JPH0867667A - Aqueous solution containing perdicarboxylic acid - Google Patents

Abstract

PURPOSE: To obtain an aqueous solution containing a perdicarboxylic acid, capable of efficiently forming a peracid by using a combined dicarboxylic acid and better in stability, performance or economical efficiency than those in the case of using a single carboxylic acid and useful for sterilizing, bleaching or cleaning. CONSTITUTION: The aqueous solution containing a perdicarboxylic acid is obtained by reacting a combined dicarboxylic acid containing glutaric acid and succinic acid with hydrogen peroxide and contains (1) 0.05-1.0mol/kg solution (expressed in terms of monoperdicarboxylic acid) perdicarboxylic acid, (2) 0.2-2.2 mol/kg solution total dicarboxylic acids except the perdicarboxlic acid, (3) 1.0-12.0mol/kg solution hydrogen peroxide and (4) a stabilizer at 0.01-3.0wt.% concentration and the succinic acid (including persuccinic acid) at a concentration within the range of 0.1-0.7mol/kg solution succinic acid at 0.1-2.0 molar ratio of the succinic acid (including persuccinic acid) to 1mol glutaric acid (including perglutaric acid).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stable perdicarboxylic acid-containing aqueous composition used for applications such as sterilization, bleaching and washing, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Percarboxylic acids are usually synthesized from carboxylic acids or carboxylic acid anhydrides and hydrogen peroxide, and are widely used as oxidants for various substances due to their oxidizing power, as well as good sterilization, bleaching and washing. It is also used in these applications because it exhibits such effects. The usage forms of these peracids are roughly classified into solid ones and aqueous ones, and peracetic acid is known as a typical one of the aqueous percarboxylic acids. Peracetic acid is its stability,
Alternatively, it is widely used for applications such as sterilization, bleaching and washing due to the generality of acetic acid as a raw material, but depending on the application, its use may be restricted by the peculiar odor of peracetic acid, which solves this problem. Therefore, various stable and odorless peracids have been studied, and Japanese Patent Laid-Open No. 53-81619 proposes a stable odorless perglutaric acid concentrate.

Other odorless peracids include perdicarboxylic acids such as persuccinic acid and peradipic acid. The peracid is produced by using the carboxylic acid and hydrogen peroxide as raw materials and the peracid produced. Since carboxylic acid and hydrogen peroxide during the reaction are more equilibrium with peroxidic acid, the higher the concentration of them, the more efficiently the peracid is produced. It has low solubility and does not efficiently form peracid, which is disadvantageous in terms of production efficiency.
In addition, since only a low concentration peracid solution can be obtained, it is disadvantageous in terms of distribution and the like. Therefore, the acid anhydride such as succinic anhydride or adipic anhydride is exclusively used for the production of these peracids. Things are used as raw materials.

However, while the peracid aqueous solution derived from these anhydrides can generate a high concentration of peracid, as the peracid is decomposed, a hardly soluble mother acid crystal precipitates in the cold state. It is easy to do and has a problem from the viewpoint of stability over time or safety, and it is accompanied by the economical reason that the raw material anhydride is relatively expensive, so general applications other than special applications It is in a state where it is rarely used.

Although perglutaric acid is excellent in water solubility, its effect on sterilization and other uses is insufficient, and pure glutaric acid as a raw material is compared with succinic acid and adipic acid. Since it is rare and expensive, it is more difficult to generally use the raw material and the economical aspect.

[0006]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a defect or a disadvantage in production efficiency and distribution due to the change with time of the perdicarboxylic acid-containing aqueous solution derived from such odorless, low-water-soluble dicarboxylic acids. For general purpose sterilization, bleaching and washing with stability or performance and economical efficiency, which has improved stability and improved action effect or economic problem of perglutaric acid aqueous solution derived from water-soluble glutaric acid. It is to provide an aqueous solution composition.

[0007]

Means for Solving the Problems As a result of intensive studies on these problems, the inventors of the present invention mixed succinic acid and adipic acid having low water solubility with glutaric acid having high water solubility,
The complex dicarboxylic acid aqueous solution in which these odorless dicarboxylic acids are dissolved can dissolve succinic acid and adipic acid, which have low water solubility, at a higher concentration with respect to the existing water, and the complex dicarboxylic acid aqueous solution can be dissolved. By adding hydrogen oxide and reacting, even if the usage ratio of glutaric acid is reduced, efficient formation of perdicarboxylic acid is carried out, and it is possible to improve the economic problem and to obtain the desired concentration composition. It was found that the dicarboxylic acid-containing aqueous solution is excellent in action and effect during use and is less likely to cause crystal precipitation during storage, thereby improving various problems of the odorless perdicarboxylic acid-containing aqueous solution derived from a single dicarboxylic acid. Therefore, it is possible to obtain a perdicarboxylic acid-containing aqueous solution that is superior in terms of stability, safety, performance, and economy. This has led to the completion of the out of the present invention.

That is, according to the present invention, (1) perdicarboxylic acid (converted to monoperdicarboxylic acid) obtained by reacting a complex dicarboxylic acid containing glutaric acid and succinic acid with hydrogen peroxide is 0.05 to 1.0 mol. / Kg solution, (2) Total dicarboxylic acids excluding perdicarboxylic acid 0.2 to 2.2 mol / Kg
Solution, (3) hydrogen peroxide 1.0-12.0 mol / Kg solution,
(4) Stabilizer is contained in a concentration of 0.01 to 3.0% by weight,
And the concentration of succinic acid (including persuccinic acid) is 0.1 to 0.7.
Succinic acid (including persuccinic acid) per mol of glutaric acid (including perglutaric acid) in the range of mol / Kg solution
(1) a percarboxylic acid-containing aqueous solution having a molar ratio of 0.1 to 2.0, and a complex dicarboxylic acid containing glutaric acid, succinic acid, and adipic acid, and hydrogen peroxide. Dicarboxylic acid (converted to monoperdicarboxylic acid) is 0.05 to 1.0 mol / Kg solution, (2) Total dicarboxylic acids excluding perdicarboxylic acid is 0.2 to 2.2 mol / Kg
Solution, (3) hydrogen peroxide 1.0-12.0 mol / Kg solution,
(4) The stabilizer is contained in a concentration of 0.01 to 3.0% by weight, the succinic acid (including persuccinic acid) concentration is 0.1 to 0.7 mol / Kg solution, and the adipic acid (including peradipic acid) concentration is
In the range of 0.02 to 0.2 mol / Kg solution, the total molar ratio of other dicarboxylic acids (including each perdicarboxylic acid) to 1 mol of glutaric acid (including perglutaric acid) is
The present invention relates to a perdicarboxylic acid-containing aqueous solution contained in a ratio of 0.1 to 2.0, and a method for producing them.

The perdicarboxylic acid-containing aqueous solution of the present invention requires glutaric acid as an essential component, and is used by combining succinic acid and adipic acid. These dicarboxylic acids are dissolved in water to prepare dicarboxylic acid having a predetermined concentration and ratio. An aqueous solution, which is further treated and purified with an ion exchange resin,
After removing the contained heavy metals, a hydrogen peroxide solution is added and reacted in the presence of a stabilizer to prepare it, but it can be further diluted with deionized water or the like to a desired concentration if necessary. .

The complex dicarboxylic acid aqueous solution used in the present invention basically comprises glutaric acid, succinic acid, adipic acid and the like in a single pure form, and these are used in a desired concentration,
A complex dicarboxylic acid aqueous solution is prepared by dissolving it in water at a ratio, but crude dicarboxylic acids in the form of a mixture of these dicarboxylic acids in stoichiometric and non-stoichiometric ratios are readily available, and industrially, these are used as raw materials for complexing. It is advantageous to prepare an aqueous dicarboxylic acid solution. In this case, once dissolved in water by heating and then cooled, the unnecessary portion of the low-solubility dicarboxylic acid is crystallized, separated and removed, or the mixed dicarboxylic acids are suspended in water and the insoluble portion is removed. The concentration or ratio of each dicarboxylic acid is adjusted by a method of separating and removing the above or a method of mixing and using the mixed dicarboxylic acid and a single dicarboxylic acid to prepare a desired aqueous solution of the complex dicarboxylic acid. In addition, if desired, the anhydrides of these dicarboxylic acids can be used by dissolving and hydrating in water.

The amount of low-solubility dicarboxylic acids such as succinic acid or adipic acid dissolved in water increases as shown in Table 1 due to the coexistence of glutaric acid, whereby the low-solubility dicarboxylic acids existing in the aqueous solution of complex dicarboxylic acids are increased. Since the dissolution ratio can be increased and a large amount of dicarboxylic acids can be dissolved in less water, the equilibrium reaction of perdicarboxylic acid can be carried out more advantageously.

[0012]

[Table 1]

The concentration of the dicarboxylic acid in the complex aqueous solution of dicarboxylic acid is related to the composition of the final aqueous solution containing the perdicarboxylic acid, and the ratio of hydrogen peroxide to dicarboxylic acid added during the reaction or the amount of hydrogen peroxide used. Since the concentration and other factors are selected, it cannot be specified unconditionally, but generally, the operability of the purification operation of the dicarboxylic acid aqueous solution using an ion exchange resin or a chelate resin, the efficiency of removing heavy metals, and / or the target According to the production efficiency of the dicarboxylic acid, the concentration of the dicarboxylic acid is 2 to 6 mol / Kg solution, preferably 3 to 5 mol / Kg solution, which is subjected to the treatment with the ion exchange resin.

The dicarboxylic acid as a raw material usually contains a trace amount of a heavy metal as an impurity and coexists during the reaction of the dicarboxylic acid with hydrogen peroxide to inhibit the formation of the perdicarboxylic acid, and is aimed at. If a concentration of perdicarboxylic acid cannot be obtained, or if it exists in the final perdicarboxylic acid-containing aqueous solution as it is, the decomposition of perdicarboxylic acid or hydrogen peroxide is promoted, and the storage stability is lowered.
In order to cause practical problems, for the purpose of removing these metal ions, dicarboxylic acids are treated with an ion exchange resin or a chelate resin after being made into an aqueous solution, and iron, copper, nickel, chromium in the aqueous solution of the composite dicarboxylic acid, The total heavy metal ion concentration of manganese and zinc is lowered to 2 mg / Kg solution or less. As the ion exchange resin here, a generally known strongly acidic cation exchange resin having a sulfonic acid group as an ion exchange functional group can be preferably used, and as the chelate resin, an iminodiacetic acid group is contained, or In addition, polyamine type generally known chelating resins can be used. The removal of metals from the aqueous solution of dicarboxylic acid can be performed by treating with a cation exchange resin or a chelate resin, and the target metal can be removed. If stabilization is desired, a further better storage stability can be obtained by further using an anion exchange resin before the cation exchange resin treatment to remove a trace amount of metal in the anion state.

Treatment of the raw material dicarboxylic acid aqueous solution with an ion exchange resin or a chelate resin is generally carried out by suspending the resin in the dicarboxylic acid aqueous solution and separating it by filtration, or by passing it through a packed column filled with the resin. It is carried out according to a conventional method, and in order to avoid crystal precipitation of dicarboxylic acids during the treatment, the concentration of the dicarboxylic acid in the treatment liquid is set to be equal to or lower than the saturation concentration at the treatment temperature, and the concentration of the heavy metals is 2.0 mg / kg. Hereinafter, it is desirably used as a 1.0 mg / kg or less aqueous solution of dicarboxylic acid for reaction with hydrogen peroxide. The cation exchange resin after the treatment is reused by recycling it with an aqueous solution of a mineral acid such as dilute sulfuric acid.

The production of perdicarboxylic acid in the present invention is as follows.
It is carried out by a method in which a complex dicarboxylic acid aqueous solution purified by the above method and a hydrogen peroxide aqueous solution are mixed in the presence of a stabilizer and reacted with stirring, and deionized water is added at the time of reaction if desired. The concentration can be adjusted by a method such as dilution or addition of a solid dicarboxylic acid. The reaction can be carried out by reacting at a low temperature such as 0 to 30 ° C. for a long time, but it is not efficient as an industrial production, and therefore it is usually performed for the purpose of increasing the reaction rate.
To 80 ° C, preferably 40 to 60 ° C, and if necessary, a reaction solution using an acidic substance such as sulfuric acid, phosphoric acid, condensed phosphoric acids, or phosphonic acids as a catalyst, if necessary. The reaction time can be further shortened by adding 1 to 10 g per Kg.

In order to allow a high reaction temperature in the reaction, it is necessary that the reaction solution is highly stabilized. If the raw material aqueous solution of dicarboxylic acid is not sufficiently purified, or the amount of the stabilizer is insufficient. If it seems to be insufficient,
As a result, the produced perdicarboxylic acid is rapidly decomposed at a high temperature, so that a perdicarboxylic acid solution having a desired concentration cannot be obtained. The reaction time is usually 2 to 80 hours,
It is preferably carried out for 4 to 50 hours, but when the final concentration of the required perdicarboxylic acid is low, such as when the reaction solution is diluted to give the final composition after the reaction, the reaction time As a result, the time required for reaching the equilibrium composition can be shortened without being restricted.

The ratio of the dicarboxylic acid and hydrogen peroxide to be mixed in the reaction can be arbitrarily selected in relation to the composition of the target final composition liquid, but the concentration of the dicarboxylic acid in the reaction liquid is constant. In the case of, when the ratio of hydrogen peroxide to dicarboxylic acid is increased, the ratio or concentration of perdicarboxylic acid produced increases, and although it is efficient in terms of production of perdicarboxylic acid, the concentration of hydrogen peroxide is also increased. Therefore, it is not preferable to use a larger amount than necessary because the increase in the peroxide concentration also increases the potential risk during handling or storage of the final composition liquid. In addition, it is not efficient to use a lower ratio than necessary because the production rate of perdicarboxylic acid decreases.
The molar ratio of hydrogen peroxide to dicarboxylic acid in the present invention is 0.2 to 15, preferably 0.5 to 10. The concentration of hydrogen peroxide used is usually 10 to 70% by weight from the viewpoint of handling or danger.However, in the case where a high concentration of perdicarboxylic acid is desired to be produced, in terms of production efficiency. It is advantageous to use higher concentrations.

The stabilizer added during the reaction is
Organic phosphonic acids such as aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid) or pyridinecarboxylic acids such as picolinic acid, dipicolinic acid, quinolinic acid Suitable, 0.01 for the reaction mixture
~ 3.0 wt%, preferably 0.05-1.0 wt% is added to carry out the reaction.

The perdicarboxylic acid-containing aqueous solution obtained by the reaction is used as it is as a final composition liquid, or if desired, water and dicarboxylic acids from which heavy metals have been removed are added,
Use an aqueous solution with a predetermined concentration range. The perdicarboxylic acid-containing aqueous solution contains dicarboxylic acids, hydrogen peroxide,
Ultimately, the equilibrium composition changes depending on the concentration of each component of water, and higher perdicarboxylic acid concentrations are permissible as the concentration of dicarboxylic acids increases, but if it is made higher than necessary, crystals will precipitate in the cold. It is easy to cause problems such as
If it is too low, the concentration of perdicarboxylic acid will be reduced more than necessary. Therefore, as dicarboxylic acids excluding perdicarboxylic acid, 0.2 to 2.2 mol / Kg solution, preferably 0.
3 to 1.8 mol / Kg solution. Regarding the concentration of hydrogen peroxide, a higher concentration of perdicarboxylic acid is allowed as the concentration is higher, but as the concentration of hydrogen peroxide or perdicarboxylic acid is increased, the potential risk of the aqueous solution is increased. Because of the problem that its utilization is restricted, 1.0 to 12 mol / Kg solution of hydrogen peroxide,
Preferably, the concentration of the solution is 1.5 to 10 mol / Kg, and the concentration of perdicarboxylic acid (in terms of monoperdicarboxylic acid) is
It is preferable to add it in the range of 0.05 to 1.0 mol / Kg solution, preferably 0.10 to 0.8 mol / Kg solution.

The concentration of glutaric acid, succinic acid or adipic acid in the percarboxylic acid-containing aqueous solution according to the present invention is an important factor related to stability over time such as crystal precipitation from the aqueous solution, and the concentration of these crystals in the cold state. To avoid precipitation
Concentration of succinic acid (including persuccinic acid) 0.1 ~
0.7 mol / Kg solution, adipic acid (including peradipic acid)
Regarding the concentration, range from 0.02 to 0.2 mol / Kg solution,
Further, the total molar ratio of other dicarboxylic acids (including respective perdicarboxylic acids) to 1 mol of glutaric acid (including perglutaric acid) is set to be 0.1 to 2.0.

In the aqueous solution of percarboxylic acid of the present invention, a surfactant, if desired, within a range not impairing the object of the present invention,
Additives such as fragrances and colorants can be added and contained.

[0023]

The perdicarboxylic acid aqueous solution according to the present invention is
Compared with the method of using low-solubility dicarboxylic acid such as succinic acid and adipic acid alone, it is not only efficient in that the concentration of perdicarboxylic acid obtained can be made higher, but these low-solubility in cold state It is more practical than the percarboxylic acid solution obtained from glutaric acid alone, and is more effective than the percarboxylic acid solution obtained from a single glutaric acid. The physical properties of the perdicarboxylic acid-containing aqueous solution derived from a single dicarboxylic acid are improved,
It is possible to obtain a percarboxylic acid-containing aqueous solution composition for sterilization, bleaching and washing which is more practical in terms of action and economy.

[0024]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples.

Examples 1 to 3 Succinic acid, adipic acid and glutaric acid were added to water, heated at 50 ° C., stirred and dissolved, and succinic acid mixed with these dicarboxylic acids 0.5 to 0.8 mol / Kg, adipic acid 0.1 to 0.3
A column filled with an aqueous solution containing mol / Kg and glutaric acid at a concentration of 0.6 to 2.9 mol / Kg, and then filled with a polystyrene sulfonic acid type strongly acidic cation exchange resin (Amberlite IR-124, manufactured by Olgano). At 30 ° C. and an SV ratio of 4 to 6, the aqueous solution of complex dicarboxylic acid having a heavy metal content of 1.0 mg / Kg or less was prepared. Furthermore, 60% by weight aqueous solution of hydrogen peroxide and 60% by weight aqueous solution of stabilizer 1-hydroxyethylidene-1,1-diphosphonic acid were added to these solutions to obtain the initial concentrations of the respective components as shown in Table 2. The reaction was carried out at ℃ for 72 hours. Table 2 shows the results of observing the concentration of percarboxylic acid and hydrogen peroxide in the obtained reaction solution, and the presence or absence of crystal precipitation when these composition solutions were allowed to stand at 2 to 3 ° C. for 4 days.

Example 4 As in Examples 1 to 3, except that succinic acid and glutaric acid were used, succinic acid 0.7 mol / Kg and glutaric acid 0.9 mol / Kg
After preparing an aqueous solution containing it at the same concentration and treating it with an ion-exchange resin in the same way, add a hydrogen peroxide solution and a stabilizer to obtain initial concentrations of succinic acid, glutaric acid, and hydrogen peroxide.
Table 2 also shows the results of preparing 0.50 mol / Kg, 0.73 mol / Kg and 4.37 mol / Kg solutions and reacting them.

[0027]

[Table 2]

Comparative Examples 1-2 Succinic acid was added to water, heated to 50 ° C., stirred and dissolved,
Solutions having succinic acid concentrations of 0.60 mol / Kg and 0.75 mol / Kg were prepared, and this solution was treated with a cation exchange resin in the same manner as in Examples 1 to 3. Furthermore, 60 wt% hydrogen peroxide solution and stabilizer 1-hydroxyethylidene-1,1-
The initial concentration of each component was 0.45 mol / K for succinic acid and hydrogen peroxide by adding 60% by weight diphosphonic acid aqueous solution.
g, 4.2 mol / Kg, and 0.56 mol / Kg, 4.5 mol / Kg solutions were prepared and reacted in the same manner as in Examples 1 to 3 to prepare equilibrium solutions, and the generated persuccinic acid was analyzed. Then, this solution was allowed to stand at 2-3 ° C. for storage, and the state of crystal precipitation was observed. The results are shown in Table 2, and the concentration of the generated percarboxylic acid was low, and the precipitation of crystals was observed in several days even though the total succinic acid concentration was the same as or lower than those in Examples 1 to 3. Was done.

COMPARATIVE EXAMPLE 3 Adipic acid was used instead of succinic acid to prepare a solution having an adipic acid concentration of 0.18 mol / Kg, and the same treatment as in Comparative Example 1 was performed to obtain initial concentrations of adipic acid and hydrogen peroxide of 0.13 mol / Kg, respectively. A solution of Kg, 4.31 mol / Kg was prepared, which was used in Examples 1 to 1.
After reacting in the same manner as in 3 to make an equilibrium solution, the produced peradipic acid was analyzed, and then this solution was left to stand at 2 to 3 ° C. for storage to observe the state of crystal precipitation. The results are shown in Table 2, and the concentration of the generated percarboxylic acid was low, and although the concentration of total adipic acid was low as in Examples 1 and 2, precipitation of crystals was observed in several days. .

Comparative Example 4 A solution having a glutaric acid concentration of 0.67 mol / Kg was prepared by replacing succinic acid with glutaric acid, and treated in the same manner as in Comparative Example 1, and the initial concentration was 0.50 mol / Kg for glutaric acid and hydrogen peroxide. ,
A solution of 4.38 mol / Kg was prepared and reacted in the same manner as in Examples 1 to 3, and the concentration of the produced perglutaric acid was analyzed. As a result, as shown in Table 2, it was 0.11 mol / Kg.

Example 5 A crude dicarboxylic acid containing succinic acid, glutaric acid, and adipic acid in proportions of 25% by weight, 64% by weight, and 11% by weight, respectively, was used as a raw material. Parts, heated to 50 ° C., dissolved with stirring, then cooled to 0 to 3 ° C., the precipitated crystals were separated by filtration to obtain succinic acid, glutaric acid, and adipic acid at 0.76 mol / Kg, respectively. A complex dicarboxylic acid solution containing 2.71 mol / Kg and 0.15 mol / Kg was prepared. Next, this solution was used as a polystyrene sulfonic acid type strong acid cation exchange resin (manufactured by Organo, Amberlite IR
-124) is passed through a column packed with -124) at room temperature with an SV ratio of 5 to 8 and the content of heavy metals is 1.0 mg / Kg solution or less (Fe, Cu, N
The total concentration of i, Mn, Zn, and Cr was 0.9 mg / Kg solution, and Cu, Mn, and Zn were 0.04 mg / Kg or less), and the solution was used for reaction with hydrogen peroxide. The reaction is 100 parts by weight of resin-treated complex dicarboxylic acid solution and 44% by weight hydrogen peroxide solution 68.
7 parts by weight and a stabilizer 1-hydroxyethylidene-1,1-diphosphonic acid 60% by weight aqueous solution 0.33 parts by weight are mixed, and each initial concentration of succinic acid, glutaric acid, adipic acid and hydrogen peroxide is 0.45 mol. / Kg, 1.61 mol / Kg, 0.09 mol / Kg and 5.26 mol / Kg, and stabilizer (pure content)
At a concentration of 0.12% by weight, and the mixture was heated at 50 ° C for 72 hours with stirring. The solution after the reaction contained 0.78 mol / Kg of perdicarboxylic acid, 1.34 mol / Kg of dicarboxylic acid excluding perdicarboxylic acid, and 4.28 mol / Kg of hydrogen peroxide. The concentrations of succinic acid (including persuccinic acid), adipic acid (including peradipic acid), and glutaric acid (including perglutaric acid) in this solution are the same as the initial concentration. The molar ratio of dicarboxylic acid was 0.35. The solution was stored at 0 to 3 ° C for 4 days, but no precipitation of crystals was observed.
The residual rate of peroxide components after storage for 95 days is 95.
It was 6%.

Example 6 A crude dicarboxylic acid containing succinic acid, glutaric acid, and adipic acid in the proportions of 25% by weight, 64% by weight, and 11% by weight, respectively, was used as a raw material. Parts, heated to 50 ° C, stirred and dissolved to prepare a complex dicarboxylic acid solution containing succinic acid, glutaric acid, and adipic acid at concentrations of 1.02 mol / Kg, 2.20 mol / Kg, and 0.34 mol / Kg, respectively. did. Then, this solution was allowed to stand at room temperature with an acrylic strong base anion exchange resin (Amberlite IRA-45, manufactured by Organo).
8) was passed through a column packed with 8) with a SV ratio of 10 and subsequently with a column packed with polystyrene sulfonic acid type strong acid cation exchange resin (Amberlite IR-124, manufactured by Olgano) at an SV ratio of 5 to form a composite. After removing heavy metals in the dicarboxylic acid solution (the total concentration of Fe, Cu, Ni, Mn, Zn, Cr in the treatment solution is 0.6 mg / Kg
Each of the solutions, Cu, Mn, and Zn was 0.04 mg / Kg or less), 100 parts by weight of a 12.6 wt% hydrogen peroxide aqueous solution to 100 parts by weight of this solution, and 1-hydroxyethylidene-1,1 as a stabilizer. -Mixed with 60% by weight aqueous solution of diphosphonic acid 0.50 parts by weight, the initial concentrations of succinic acid, glutaric acid, adipic acid and hydrogen peroxide were 0.51 mol / Kg and 1.10, respectively.
Mol / Kg, 0.16 mol / Kg and 1.85 mol / Kg, and a stabilizer (pure content) of 0.15% by weight at 50 ° C
The reaction was carried out for 72 hours while heating and stirring. The solution after the reaction contained 0.18 mol / Kg of perdicarboxylic acid, 1.59 mol / Kg of dicarboxylic acid excluding perdicarboxylic acid, and 1.66 mol / Kg of hydrogen peroxide. The concentrations of succinic acid (including persuccinic acid), adipic acid (including peradipic acid), and glutaric acid (including perglutaric acid) in this solution are the same as the initial concentration. The molar ratio of the dicarboxylic acid was 0.61. When this solution was stored at 0 to 3 ° C for 4 days, precipitation of crystals was not observed, and the residual ratio of the peroxide component when stored at 50 ° C for 7 days was 97.9%.

Comparative Example 5 Heavy metal Fe, Cu, N prepared by dissolving a crude dicarboxylic acid in water
With respect to the composite dicarboxylic acid solution containing the total concentration of i, Mn, Zn and Cr at 2.8 mg / Kg, the same reaction as in Example 5 was carried out except that the heavy metal removal treatment with the cation exchange resin was not carried out. After the reaction, the solution contains 0.25 mol / K of perdicarboxylic acid.
It was contained only at a concentration of g.

Example 7 A crude dicarboxylic acid containing succinic acid, glutaric acid, and adipic acid in the proportions of 25% by weight, 64% by weight, and 11% by weight, respectively, was used as a raw material. In addition, 50
Heat to ℃, stir to dissolve, succinic acid, glutaric acid, adipic acid 1.02mol / Kg, 2.20mol / Kg, 0.3
A complex dicarboxylic acid solution containing 4 mol / Kg was prepared. Then, this solution was allowed to stand at room temperature with polystyrene sulfonic acid type strong acid cation exchange resin (manufactured by Organo, Amberlite 200).
After passing through the column filled with C) at an SV ratio of 5 to remove heavy metals in the complex dicarboxylic acid solution, 200 parts by weight of 60% by weight hydrogen peroxide and 98% by weight concentrated sulfuric acid are added to 100 parts by weight of this solution. 2 parts by weight, 1-hydroxyethylidene-1,1 as a stabilizer
-1 part by weight of a 60% by weight aqueous solution of diphosphonic acid and 0.5 part by weight of dipicolinic acid were mixed, and the reaction was carried out for 3 hours while heating and stirring at 50 ° C. 4 parts of water to 100 parts by weight of this reaction solution
0 parts by weight was added to make a solution containing 0.61 mol / Kg of perdicarboxylic acid, 0.23 mol / Kg of dicarboxylic acid excluding perdicarboxylic acid, and 7.67 mol / Kg of hydrogen peroxide. After storage for 24 hours, an equilibrium composition liquid was obtained in which the component compositions were changed to 0.45 mol / Kg, 0.39 mol / Kg, and 7.81 mol / Kg, respectively. When the equilibrium composition liquid is stored at 50 ° C for 7 days, the residual ratio of peroxide component is 98.8%,
The concentrations of succinic acid (including persuccinic acid), glutaric acid (including perglutaric acid), and adipic acid (including peradipic acid) in the liquid are 0.24 mol / Kg and 0.51 mol / Kg, respectively.
The molar ratio of other dicarboxylic acid to glutaric acid was 0.08 mol / Kg, and was 0.63. In addition, this solution 0-3
It was stored at a low temperature of ° C for 4 days, but no precipitation of crystals was observed.

Example 8 A crude dicarboxylic acid containing succinic acid, glutaric acid and adipic acid in the proportions of 25% by weight, 64% by weight and 11% by weight, respectively, was used as a raw material. In addition, 50
Heat to ℃, stir to dissolve, succinic acid, glutaric acid, adipic acid 1.02mol / Kg, 2.20mol / Kg, 0.3
A complex dicarboxylic acid solution containing 4 mol / Kg was prepared. Then, this solution was allowed to stand at room temperature with polystyrene sulfonic acid type strong acid cation exchange resin (manufactured by Organo, Amberlite 200).
After passing through the column filled with C) at an SV ratio of 5 to remove the heavy metals in the complex dicarboxylic acid solution, 60 parts by weight of hydrogen peroxide 40 parts by weight and 98% by weight concentrated sulfuric acid 1 to 100 parts by weight of this solution 1
Parts by weight, 1 part by weight of a 60% by weight aqueous solution of 1-hydroxyethylidene-1,1-diphosphonic acid as a stabilizer and 0.
5 parts by weight were added and mixed, and the mixture was reacted for 2 hours while being heated to 50 ° C. with stirring. After diluting 100 parts by weight of this solution with 140 parts by weight of water, the mixture was allowed to stand at room temperature, and after 1 week, 0.13 mol / Kg of perdicarboxylic acid, 0.91 mol / Kg of dicarboxylic acid excluding perdicarboxylic acid and peroxide were added. Hydrogen is 1.93 mol / Kg
An equilibrium composition liquid containing it in the proportion of was obtained. 50 of equilibrium composition liquid
The residual rate of peroxide components after storage at 7 ℃ for 7 days was 99.1%, and succinic acid (including persuccinic acid), glutaric acid (including perglutaric acid), adipic acid (peradipine) Acid (including acid) was 0.30 mol / Kg, 0.64 mol / Kg, 0.10 mol / Kg, and the molar ratio of other dicarboxylic acid to glutaric acid was 0.63. Further, this solution was stored at a low temperature of 0 to 3 ° C. for 4 days, but no precipitation of crystals was observed.

Example 9 and Comparative Example 6 The perdicarboxylic acid-containing aqueous solution obtained in Examples 1, 4 and 5 and the aqueous solution obtained in Comparative Example 4 were tested for bactericidal action by the following method, and the results are shown. The results are shown in Table 3. [Test method] Sewage treatment plant sewage was used as a test stock solution, and a perdicarboxylic acid-containing aqueous solution was added to this fixed amount so that the perdicarboxylic acid concentration became a predetermined concentration, and the mixture was stirred and contacted at room temperature for 60 minutes. The number of Escherichia coli was calculated according to the coliform group (plate culture method using desoxycholate medium) of the sewage test method (sewerage method), and the same method was used for the test stock solution without adding the perdicarboxylic acid-containing aqueous solution. The number of Escherichia coli in the stock solution was calculated with, and the bactericidal effect of the aqueous solution containing perdicarboxylic acid was displayed as the survival rate value calculated by the following calculation formula. Survival rate = (number of bacteria in treatment solution containing perdicarboxylic acid-containing aqueous solution) x 100 / (number of bacteria in undiluted solution) Perdicarboxylic acid-containing aqueous solution from complex dicarboxylic acid is a perdicarboxylic-acid-containing aqueous solution derived from glutaric acid only The bactericidal action per mol of perdicarboxylic acid was better than that.

[0037]

[Table 3]

Example 10 and Comparative Example 7 Using the perdicarboxylic acid-containing aqueous solution prepared in Example 6 and the perdicarboxylic acid-containing aqueous solution prepared only from glutaric acid, the minimum bactericidal concentration against E. coli was measured by the following method. It was As a result, as shown in Table 4, the perdicarboxylic acid-containing aqueous solution according to the present invention exhibited a bactericidal action at a lower concentration than the perdicarboxylic acid-containing aqueous solution derived from glutaric acid alone. [Test method] Dilute the perdicarboxylic acid-containing aqueous solution with distilled water and adjust the perdicarboxylic acid concentration to a predetermined concentration in 10 ml of diluted test solution and 0.1 ml of proliferating Escherichia coli solution adjusted to about 10 ⁷ cells / ml. Was added, and after contacting for 30 minutes, 0.1 ml of the mixture was inoculated into 10 ml of Brain Heart Infusion Medium, 37
The cells were cultured at ℃ for 48 hours, and the presence or absence of E. coli growth was determined based on the presence or absence of turbidity.

[0039]

[Table 4]

Example 11 and Comparative Example 8 A bleaching solution prepared by using the aqueous solution containing perdicarboxylic acid prepared in Example 6 and the aqueous solution containing perdicarboxylic acid prepared only from glutaric acid, and diluting these with water and adjusting the pH. Was tested for bleaching action by the following method, and the results are shown in Table 5.

[Bleaching test] Tap water was added to a predetermined amount of the perdicarboxylic acid-containing aqueous solution to dilute it, and an aqueous sodium hydroxide solution was added to adjust the pH to a predetermined value. A bleaching solution having A bleaching solution amount of 50 times the weight of the contaminated cloth was used, and the tea contaminated cloth was immersed in the bleaching solution and bleached at 40 ° C. for 30 minutes.
After the bleached cloth is washed with water, dried and ironed,
The reflectance was measured with a color difference meter, and the bleaching rate was calculated from the following formula. Bleaching rate (%) = (B−A) × 100 / (C−A), where A is the reflectance of the stained cloth before bleaching, B is the reflectance of the stained cloth after bleaching, and C is the white cloth before staining with black tea. Represents the reflectance.

[0042]

[Table 5]

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Claims (3)

[Claims] 1. A (1) perdicarboxylic acid (converted to monoperdicarboxylic acid) obtained by reacting a complex dicarboxylic acid containing glutaric acid and succinic acid with hydrogen peroxide.
0.05 to 1.0 mol / Kg solution, (2) 0.2% total dicarboxylic acids except perdicarboxylic acid
~ 2.2 mol / Kg solution, (3) Hydrogen peroxide is 1.0 ~ 12.0 mol / Kg solution, (4) Stabilizer is contained at a concentration of 0.01 ~ 3.0 wt%, and succinic acid (including persuccinic acid) concentration Is in the range of 0.1-0.7 mol / Kg solution, and the molar ratio of succinic acid (including persuccinic acid) to 1 mol of glutaric acid (including perglutaric acid) is 0.1-2.0. Containing aqueous solution. 2. A (1) perdicarboxylic acid (converted to a monoperdicarboxylic acid) obtained by reacting a complex dicarboxylic acid containing glutaric acid, succinic acid and adipic acid with hydrogen peroxide.
0.05 to 1.0 mol / Kg solution, (2) 0.2% total dicarboxylic acids except perdicarboxylic acid
~ 2.2 mol / Kg solution, (3) Hydrogen peroxide is 1.0 ~ 12.0 mol / Kg solution, (4) Stabilizer is contained at a concentration of 0.01 ~ 3.0 wt%, and succinic acid (including persuccinic acid) concentration 0.1-0.7 mol / Kg solution, adipic acid (including peradipic acid) concentration
In the range of 0.02 to 0.2 mol / Kg solution, the total molar ratio of other dicarboxylic acids (including each perdicarboxylic acid) to 1 mol of glutaric acid (including perglutaric acid) is
A perdicarboxylic acid-containing aqueous solution that is contained at a ratio of 0.1 to 2.0. 3. A composite dicarboxylic acid aqueous solution in which dicarboxylic acids are dissolved in water is treated with an ion exchange resin or a chelate resin, and the total metal concentration of iron, copper, nickel, chromium, manganese, and zinc contained is 2.0 mg / kg or less. The method for producing a perdicarboxylic acid-containing aqueous solution according to claim 1, wherein the complex dicarboxylic acid aqueous solution described above is reacted with hydrogen peroxide in the presence of a stabilizer.