KR102258034B1 - Organic Volatile Acid-Base Sensitive Discoloration Film - Google Patents

Abstract

This cationic pH dye and anionic pH dye are formed by ion pairing, providing a complex and solving the conventional problems that occurred to detect organic volatile acid-bases, high price, limited types of detection materials, and difficulty in real-time detection. It is about the provision.

Description

Organic Volatile Acid-Base Sensitive Discoloration Film

The present invention relates to an organic volatile acid-volatile base sensing discoloration film, and specifically, to a film including a composite including a material in which a cationic pH dye and an anionic pH dye are ion-paired.

Volatile organic compounds (VOCs) refer to gaseous volatile substances having carbon at room temperature and pressure, and among them, substances having an acid or base are referred to as volatile organic acids, respectively. VOAs), called volatile organic bases. Since these organic volatile acids or volatile bases are produced as metabolic by-products of various organisms, they are treated with great importance in the food or pharmaceutical field. In addition, it may play the role of a reactant and a catalyst in a chemical reaction, and may also be produced as a product of a reaction. Above all, since it is a kind of organic volatile matter, such as acetic acid and formaldehyde, when present in high concentrations in the air, it is harmful to the human body. Due to the harmfulness to the human body, there are many substances that have standards for indoor air quality.

With the recent incident of fine dust and humidifier disinfectants from China and the strengthening of indoor air quality management laws, research on the detection of organic volatile acids or volatile bases, which is one of the criteria for measuring air pollution, is indispensable. It appears as a field. However, the current detection method relies only on a mechanical method, which acts as a big limitation in terms of price and portability. Of course, detection devices with enhanced portability are being developed, but still have disadvantages of high price, limited types of detection materials, and difficulty in real-time detection.

Under this background, the present inventors have made diligent efforts to overcome the shortcomings of the conventional sensing technology, and as a result of the present invention, manufacturing a sensing discoloration film for an organic volatile acid or volatile base material that is inexpensive, simple, and capable of real-time detection. By confirming, the present invention was completed.

Korean Patent Registration 10-1738761

One object of the present invention is to provide a complex formed by ion pairing of a cationic pH dye and an anionic pH dye.

Another object of the present invention is to provide an organic volatile acid-volatile base-sensitive composition comprising a complex as an active ingredient, formed by ion pairing of a cationic pH dye and an anionic pH dye.

Another object of the present invention is to stir an aqueous solution containing a cationic pH dye and an anionic pH dye to form an ion-paired complex in the aqueous solution; And

To provide a method for producing an organic volatile acid-volatile base-sensitive composition comprising the; step of extracting the organic solvent phase by adding an organic solvent as an extraction solvent to an aqueous solution containing the complex.

Another object of the present invention is a solid support; And it is to provide an organic volatile acid-volatile base-sensitive film comprising the organic volatile acid-volatile base-sensitive composition of any one of claims 5 to 11 coated on the solid support.

This will be described in detail as follows. Meanwhile, each description and embodiment disclosed in the present invention can be applied to each other description and embodiment. That is, all combinations of various elements disclosed in the present invention belong to the scope of the present invention. In addition, it cannot be seen that the scope of the present invention is limited by the specific description described below.

As used herein, the term "organic volatile acid-volatile base" refers to a volatile organic compound including organic volatile acid and a volatile base. Volatile organic compounds (VOCs) are liquid or gaseous organic compounds that are easily evaporated into the atmosphere due to their low boiling point. It is very diverse, ranging from organic gas, to liquid fuels with low boiling points, paraffins, olefins, aromatic compounds, and other hydrocarbons that are commonly used around life. VOCs generate photochemical oxidizing agents such as ozone through a photochemical reaction together with nitrogen oxides (NOx) in the atmosphere to cause photochemical smog, and substances such as benzene are carcinogenic substances that are very harmful to the human body, and most VOCs including styrene Can be classified as a substance that causes odor. The main emission sources include anthropogenic emission sources such as organic solvent use facilities, painting facilities, laundry, storage stations, gas stations and exhaust gas from various transportation means, and natural emission sources such as trees. Among them, substances that exhibit acid or base are referred to as volatile organic acids (VOAs) and volatile organic bases, respectively.

In the present specification, the term "pH dye" refers to a reagent that changes color with a change in hydrogen ion concentration, and refers to a conventional acid base indicator. An acid-based indicator is a pigment that is itself a weak acid or a weak base, and its ionic color and structure are different from the color and structure of the non-dissociated type. In the discoloration range, two forms are common in various ratios, one of which is usually present in the lower pH range, and the other form in the pH range higher than this discoloration range. The former color is called acidic color, and the latter color is called basic or alkaline color. In the discoloration range, the colors of the two types are mixed. The acid phosphorus indicator is called the acid indicator, and the base phosphorus indicator is called the basic indicator.

In the present specification, "extraction" is a method of separating a component from a mixture using distribution caused by selective solubility, and after quenching the reaction in organic chemistry, an organic compound during the work-up process This is a typical process for separating. It refers to the process of drawing organic compounds into the organic solvent layer by using the property that the organic compounds mixed in the water layer are well soluble in the organic solvent.

In the present specification, "ion pairing" refers to an association of two ions having the same properties while having an opposite charge, and means that a pair of a cation and an anion approaching according to an electrostatic interaction become a pair.

In the present specification, "to be ion paired", "to form ion pairing", and "to form ion pairing" means that the cationic pH dye and the anionic pH dye of the present invention are ionically bonded to form a complex, each The water-soluble cationic pH dye and the anionic pH dye are ion-paired to form a complex and become oil-soluble, thereby having increased hydrophobicity. Unless otherwise specified, the terms are used interchangeably.

A first aspect of the present invention for achieving the above object relates to a complex formed by ion pairing of a cationic pH dye and an anionic pH dye.

In one embodiment of the present invention, one of the dyes constituting the complex may react with an acidic substance and the other react with a basic substance. For example, the unshared electron pair in the reactive group or the reaction stage of the cationic dye reacts to the acidic substance that accepts the electron pair, causing discoloration. In addition, the hydrogen proton in the reactive group or the reaction stage of the anionic dye reacts with a basic substance that is an electron pair donor to cause discoloration. As a result, each of the two different dyes can react with both acidic and basic substances, respectively, which provides the effect of simultaneously detecting organic volatile acids and organic volatile bases.

In one embodiment of the present invention, the cationic pH dye is crystal violet (CV), malachite green, Astrazon orange G, rhodamine BRhodamin B) or Nile red chloride (Nile red Chloride), but is not limited thereto, and may be used as long as it is a pH dye (pH indicator) in which a cation (X+) portion is present.

The CV changes from acidic green to basic blue at around pH 1.5. In aqueous solution, discoloration is not sensitive and the acid form is unstable. In addition, it is used for titration of a solvent other than water, in particular, titration of an acid base using glacial acetic acid as a solvent. In this case, the acid color is yellow and the basic color is blue.

In one embodiment of the present invention, the anionic pH dye is thymol blue, bromophenol blue, bromocresol green, bromocresol purple, bromo thymol Blue (Bromothymol blue), phenol red (Phenol red), naphtholphthalein (Naphtholphthalein) or cresol red (Cresol red) may be, but is not limited thereto, a pH dye (pH indicator) in which an anion (Y-) part is present ), you can use it.

The cresol red sodium salt has two discoloration ranges, and changes from red to yellow at pH 0.4 to 2.2 and from yellow to red at pH 7.2 to 8.8.

In one embodiment of the present invention, the complex has a discoloration range of pH 1 to 14, specifically 2 to 14, and can simultaneously detect organic volatile acids and volatile bases.

In addition, in the complex according to the present invention, the solubility property may be changed from water-soluble to oil-soluble by ion pairing between a cationic pH dye and an anionic pH dye.

A second aspect of the present invention for achieving the above object relates to an organic volatile acid-volatile base-sensitive composition comprising the complex of the first aspect as an active ingredient.

In one embodiment of the present invention, the sensitive composition has a discoloration range of pH 1 to 14, specifically 2 to 14, and can simultaneously detect organic volatile acids and volatile bases.

In one embodiment of the present invention, the composition may further include a polymer urethane, but is not limited thereto.

As used herein, the term "polymer polymer" refers to a polymer material capable of carrying a pH dye, more specifically, the above-described composite, and the polymer polymer is used as a base material for forming a polymer matrix.

Examples of the polymer polymer may include a urethane-based polymer, a styrene-based, acrylic-based, or ethylene-based polymer, preferably a urethane-based polymer.

The urethane-based polymer refers to a polymer having a urethane bond -NHCOO- in the center of the main chain. That is, it is generally obtained from a reaction of a compound containing a hydroxyl group and a compound having an isocyanate group. There are thermosetting and thermoplastic. It is rich in rubber elasticity, and has abrasion resistance, aging resistance, and oil resistance. It means that it is widely used in synthetic leather, adhesives, and paints.

The mixing ratio of the composite and the polymer polymer may be 5wt% to 90wt% based on the weight of the composite, but is not limited thereto, and depending on the environment, the polymer content is increased in an environment where the solvent is frequently contacted to prevent the elution of the pH dye. The polymer content can be appropriately changed to prevent it and maintain it in the form of a film.

If the polymer is less than 5wt%, the pH dye may be easily eluted, and if it exceeds 90wt%, the thickness of the film increases, thereby reducing the transmittance of the sensing material and reducing the sensitivity to discoloration.

By adjusting the polymer content of the polymer, the sensitivity to the sensing material can be adjusted, and at the same time, the elution of the pH dye material can be reduced.

In one embodiment of the present invention, the composition is a sensitivity modulating material DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), pyridine (Pyridine), alkane amines (Alkanamine, ex: Methylamine), already Dazole (Imidazole), benzimidazole (Benzimidazole), histidine (Histidine), guanidine (Guanidine) may further include a phosphazine base (Phosphazene base), but is not limited thereto.

The sensitivity adjusting material may provide an effect of increasing the sensitivity in order to detect organic volatilization.

Since the complex formed by ion pairing of the present invention is in a strongly acidic state, there is a problem that it is difficult to cause a discoloration reaction to organic volatile acid that reduces the pH. Therefore, since the already ion-paired complex has a low pH, the pH is no longer reduced by organic volatilization. As a result, the discoloration reaction due to organic volatilization may not occur. Therefore, adding a small amount of the sensitivity control material (DBU), which is a basic material, changes the ion-paired complex to a basic state, thereby reducing the pH change due to organic volatilization. You can improve your ability to sense. The film to which the sensitivity control material (DBU) is added and the film to which the sensitivity control material (DBU) is added can be composed of a single conjugate medium complex, and such a conjugate or complex can be provided as a single color change system capable of simultaneously detecting organic volatile acid and organic volatile base have.

The content of the sensitivity control material may be greater than 0 to 10 wt%, but is not limited thereto.

When the content of the sensitivity modifier is close to 10wt% to 0wt%, the sensitizing composition may act sensitively in detecting the basic sensing substance as it is relatively acidic, but if it exceeds 10wt%, it reacts sensitively to basic sensing. I can't.

The composition may be applied, absorbed, or coated on a polymeric support, but is not limited thereto.

A third aspect of the present invention for achieving the above object is a step of stirring an aqueous solution containing a cationic pH dye and an anionic pH dye to form an ion-paired complex in the aqueous solution; And extracting an organic solvent phase by adding an organic solvent as an extraction solvent to an aqueous solution containing the complex. It relates to a method for preparing an organic volatile acid-volatile base-sensitive composition.

Since the cationic pH dye and the anionic pH dye of the present invention have hydrophilicity, they may be dissolved in water and exist in a solution state, but the ion-paired complex by stirring them may have oil-soluble properties and thus have increased hydrophobicity. Accordingly, the composite of the present invention may be mixed with an organic solvent to exist in an organic solvent phase, and separated into an organic solvent layer and an aqueous layer through layer separation, and then only the organic solvent phase may be separated to extract the composite.

In the step of forming the complex, the cationic pH dye and the anionic pH dye may be mixed and stirred at a mixing ratio of about 1:1 based on the weight.

It may be preferable in terms of the yield of the complex to have a mixing ratio of 1:1 between the cationic pH dye and the anionic pH dye, and the yield may decrease as the mixing ratio exceeds the above. Any residual pH dye that did not form a complex in this step can be removed through an extraction process.

Stirring in the step of forming the complex may be performed under conditions of a stirring speed of about 30 RPM to 5000 RPM.

More specifically, the stirring speed may range from 50 RPM to 1500 RPM. It may be preferable that it is in the range of 500 RPM to 1000 RPM, but it can be appropriately changed according to reaction conditions and circumstances.

The temperature of the step of forming the composite may be 20 ℃ to 30 ℃. The complex formation step may be preferably performed at room temperature, but may be appropriately changed according to reaction conditions and circumstances.

When the temperature is less than 20° C., the reaction rate is slow, making it difficult to form a complex, and when the temperature exceeds 30° C., the solvent may be evaporated and thus it may be difficult to form a complex.

The pressure in the step of forming the composite may be approximately atmospheric pressure (1 atm), but is not limited thereto.

The step of forming the complex may be performed for about 5 to 24 hours. It may be desirable to proceed for 6 hours, but it can be appropriately changed depending on the reaction conditions and circumstances.

If the reaction time is less than 5 hours, the yield may decrease, and if the reaction time exceeds 24 hours, a significant increase in yield cannot be expected since sufficient reaction has already been made. Considering the overall efficiency, the reaction exceeds 24 hours excessively. It may be unnecessary to maintain.

In the step of extracting the organic solvent phase, the mixing amount of the organic solvent may be 0.5 to 3 times the volume of the solution containing the formed composite, but is not limited thereto.

The organic solvent may include methyl ethyl ketone (MEK), ethyl acrylate (EA), or a mixture thereof, but is not limited thereto.

Specifically, the organic solvent methyl ethyl ketone and ethyl acrylate may be mixed and used in a 5:5 weight ratio, but is not limited thereto.

The temperature of the step of extracting the organic solvent phase may be 0 ℃ to 30 ℃. Specifically, the extraction temperature may be preferably room temperature, but may be appropriately changed according to the reaction conditions and circumstances.

When the temperature is less than 0°C, extraction may be difficult as the state of the solvent changes from liquid to solid, and when the temperature exceeds 30°C, the solvent may be vaporized and extraction may be difficult.

The step of extracting the organic solvent phase may be performed under approximately atmospheric pressure (1 atm). The extraction pressure may be preferably normal pressure, but may be appropriately changed according to reaction conditions and circumstances.

The step of extracting the organic solvent phase may be performed for about 20 to 30 hours. Specifically, the extraction time may be preferably 24 hours, but can be appropriately changed according to the reaction conditions and circumstances.

If the reaction time is less than 20 hours, layer separation is not smooth, and the two different solutions are present in a partially mixed state. Accordingly, the yield and purity may decrease. If the reaction time exceeds 30 hours, after sufficient reaction has already been made. Therefore, a significant increase in yield cannot be expected, and considering the overall efficiency, it may be unnecessary to maintain the reaction excessively exceeding 30 hours.

The method for preparing an organic volatile acid-volatile base sensitive composition of the present invention includes the steps of concentrating the extracted organic solvent phase after the step of extracting the organic solvent phase; And

Drying the concentrated organic solvent phase to form a powder; may further include.

In the present specification, the term "concentration" means increasing the concentration of a solute by removing the solvent in the solution, and can be applied by selecting an appropriate method from a conventional concentration method in the art. Examples of such a conventional concentration method include vacuum concentration, ventilation concentration, frozen concentration, and spray concentration.

The concentration of the complex is increased by the concentration of the organic solvent phase containing the complex of the present invention by the above extraction.

Since the concentration can increase the concentration rate while lowering the heating temperature, it may be preferable to proceed using reduced pressure distillation.

The method for preparing an organic volatile acid-volatile base sensitive composition of the present invention may further include washing after the step of extracting the organic solvent phase and adding magnesium sulfate.

The addition of magnesium sulfate is one of materials widely used together with sodium sulfate when removing moisture (water) from an organic solvent, and may be an absorbent material that completely removes moisture. It can bring about the effect of preventing physical and chemical deterioration caused by a trace amount of moisture.

The magnesium sulfate may be removed by optionally removing it before the concentration step.

After the magnesium sulfate is extracted, the magnesium sulfate absorbs a trace amount of moisture present in the organic solution layer, and then, it can be removed through a filter. In a manner widely used in extraction, since it is a heterogeneous material used as an absorbent, magnesium sulfate may be removed so as not to exert any role on the final product.

The term "drying" in the present invention means removing all of the solvent to make it free of solvent. That is, it means evaporating the solvent using a generally used physical method (eg, lyophilization), a chemical method (eg, using a desiccant), a mechanical method (eg, a dryer), or a combination thereof.

Specifically, the drying may be performed in a vacuum oven for 20 to 48 hours, but is not limited thereto.

The concentrated organic solvent phase of the present invention can be dried in a vacuum oven for more than one day to remove all remaining solvents to form a powder, which is a solid dye powder.

A fourth aspect of the present invention for achieving the above object relates to an organic volatile acid-volatile base-sensitive film comprising the organic volatile acid-volatile base-sensitive composition of the second aspect.

The composition may be provided as an organic volatile acid-volatile base-sensitive film by forming a film with only the composition without a support, but is not limited thereto.

A fifth aspect of the present invention for achieving the above object is a solid support; And

It relates to an organic volatile acid-volatile base sensitive film comprising the organic volatile acid-volatile base sensitive composition of the second aspect coated on the solid support.

The film may be prepared by coating on another solid support.

As used herein, the term "solid support" means any solid support capable of fixing the film of the present invention.

The solid support may include a PET film, but is not limited thereto.

Specifically, the film of the present invention may be coated on the PET film using a coating machine, for example, a bar coater, on the solid support PET film, and then dried using a heat gun to coat the solid support PET film. You can complete it.

The organic volatile acid-volatile base sensing complex according to the present invention, the sensing composition including the complex, and the sensing discoloring film including the complex and/or composition easily and conveniently contain organic volatile acids and volatile base substances, In addition, since it can be detected in real time, the manufacturing cost is also inexpensive, and the scope of application is wide, the industrial application value is high.

Figure 1 (a) is a reaction formula showing the ion pairing of cationic and anionic pH dyes of the present invention, (b) is a schematic diagram showing a method of manufacturing the same, and (c) is a photograph comparing the difference in hydrophilicity and hydrophobicity before and after ion pairing. to be.
2 is a graph showing solution H-NMR (NMR) analysis of CV, CR, and ion-paired CV and CR.
3 is a graph showing the color of each dye according to the pH of the aqueous solution, and (b), (c), and (d) the UV-Vis absorbance analysis results thereof.
Figure 4 shows (a) pH 2.05, (b) pH 5.98, (c) pH 10.00, (d) pH 13.81 CV, CR, [CV] [CR] color differences (L*, a*, b*) This is a graph showing the analysis result.
Figure 5 (a) is a photograph showing the sensing discoloration film prepared in the example, (b) is a schematic diagram showing the organic volatile acid and base measurement method, and (c) is a photograph showing the discoloration result after exposure.

Hereinafter, the present invention will be described in more detail through examples. These examples are for explaining the present invention more specifically, and the scope of the present invention is not limited by these examples.

Preparation Example 1: Preparation of organic volatile acid-volatile base sensing film

In order to manufacture a film capable of simultaneous detection of organic volatile acids and volatile bases, a material having a charge opposite to that of the target material was used as a phase transfer catalyst using ion pairing. By using a pH dye, a method in which each other acts as a phase transfer catalyst was used.

Specifically, the preparation of the ion pairing material was performed in the following order, at room temperature and under normal pressure. When ion pairing is performed, conventionally water-soluble pH dyes are oil-soluble, and they are purified through an extraction method using an organic solvent, and ion-paired substances of two different pH dyes are obtained. A color-changing film was prepared using this material.

Step 1: Prepare an aqueous solution 1 by dissolving 0.5 g of crystal violet (CV) in 100 mL of water.

Step 2: Prepare aqueous solution 2 by dissolving 0.5 g of cresol red sodium salt (CR) in 100 mL of water.

Step 3: Prepare 200 ml of aqueous solution 3 by mixing each of the previously prepared aqueous solutions 1 and 2 and stirring at 500 RPM for about 6 hours.

Step 4: To the prepared aqueous solution 3, 200 ml of an organic solvent mixed with methyl ethyl ketone (MEK) and ethyl acrylate (EA: ethyl acrylate) at a volume ratio of 5:5 was added to separate the aqueous phase and the organic phase to completely separate the two layers. Extraction (Liquid-Liquid extraction) is performed.

Step 5: Separate the organic phase from the resulting two phases, and then wash three or more times with water.

Step 6: Magnesium sulfate (MgSO ₄ ) was added to the washed organic solvent, and stirred for a day (about 24 hours).

Step 7: Using filter paper, remove magnesium sulfate from the organic solvent phase.

Step 8: The organic solvent phase from which magnesium sulfate has been removed is concentrated to a high concentration using distillation under reduced pressure.

Step 9: Put the concentrated organic solvent phase in a vacuum oven and dry for more than one day to remove all remaining solvent.

Step 10: Obtain 0.87 g of dark blue solid powder (ion pairing complex material).

Step 11: Dissolve 40 g of urethane polymer (manufactured by Hanwha Chemical's L-75) at 40 wt% in 60 g of a mixed solvent of MEK and EA to obtain 100 g of a urethane polymer solution.

Step 12: The solid powder (ion pairing composite material) is dissolved in 0.5 wt% in the urethane-based polymer solution obtained in the previous step to prepare a composition (coating solution) for detecting organic volatile acid-volatile base. At this time, a small amount (0.1g, 0.1wt) of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) is added to improve the detection ability of organic volatilization.

Step 13: The prepared solution is coated on a PET film having a thickness of about 0.2 mm under conditions of room temperature and pressure using a bar coater No. 9.

Step 14: Dry for 60 seconds using a heat gun.

As shown in FIG. 1, an organic volatile acid or base sensing discoloration film was prepared using a urethane-based polymer as a matrix. The detection principle for organic volatile acids or bases is the same as for conventional pH dyes. The unshared electron pair of the amine part present in the CV reacts to the acidic substance that accepts the electron pair, causing discoloration. In addition, the hydrogen proton of the phenol part present in CR reacts with the basic substance, which is an electron pair, to cause discoloration. As a result, the prepared film can react with both an acidic substance and a basic substance, respectively, as the composite formed by ion pairing of two pH dyes having different discoloration ranges is stably maintained, which means that the film can react with organic volatile acids and organic substances. It means that volatile bases can be detected at the same time.

Looking at the manufacturing process of the sensing film of Preparation Example 1, only the organic volatile acid sensing film is manufactured by adding a small amount of DBU, which is a basic material. This is because the ion-paired pH dye before DBU is added is in a strongly acidic state, so it is highly likely that it may not exhibit a discoloration reaction to organic volatile acids that reduce the pH, and thus may not exhibit the ability to detect organic volatile acids. In other words, since the ion-paired pH dye obtained in step 10 has a low pH, the pH is no longer reduced by organic volatilization. As a result, a discoloration reaction due to organic volatilization does not occur. Therefore, by adding a small amount of a basic substance (DBU) to change the ion-paired pH dye to a basic state, it was intentionally designed to detect a pH change due to organic volatilization. It was confirmed that a single discoloration system capable of sensing organic volatile acids and volatile bases at the same time was successfully implemented by configuring the two types of sensing films with and without DBU as a single combination.

Test Example 1: NMR analysis

The ion pairing material of Preparation Example 1 was subjected to NMR analysis to confirm the structural formula before and after ion pairing using d-methanol (MeOD) as a solvent.

As shown in Figure 2, CV, CR, and solution-phase proton nuclear magnetic resonance (solution H-NMR) analysis of ion-paired [CV][CR], CV and CR were analyzed alone to obtain a peak result, By NMR analysis of [CV][CR], it was confirmed that all peaks present in the above CV and CR were at the same time. In addition, according to the result of quantitative analysis using the peak area, it can be confirmed that CV and CR exist in a ratio of exactly 1:1 in [CV][CR], so that complete ion pairing was achieved in a ratio of 1:1 with each other. It can be concluded.

Test Example 2: UV-Vis analysis

Each dye according to the pH of the aqueous solution prepared by using hydrochloric acid (HCl) and sodium hydroxide (NaOH) for the ion pairing material ([CV] [CR]) of Preparation Example 1 and CV and CR before ion pairing It was analyzed to confirm the color and UV-Vis absorbance analysis. Specifically, each of the UV-Vis cells (cell) is ethanol (ethanol, each dye (CV, CR and [CV] [CR]) dissolved in 0.05 wt% in an aqueous solution of 3 mL of which the pH is adjusted to 0.01 to 13.81, EtOH) solution 100 μL was added.

As shown in FIG. 3, CV, CR, and [CV][CR] according to the pH aqueous solution are shown, and the discoloration range and color and absorption wavelength of CV and CR can be confirmed. Then, the ion paired [ Through the range of color change and absorption wavelength according to the pH of CV][CR], it was confirmed that the sum of the above CV and CR and each property were retained, and the possibility of detecting organic volatile acids and volatile bases was confirmed. .

Test Example 3: Analysis of chromaticity table

For the ion-paired composite material ([CV][CR]) of Preparation Example 1, and each CV and CR before ion-pairing, color difference in aqueous solutions (pH 2.05, 5.98, 10.00, 13.81) having a preset pH Was analyzed.

As shown in FIG. 4, the UV-Vis absorbance in each preset pH aqueous solution was converted using the color difference (L*, a*, b*) obtained using the Color Master View program and analyzed using a color chart. As a result, it was confirmed that the ion-paired composite material exhibited a different color difference depending on the pH, so that organic volatile acids, organic volatile acids, and organic volatile bases could be detected at the same time.

Test Example 4: Analysis of discoloration of the film after exposure to organic volatile acid and volatile base

The film prepared in Preparation Example 1 was reacted with an organic volatile acid and an organic volatile base to analyze the discoloration result. Specifically, after attaching a sensing discoloration film to the upper surface of a petri dish, an organic volatile substance was injected into the lower surface to detect only gaseous substances generated by volatilization. The reaction with the organic volatile acid and the organic volatile base was exposed for 30 minutes to allow sufficient color change time, and the results were analyzed.

RGB analysis results before and after exposure to organic volatile acids and volatile bases No DBU added DBU addition Acetic acid Formic acid Acetic acid Formic acid R G B R G B R G B R G B Before exposure 125 128 186 129 131 186 169 167 182 155 152 169 After exposure 126 117 185 126 132 185 177 170 169 154 144 173 Change

11.09 3.32 15.56 9.00 ammonia Triethylamine ammonia Triethylamine R G B R G B R G B R G B Before exposure 112 114 171 120 122 179 154 153 171 152 149 165 After exposure 155 149 155 126 127 178 149 149 170 157 154 165 Change

57.71 7.87 6.48 7.07

As shown in Tables 1 and 5, through contrast and reading of pictures taken before and after exposure of each organic volatile acid and volatile base of the organic volatile acid-volatile base-sensing color change film of Preparation Example 1, before exposure and exposure After that, a clear color change appeared, and it was confirmed that the detection of organic volatile substances was possible. According to the RGB change value, in the case of organic volatile acid, it was found that the change value was increased when DBU was added compared to the case where DBU was not added, and the detection ability of organic volatile acid was increased. More specifically, the ion-paired pH dye complex before DBU is added is strongly acidic, but the acidity of the pH dye is changed to a basic state due to DBU addition, so that it is converted into an advantageous state to exhibit a discoloration reaction to organic volatile acid. It was confirmed that the simultaneous detection capability of organic volatile acids, and further organic volatile acids and volatile bases, was also improved.

In the synthesis of Preparation Examples 1 to 5 of the present invention, the organic volatile acid-volatile base-sensing color change film can simultaneously detect the volatile acid and the volatile base, and a small amount of basic material is formed after the formation of the ion-paired composite material. By adding it, it can be seen that the detection ability and sensitivity to organic volatile acids can be adjusted.

From the above description, those skilled in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features thereof. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not limiting. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the claims to be described later rather than the above detailed description and equivalent concepts are included in the scope of the present invention.

Claims (19)

delete delete delete delete Including a complex formed by ion pairing of a cationic pH dye and an anionic pH dye,
The cationic pH dye is crystal violet (CV), the anionic pH dye is Cresol red (CR),
The crystal violet and the cresol red are ionically bonded in a molar ratio of 1:1 to show fat solubility,
An organic volatile acid-volatile base sensitive composition further comprising DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) as a sensitivity adjusting material for sensing organic volatile acids.
The method of claim 5,
One of the pH dyes reacts with an acidic substance and the other reacts with a basic substance. Organic volatile acid-volatile base sensitive composition.
The method of claim 5,
The composition further comprises a polymer polymer, organic volatile acid-volatile base sensitive composition.
The method of claim 7,
The high-molecular polymer comprises a urethane-based polymer, organic volatile acid-volatile base-sensitive composition.
The method of claim 7,
The mixing ratio of the polymer polymer to the composite is 5wt% to 90wt% based on the weight of the composite, organic volatile acid-volatile base sensitive composition.
delete The method of claim 5,
The content of the sensitivity control material is 0 wt% to 10 wt%, organic volatile acid-volatile base-sensitive composition.
The method of claim 5,
The composition is one that can be coated on a polymeric support, organic volatile acid-volatile base-sensitive composition.
Stirring an aqueous solution containing a cationic pH dye and an anionic pH dye to form an ion-paired complex in the aqueous solution; And
Including; adding an organic solvent as an extraction solvent to the aqueous solution containing the complex to extract the organic solvent phase; Including,
The cationic pH dye is crystal violet (CV), the anionic pH dye is Cresol red (CR),
The crystal violet and the cresol red are ionically bonded in a molar ratio of 1:1 to show fat solubility,
A method for preparing an organic volatile acid-volatile base sensitive composition further comprising DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) as a sensitivity adjusting material for detecting organic volatile acid.
delete The method of claim 13,
The organic solvent is methyl ethyl ketone (MEK: methyl ethyl ketone), ethyl acrylate (EA: EthylAcrylate), or a mixture thereof, organic volatile acid-a method for producing a volatile base-sensitive composition.
The method of claim 13,
Concentrating the extracted organic solvent phase after extracting the organic solvent phase; And
Drying the concentrated organic solvent phase to form a powder; which further comprises, organic volatile acid-a method for producing a volatile base-sensitive composition.
An organic volatile acid-volatile base-sensitive film consisting of the organic volatile acid-volatile base-sensitive composition according to claim 5.
Solid support; And
An organic volatile acid-volatile base-sensitive film comprising the organic volatile acid-volatile base-sensitive composition according to claim 5 coated on the solid support.
The method of claim 18,
The solid support will include a PET film, organic volatile acid-volatile base-sensitive film.

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