JP2012246185A - Azulminic acid mixed liquid and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an azulminic acid mixed liquid in which azulminic acid has high solubility.SOLUTION: The method for producing an azulminic acid mixed liquid includes a step of coexisting the azulminic acid and an organic acid.

Description

  The present invention relates to an azulmic acid mixed solution and a method for producing the same.

  By polymerizing hydrocyanic acid, a hydrocyanic acid polymer called azulmic acid is obtained. Azulmic acid has appeared in some research papers on chemical evolution in which amino acids are produced from hydrocyanic acid, but has rarely been reported in recent years. Since azulmic acid is insoluble in a solvent (see, for example, Non-Patent Document 1), its structure has not yet been clarified, and its use has hardly been studied.

  Under these circumstances, the present inventor has found that a nitrogen-containing carbon material containing a large amount of nitrogen can be obtained by carbonizing azulmic acid as a development of the use of azulmic acid (see Patent Document 1). It has been found that the obtained nitrogen-containing carbon material has an excellent function as an electrode of a lithium ion secondary battery (see Patent Document 2).

  By the way, in general, if a polymer can be dissolved in a solvent, it will be easy to analyze the structure, obtain knowledge of development of use, and also consider direct application. As an application example that can be considered, it is possible to form a film that is difficult with powder by obtaining a polymer solution. In addition, it is possible to mix the polymer with other organic compounds and polymers to react with each other, and it is easy to develop new materials.

  Although azurmic acid is a polymer of a monomer having a nitrile group called cyanic acid, a solvent that dissolves azulmic acid well is not known. Therefore, structural analysis has not been sufficiently performed. The fact that azulmic acid is insoluble or hardly soluble in a solvent is a factor that hinders the spread of its use from a practical viewpoint.

  Under these circumstances, the present inventor has previously found that a solution in which azulmic acid is dissolved can be obtained by mixing azulmic acid with a solvent having an amino group such as ethylenediamine or cyclohexylamine (patent). Reference 3).

International Publication No. 2007/043311 Pamphlet International Publication No. 2008/123380 Pamphlet JP 2010-260773 A

Angew. Chem. 72, p379-384 (1960)

  However, even with the method disclosed in Patent Document 3, the solubility of azulmic acid is still not sufficient. In addition, ethylenediamine having the highest solubility in Patent Document 3 has a problem that white smoke is generated in the air and is difficult to handle, and a solvent having an amino group has a unique amine odor and is difficult to handle. .

  The present invention has been made in view of such circumstances. That is, an object of the present invention is to provide a method for producing an azulmic acid mixed solution having a high solubility of azulmic acid and a mixed solution containing azulmic acid.

  As a result of intensive studies to solve the above problems, the present inventors have surprisingly found that azulmic acid exhibits solubility in organic acids, and have completed the present invention.

That is, the present invention is as follows.
(1) Azulmic acid mixed solution containing azurmic acid and organic acid.
(2) A method for producing an azulmic acid mixed solution, which comprises a step of allowing azulmic acid and an organic acid to coexist.

  ADVANTAGE OF THE INVENTION According to this invention, the azurmic acid mixed liquid with high solubility of azurmic acid and its manufacturing method can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The present embodiment is an example for explaining the present invention, and the present invention is not limited only to the embodiment. That is, the present invention can be variously modified without departing from the gist thereof.

  The method for producing an azulmic acid mixed solution according to the present embodiment includes a step of allowing azulmic acid and an organic acid to coexist, and may include a step of producing azulmic acid prior to the step.

  Azulmic acid is a general term for polymers obtained by polymerizing hydrocyanic acid (hydrogen cyanide). What was manufactured by the well-known method can be used for cyanuric acid, and the manufacturing method is not specifically limited. For example, hydrocyanic acid is by-produced in a method for producing acrylonitrile or methacrylonitrile by a gas phase catalytic reaction in which propylene, isobutylene, tert-butyl alcohol, propane, isobutane or the like is reacted with ammonia and an oxygen-containing gas in the presence of a catalyst. According to this method, it is possible to obtain hydrocyanic acid at a very low cost. In addition, since this type of gas phase contact reaction is a known reaction, the reaction conditions may be any known one. In addition, in the production of acrylonitrile and methacrylonitrile, in order to increase the production of by-product hydrocyanic acid, a raw material (for example, methanol or the like) that produces hydrocyanic acid by an ammoxidation reaction may be supplied to the reactor.

  Cyanic acid is also produced by the Andrewsso process in which methane, which is the main component of natural gas, is reacted with ammonia and an oxygen-containing gas in the presence of a catalyst. This method also makes it possible to obtain hydrocyanic acid at a very low cost.

  Of course, hydrocyanic acid can also be produced by a laboratory production method using soda hydride or the like, and those obtained in this way can also be used. However, from the viewpoint of being able to produce hydrocyanic acid in a large amount and at a low cost, those produced industrially, such as the production of acrylonitrile and methacrylonitrile and the Andrewsso method are preferred.

  In the step of producing azulmic acid, the raw material containing hydrocyanic acid obtained as described above is polymerized to obtain azulmic acid which is a black to brown polymer. Here, from the viewpoint of obtaining high-purity azulmic acid, the content of the polymerizable substance other than hydrocyanic acid is preferably 40% by mass or less, more preferably 10% by mass with respect to the total amount of the raw material. % Or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less. In other words, the content of hydrocyanic acid in the raw material is preferably 60% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 99% by mass with respect to the total amount of the raw material. It is at least mass%.

  Azulmic acid can be produced by polymerizing hydrocyanic acid and optionally a small amount of other polymerizable substances in various ways. As the polymerization method, for example, a method of heating liquefied hydrocyanic acid or an aqueous solution of hydrocyanic acid, a method of leaving them for a long time, a method of adding a base to them, a method of irradiating them with light, and radiating them with high energy Examples thereof include a method, a method of performing various discharges in the presence thereof, and a method of electrolyzing an aqueous potassium cyanide solution.

In a method in which a base is added to liquefied hydrocyanic acid or an aqueous solution of hydrocyanic acid and the hydrocyanic acid is polymerized in the presence of the base, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, organic base, ammonia, aqueous ammonia are used as the base. It can be illustrated. Examples of the organic base include primary amine (R ¹ NH ₂ ), secondary amine (R ¹ R ² NH), tertiary amine (R ¹ R ² R ³ N), and quaternary ammonium salt (R ¹ R ² R). ³ R ⁴ N ⁺ ). Here, R ¹ , R ² , R ³ and R ⁴ represent an alkyl group having 1 to 10 carbon atoms which may be the same or different from each other, a phenyl group, a cyclohexyl group, or a group obtained by combining these, These may further have a substituent. Of these organic bases, aliphatic or cycloaliphatic tertiary amines are preferred. Examples of such tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, tetramethylammonium hydroxide, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0]. Undec-7-ene (DBU). The bases exemplified above are used singly or in combination of two or more.
In addition, azurmic acid can be obtained by collecting deposits from the apparatus in the purifying process of cyanuric acid by-produced in the ammoxidation process such as propylene.

  The composition of azulmic acid can be measured using a CHN analyzer. The ratio of the number of moles of nitrogen to the number of moles of carbon atoms in azulmic acid ((number of moles of nitrogen atoms) / (number of moles of carbon atoms)) is preferably 0.2 to 1.0, more Preferably it is 0.3-1.0, More preferably, it is 0.6-0.95.

Azulmic acid used in the present embodiment, the spectrogram by laser Raman spectroscopic analysis of wave number 1000～2000Cm ^-1, the Raman shift 1300～1400Cm ^-1, to exhibit peaks at any position of 1500～1600Cm ^-1 It is particularly preferable that a peak is exhibited at any position of 1360 to 1380 cm ⁻¹ and 1530 to 1550 cm ⁻¹ .

  Azulmic acid used in the present embodiment exhibits a strong peak at a diffraction angle (2θ) of 26.8 ± 1 ° in the range of 10 to 50 ° of an X-ray diffraction diagram obtained using CuKα rays as an X-ray source. Is. This peak is preferably shown at a position of 26.8 ± 0.5 °, more preferably at a position of 26.8 ± 0.2 °. In addition to the above-mentioned peak, the azurmic acid used in the present embodiment has a diffraction angle (2θ) of 12.3 ± in the range of 10 to 50 ° in an X-ray diffraction diagram obtained using CuKα rays as an X-ray source. A peak may be shown at a position of 1 °, preferably at a position of 12.3 ± 0.5 °.

  The azulmic acid used in this embodiment has a main peak at 399.0 ± 0.7 eV, preferably at 399.0 ± 0.4 eV, particularly preferably at 399.0 ± 0.2 eV in the XPS spectrum diagram of N1s. It is preferable to have.

  In addition, azulmic acid can be used individually by 1 type or in combination of 2 or more types from which the manufacturing method, a composition, and a manufacturing lot differ.

  Next, in the step of coexisting azulmic acid and organic acid, an azulmic acid mixed solution can be produced by coexisting them. At this time, as long as a coexistence state can be obtained, either of these may be added to either. That is, an organic acid may be added to a container in which azulmic acid is accommodated, and conversely, azulmic acid may be added to a container in which an organic acid is accommodated, or they may be put into the container at the same time. Good.

  As an organic acid, the organic compound which has a carboxyl group, and the organic compound which has a sulfone group can be illustrated.

  Specifically, organic compounds having a carboxyl group include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid , Myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, tuberculostearic acid, arachidic acid, arachidonic acid, eicosapentaenoic acid, behenic acid, docosahexaenoic acid, lignoceric acid, cerotic Acid, montanic acid, mellicic acid, salicylic acid, trihydroxybenzoic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, melittic acid, pyruvic acid, oxalic acid, lactic acid, tartaric acid, maleic acid, fumaric acid, Malonic acid, succinic acid, malic acid, citric acid, glycol , Aconitic acid, glutaric acid, adipic acid, itaconic acid, can be exemplified acrylic acid, methacrylic acid and trifluoroacetic acid.

  Examples of the organic compound having a sulfone group include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and cyclohexanesulfonic acid.

Among these, the organic acid is preferably an organic compound having a carboxyl group from the viewpoint of high solubility. From the same viewpoint, the organic acid is more preferably an organic compound having a carboxyl group and an aldehyde group, and an organic compound having a carboxyl group and a hydroxyl group. Examples of preferred organic acids include formic acid, acetic acid, glycolic acid and trifluoroacetic acid. As an example of an organic compound having a carboxyl group and an aldehyde group, formic acid can be exemplified. As an example of an organic compound having a carboxyl group and a hydroxyl group, glycolic acid can be exemplified.
Further, for example, an organic acid having a low molecular weight is preferable from the viewpoint of removing an organic acid by volatilization by heating drying or drying under reduced pressure after the azulmic acid mixed solution is formed into a thin film or the like. The molecular weight of the organic acid is preferably 500 or less, more preferably 200 or less, and still more preferably 100 or less.

  From the viewpoint of obtaining a state in which a sufficient amount of azulmic acid is dissolved or mixed in the mixed solution, the number of moles of the organic acid is 1 or more in terms of mole ratio with respect to the number of moles of hydrocyanic acid units of azulmic acid. preferable. Here, “the number of moles of hydrocyanic acid unit of azulmic acid” is a value obtained by dividing the mass (g) of azulmic acid by 27, which is the molecular weight of hydrocyanic acid. The molar ratio is more preferably 5 or more, and still more preferably 10 or more. From the viewpoint of preventing excessive energy required for separating the organic acid and azulmic acid, the molar ratio is preferably 100,000 or less, more preferably 10,000 or less, and even more preferably 1000 or less. .

  The organic acid itself may be used as a solvent, or may be used as a solution by mixing with water and / or an organic solvent. In the case of an organic acid aqueous solution, the concentration (mass basis) of the organic acid is not particularly limited, but is generally preferably 10 to 90%, more preferably 20 to 80%. In addition, you may use an organic acid individually by 1 type or in combination of 2 or more types.

  When azulmic acid is in a mixed solution state, preferably in a solution state, it is advantageous from a practical viewpoint as compared with a powder state. For example, azurmic acid can be easily formed into a film, or azurmic acid can be mixed with other organic compounds or polymers to promote the reaction with them. In addition, from the viewpoint of basic research, it will be easier to proceed with structural analysis, and if the structural analysis proceeds, it will be possible to expand the practical use of azulmic acid.

An example of a more specific method for producing an azulmic acid mixed solution will be described below.
In addition, at the stage before manufacturing a liquid mixture, an azulmic acid may be a powder or a block shape. Further, it is preferable that the powdered or massive azulmic acid is pulverized in advance with a ball mill or the like to be used as a raw material of the mixed solution.

  In the step of coexisting azulmic acid and organic acid, an organic acid or a solution thereof is added to a container containing azulmic acid powder, and azulmic acid powder is added to a container containing the organic acid or solution thereof. Or after putting both into a container simultaneously, it is preferable to shake the container, to stir, or to apply an ultrasonic wave with respect to the container, and to mix. At this time, the container may be heated from the viewpoint of facilitating dissolution of azulmic acid.

  Although the temperature at the time of mixing them is not specifically limited, 0-200 degreeC is preferable, More preferably, it is 10-150 degreeC. The temperature is more preferably 20 to 70 ° C. from the viewpoint of the solubility of azulmic acid and the stability of the organic acid.

  Although the pressure at the time of mixing them is not specifically limited, 2 MPa or less is preferable, 1 MPa or less is more preferable, More preferably, it is 0.2 MPa or less. Moreover, as mixing time, 1 minute-100 hours may be sufficient, for example, Preferably it is 10 minutes-20 hours, More preferably, it is 30 minutes-2 hours.

  In the present specification, the “azurmic acid mixed solution” includes an azulmic acid solution in which azulmic acid is completely dissolved. Therefore, the azulmic acid may be completely dissolved or may be partially dissolved. The mode of the azulmic acid mixed solution, such as the degree of dissolution of azulmic acid and the concentration of the azulmic acid mixed solution, may be properly used depending on the application.

  For example, the concentration of the azulmic acid mixed solution (azurmic acid concentration in the mixed solution) is preferably 0.000001% by mass to 50% by mass, more preferably 0.00001% by mass to 30% by mass, based on mass. Can also be used. If an azurmic acid mixed solution is used to produce a thin film, the concentration is preferably low, and can be exemplified by 0.000001% by mass to 0.1% by mass. On the other hand, if an azulmic acid mixed solution is used to produce a thick film, the concentration is preferably high to some extent, and can be exemplified by 0.1 to 50% by mass. If an azurmic acid mixed solution is used to promote the reaction by mixing with another organic compound or polymer, the concentration is preferably somewhat high, and can be exemplified by 0.1 to 50% by mass.

  According to this embodiment, it is possible to provide an azulmic acid mixed solution that can dissolve azurmic acid with high solubility and a method for producing the same. Moreover, when manufacturing and using the azurmic acid mixed liquid of this embodiment, it becomes possible to suppress generation | occurrence | production of white smoke and an amine odor.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, these are illustrative and this invention is not limited to these. Accordingly, those skilled in the art can implement the present invention by making various modifications to the embodiments described below, and such modifications are included in the scope of the claims of the present application.

<Production example>
(Manufacture of azulmic acid)
An aqueous solution in which 150 g of hydrocyanic acid was dissolved in 350 g of water was prepared in a container, and 120 g of a 25% aqueous ammonia solution was added over 10 minutes while stirring the aqueous solution, and the resulting mixture was heated to 35 ° C. Then, polymerization of hydrocyanic acid started and a blackish brown polymer started to precipitate, and the temperature gradually increased to 45 ° C. Two hours after the start of polymerization, a 30% by mass aqueous solution of hydrocyanic acid was added at a rate of 200 g / h, and 800 g was added over 4 hours. During the addition of the aqueous hydrocyanic acid solution, the container was cooled and controlled so that the reaction temperature was maintained at 50 ° C. Stir at this temperature for 100 hours. The resulting black precipitate was separated by filtration. The yield of the precipitate at this time was 96% with respect to the total amount of hydrocyanic acid used. The separated precipitate was washed with water and then dried at 120 ° C. for 4 hours in a drier to obtain azulmic acid.

<Azuric acid analysis>
(CHN analysis)
Using an elemental analyzer (trade name “MICRO CORDER JM10”) manufactured by J Science Lab, a sample stage was filled with 2500 μg of azulmic acid sample, and CHN analysis was performed. The temperature of the sample furnace is 950 ° C., the temperature of the combustion furnace (copper oxide catalyst) is 850 ° C., and the temperature of the reduction furnace (consisting of a silver grain + copper oxide zone, a reduced copper zone and a copper oxide zone) is 550 ° C. Set to. The oxygen flow rate was set to 15 mL / min, and the He flow rate was set to 150 mL / min. TCD was used as a detector. Calibration was performed by the method described in the manual using Antipyrine.

  As a result, the composition of azulmic acid obtained in the above production example was 40.0% by weight of carbon element, 29.8% by weight of nitrogen element, and 4.1% by weight of hydrogen element. Here, since the adsorbed water remains under the above-described drying conditions, the difference is considered to be mainly derived from the oxygen element and the hydrogen element in the adsorbed water.

(Measurement of laser Raman spectrum)
The Raman spectrum of azulmic acid was measured under the following conditions by crushing an azulmic acid sample with an agate mortar and filling it in a powder cell.
Apparatus: Trade name “System-3000” manufactured by Reninshaw, light source: Ar laser (wavelength 540 nm, 2 mW), beam size: 5 μm, operation range: 1000 to 2000 cm ⁻¹ , integration time: 5 minutes.
As a result, the azulmic acid obtained in the above Production Examples, among 1000~2000cm ^-1, 1543cm ^-1, and had a strong peak at 1375 cm ^-1.

(Measurement of X-ray diffraction)
The X-ray diffraction pattern of azulmic acid was measured under the following conditions after azulmic acid sample was pulverized in an agate mortar and filled in a powder cell.
Apparatus: Trade name “Rint2500” manufactured by Rigaku Corporation, X-ray source: Cu tube (Cu-Kα ray), tube voltage: 40 kV, tube current: 200 mA, spectral crystal: yes, scattering slit: 1 °, diverging slit: 1 °, light receiving slit: 0.15 mm, scanning speed: 2 ° / min, sampling width: 0.02 °, scanning method: 2θ / θ method.
Further, X-ray diffraction angle data obtained for silicon powder was used for correcting the X-ray diffraction angle (2θ).
As a result, the azulmic acid obtained in the above production example had the strongest peak at 27.0 ° and the broad peak at around 12.3 ° between 5 ° and 50 °.

<Chloroform treatment>
10 g of azulmic acid was washed for 5 hours by a Soxhlet extraction method using 300 g of chloroform. This washing is intended to extract and remove components that are relatively soluble in a solvent, such as low molecular weight substances and linear structures contained in azulmic acid. Residual azulmic acid is clearly poorly soluble, but by adding azulmic acid obtained by polymerization into a basic or acidic aqueous solution or a basic or acidic aqueous solution, the solubility of azulmic acid by this operation Can be evaluated.
In addition, chloroform after this washing | cleaning was transparent and colorless, and most azurmic acid was collect | recovered as a residue.

[Example 1]
200 g of formic acid was added as a solvent to 1 g of azulmic acid obtained through the above chloroform treatment and stirred at 50 ° C. for 1 hour to obtain an azulmic acid mixed solution. The azulmic acid mixture was colored black. Next, the obtained azulmic acid mixed solution was subjected to suction filtration using a filter having a pore size of 1 μm, and the solid content was separated and removed therefrom to obtain a filtrate. As the filter, a hydrophilic PTFE filter manufactured by ADVANTEC (trade name “H100A090C” was used. Then, the solvent was removed from the obtained filtrate by evaporation using an evaporator, and the mass of the collected precipitates. The dissolution rate in the solvent was calculated by measuring the dissolution rate in the solvent, which is expressed by the following formula.
(Mass of precipitate recovered from the evaporator) / (Mass of azulmic acid contained in the azulmic acid mixed solution) × 100

  Table 1 shows the results of the dissolution rate and the presence or absence of white smoke from the solvent. Whether or not white smoke was generated from the solvent was judged by visually confirming whether white smoke was generated when the azurmic acid mixed solution was brought into contact with air in the container.

[Example 2]
An azulmic acid mixed solution was obtained in the same manner as in Example 1 except that formic acid was replaced with a formic acid aqueous solution (formic acid and water mixed at a mass ratio of 1: 1). About the azurmic acid mixed solution, the dissolution rate was measured in the same manner as in Example 1 to confirm whether white smoke was generated from the solvent. The results are shown in Table 1.

[Example 3]
An azulmic acid mixed solution was obtained in the same manner as in Example 1 except that formic acid was replaced with acetic acid. About the azurmic acid mixed solution, the dissolution rate was measured in the same manner as in Example 1 to confirm whether white smoke was generated from the solvent. The results are shown in Table 1.

[Example 4]
An azulmic acid mixed solution was obtained in the same manner as in Example 1 except that formic acid was replaced with trifluoroacetic acid. About the azurmic acid mixed solution, the dissolution rate was measured in the same manner as in Example 1 to confirm whether white smoke was generated from the solvent. The results are shown in Table 1.

[Example 5]
An azulmic acid mixed solution was obtained in the same manner as in Example 1 except that formic acid was replaced with a 20% oxalic acid aqueous solution and the temperature during stirring was changed from 50 ° C to 110 ° C. About the azurmic acid mixed solution, the dissolution rate was measured in the same manner as in Example 1 to confirm whether white smoke was generated from the solvent. The results are shown in Table 1.

[Example 6]
An azulmic acid mixed solution was obtained in the same manner as in Example 1 except that formic acid was replaced with a 70% glycolic acid aqueous solution. About the azurmic acid mixed solution, the dissolution rate was measured in the same manner as in Example 1 to confirm whether white smoke was generated from the solvent. The results are shown in Table 1.

[Example 7]
An azulmic acid mixed solution was obtained in the same manner as in Example 1 except that the temperature during stirring was changed from 50 ° C to 20 ° C. About the azurmic acid mixed solution, the dissolution rate was measured in the same manner as in Example 1 to confirm whether white smoke was generated from the solvent. The results are shown in Table 1.

[Example 8]
An azulmic acid mixed solution was obtained in the same manner as in Example 6 except that the temperature during stirring was changed from 50 ° C to 20 ° C. About the azurmic acid mixed solution, the dissolution rate was measured in the same manner as in Example 1 to confirm whether white smoke was generated from the solvent. The results are shown in Table 1.

[Comparative Example 1]
An azulmic acid mixed solution was obtained in the same manner as in Example 1 except that formic acid was replaced with ethylenediamine. About the azurmic acid mixed solution, the dissolution rate was measured in the same manner as in Example 1 to confirm whether white smoke was generated from the solvent. The results are shown in Table 1.

[Comparative Example 2]
An azulmic acid mixed solution was obtained in the same manner as in Example 1 except that formic acid was replaced with ethylenediamine and the stirring temperature was changed from 50 ° C to 110 ° C. About the azurmic acid mixed solution, the dissolution rate was measured in the same manner as in Example 1 to confirm whether white smoke was generated from the solvent. The results are shown in Table 1.

  From the above results, it was found that the solubility of azulmic acid was remarkably improved according to the production method of the present invention. Moreover, even if the azurmic acid liquid mixture based on this invention contacted air, it turned out that generation | occurrence | production of white smoke can be suppressed.

  According to the present invention, an azulmic acid mixed solution in which azulmic acid is well dissolved can be obtained. By making azulmic acid into a mixed solution, it is possible to form a film compared to the powdered state, and it is possible to promote the reaction by mixing with other organic compounds and polymers. Have advantages. In addition, from the viewpoint of basic research, the structure analysis of azulmic acid can be carried out efficiently by using a mixed solution, so that the practical use of azulmic acid can be further expanded. . Therefore, the present invention can be used widely and usefully in the field of electronic materials, electronic / electrical materials including the same, electronic / electrical devices, and various devices, facilities, systems, and the like including the electronic / electrical materials.

Claims (2)

  Azulmic acid mixed solution containing azulmic acid and organic acid.   A method for producing an azulmic acid mixed solution, comprising a step of allowing azurmic acid and an organic acid to coexist.