiated with sunlight, and is left to stand for 4 hours. As for the irradiation of sunlight, the average global solar radiation is 0.45 kW / m ² and the UV-B average amount is 0.25 W / m ² . In addition, each is exposed to a state where the ozone concentration is 0.03 ppm in the absence of sunlight, and is left for 5 hours. Moreover, about the discoloration state of the result of these tests, in ozone detection sheet A-9, the reflectance in wavelength 440nm is measured before and behind exposure, and in comparison sheet B-9, the wavelength in wavelength 620nm is measured before and after exposure. The test results are shown in Table 11 below. Table 11 shows the difference (reflectance difference) between the wavelength measurement results before and after exposure.

  As shown in Table 11, in the ozone detection sheet A-9, there is no difference in the reflectance difference before and after the exposure when exposed to sunlight (irradiated) and when not exposed to sunlight. This reflectance difference may be considered to have occurred due to exposure to ozone. On the other hand, in Comparative Sheet B-9, there is a difference in the reflectance before and after exposure when the sunlight is applied and when the sunlight is not applied, and the difference in the reflectance is greater when the sunlight is applied. large. From this, it is considered that a change (fading) due to exposure to sunlight also occurs in the comparative sheet B-9. In Comparative Sheet B-9 using indigo carmine as a pigment, the change due to irradiation with sunlight is about 40% of the change due to ozone. The result of the comparison sheet B-9 is the same as the result of the comparison sheet B-8 described above.

  Next, the resistance to artificially generated ultraviolet rays when Orange I is used as a pigment will be described.

  First, 0.034 g of Orange I is dissolved in 25 ml of an aqueous sodium hydroxide solution having a concentration of 0.1 mol / liter, and water is added to 10 g of glycerin as a humectant to make 50 g, thereby producing a detection solution A-10. The ozone detection sheet A-10 is produced in the same manner as described above by immersing cellulose filter paper (No. 2) manufactured by Advantech (Toyo Roshi Kaisha, Ltd.) for 30 seconds in this detection solution A-10. The ozone detection sheet A-10 is formed in a state exhibiting rose pink. This is the same as the ozone detection sheet A-8.

  Next, the comparison sheet B-10 shown below is produced as a comparison with the ozone detection sheet A-10. First, 0.045 g of indigo carmine is dissolved in 25 ml of water together with 3.5 g of citric acid, and water is added to 15 g of glycerin as a humectant to make 50 g, thereby preparing a solution B-10. A comparative sheet B-10 is produced in the same manner as described above by immersing cellulose filter paper (No. 2) manufactured by Advantech (Toyo Roshi Kaisha, Ltd.) for 30 seconds in this solution B-10. The comparison sheet B-10 is formed in a blue state. This is the same as Comparative Sheets B-8 and B-9.

Each of the ozone detection sheet A-10 and the comparison sheet B-10 described above is irradiated with ultraviolet rays (standard illuminance: 60 W / m ² ) from an artificial ultraviolet light source for 5 minutes. Regarding the state of discoloration before and after this irradiation (ultraviolet light exposure), in the ozone detection sheet A-10, the reflectance at a wavelength of 520 nm is measured before and after the irradiation, and in the comparative sheet B-10, the wavelength at a wavelength of 620 nm is measured before and after the irradiation. To do. The test results are shown in Table 12 below. Table 12 shows the difference (reflectance difference) between the wavelength measurement results before and after irradiation.

  As shown in Table 12, in the ozone detection sheet A-10, the reflectance difference before and after the ultraviolet irradiation is as low as 0.015. On the other hand, in the comparison sheet B-10, the difference in reflectance before and after the ultraviolet irradiation is as large as 0.33. Since the reflectance difference in the completely faded state is 0.54, the comparative sheet B-10 has 60% fade. Similarly, when the light resistance by artificial ultraviolet rays is investigated in the case of Tropeolin O, the difference in reflectance is about 0.01. Moreover, when the light resistance by the same artificial ultraviolet ray is investigated for Orange II, Crocein Orange G, Acid Alizarin Violet N, Modern Blue 13, and Chalcone, the reflectance difference is in the range of 0.1 to 0.3. there were.

  Next, Orange II, Crocein Orange G, Acid Alizarin Violet N, Modern Blue 13, and Chalcone, Orange I and Tropeolin O are examined.

  First, Orange II, Crocein Orange G, Acid Alizarin Violet N, Modern Blue 13, and Chalcone are azo dyes having a hydroxy group (—OH) at the o-position with respect to the azo group. On the other hand, orange I and tropeoline O are azo dyes in which a hydroxy group is present at the p-position with respect to the azo group. Due to these differences, it is considered that the difference in light resistance described above when applied to the gas detection element in the present embodiment has occurred.

  Further, in the benzene ring bonded to the azo group constituting the dye, such as orange I and tropeoline O, in the hydroxy group bonded to the p-position with respect to the azo group, the above-described hydrogen desorption is performed. Separation and ozone uptake are more likely to occur than in the o-position. For this reason, by using an azo dye having a hydroxy group bonded to the p-position with respect to the azo group on the benzene ring bonded to the azo group, the ozone detection sheet of the ozone detection sheet can be compared with other azo dyes. It is considered possible to increase the ozone detection sensitivity.

  In the above-described embodiment, the measurement target gas is not forcibly passed through the ozone detection sheet. However, the measurement target gas may be forcibly passed through a pump or the like. By doing in this way, the integrated amount of ozone can be measured in a shorter time. Moreover, it is also possible to use as an ozone detection seal | sticker by apply | coating an adhesive agent to either surface of an ozone detection sheet.

  In the above description, filter paper is used. However, the present invention is not limited to this. Any sheet-like material composed of cellulose fibers, such as ordinary paper, can be used as a sheet-like carrier. Further, not only cellulose but also a sheet-like material (nonwoven fabric or the like) composed of other fibers such as nylon or polyester can be used as a sheet-like carrier. In particular, the fiber surface should be hydrophilic. The sheet carrier is preferably white, but is not limited thereto. As long as it is possible to confirm a change in color in a state stained with an azo dye such as tropeoline O, other color states may be used.

  In the above description, sodium hydroxide is used as the alkaline substance that makes the aqueous solution alkaline. However, the present invention is not limited to this. For example, it may be a base such as an alkali metal hydroxide such as potassium hydroxide or potassium hydroxide, or an alkaline earth metal hydroxide such as calcium hydroxide. Moreover, even if it is a salt, if an aqueous solution such as sodium hydrogen carbonate is an alkaline substance, an azo dye having an hydroxy group such as tropeoline O (an aqueous solution thereof) can be brought into an alkaline state.

It is process drawing explaining the example of the manufacturing method of the ozone detection sheet in embodiment of this invention. It is a characteristic view which shows the spectrum of orange I. It is a characteristic view which shows the spectrum of orange II. It is a characteristic view showing a spectrum of crocein orange G. It is a characteristic view which shows the spectrum of tropeoline O. It is a characteristic view which shows the spectrum of acid alizarin violet N. FIG. 6 is a characteristic diagram showing a spectral spectrum of modern blue 13. It is a characteristic view which shows the spectrum of chalcone.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 101 ... Detection solution, 102 ... Container, 103 ... Sheet-like carrier, 104 ... Impregnation sheet, 105 ... Ozone detection sheet, 111 ... Dye, 112 ... Alkaline substance, 113 ... Moisturizer.

Claims (10)

A sheet-like carrier composed of fibers;
An azo dye having a sulfite group supported on the carrier and bonded to a position not adjacent to the hydroxy group and the azo group;
An ozone detection sheet characterized in that the aqueous solution carried on the carrier is at least composed of an alkaline substance that becomes alkaline. In the ozone detection sheet according to claim 1,
The ozone detection sheet, wherein the azo dye is selected from the group consisting of orange I, orange II, crocein orange G, tropeoline O, acid alizarin violet N, modern blue 13, and chalcone. In the ozone detection sheet according to claim 1 or 2,
The ozone detecting sheet, wherein the azo dye comprises two hydroxy groups bonded adjacent to the azo group on different sides with respect to the azo group. In the ozone detection sheet according to claim 3,
The ozone detection sheet, wherein the azo dye is selected from Acid Alizarin Violet N, Modern Blue 13, and Chalcone. In the ozone detection sheet according to claim 1 or 2,
The ozone detection sheet, wherein the azo dye has a hydroxy group bonded to the p-position with respect to the azo group. In the ozone detection sheet according to claim 5,
The ozone detection sheet, wherein the azo dye is selected from orange I or tropeoline O. In the ozone detection sheet according to any one of claims 1 to 6,
The ozone detection sheet, wherein the alkaline substance is sodium hydroxide. In the ozone detection sheet according to any one of claims 1 to 7,
The ozone detection sheet is
It is formed by immersing the carrier in a detection solution made alkaline by dissolving the dye and dissolving the alkaline substance, impregnating the carrier with the detection solution, and drying. Ozone detection sheet characterized by In the ozone detection sheet according to any one of claims 1 to 8,
An ozone detection sheet comprising a humectant supported on the carrier together with the dye. In the ozone detection sheet according to claim 9,
The humectant is at least one of glycerin, ethylene glycol, and propylene glycol.

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