JP3537540B2 - Aqueous solution containing perdicarboxylic acid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stable aqueous solution of a perdicarboxylic acid for use in applications such as sterilization, bleaching and washing, and a process for producing the same.

[0002]

2. Description of the Related Art Percarboxylic acids are usually synthesized from carboxylic acid or carboxylic anhydride and hydrogen peroxide, and are widely used as oxidizing agents for various substances due to their oxidizing power. It is also used in these applications because it exhibits such effects as the above. Use forms of these peracids are roughly classified into solid forms and aqueous forms. Peracetic acid is known as a typical aqueous carboxylic acid. Peracetic acid has its stability,
Alternatively, it is widely used for sterilization, bleaching, washing, etc. due to the generality of acetic acid as a raw material, but depending on the application, its use may be restricted by the peculiar smell of peracetic acid, which solves this problem. For this reason, various stable and odorless peracids have been studied, and JP-A-53-81619 proposes an odorless and stable perglutaric acid concentrated solution.

[0003] Other odorless peracids include perdicarboxylic acids such as persuccinic acid and peradipic acid. The production of peracid is based on the carboxylic acid and hydrogen peroxide used as raw materials and the produced peracid. Since the concentration of carboxylic acid and hydrogen peroxide during the reaction is higher, the higher the concentration, the more efficiently the peracid is generated, whereas the succinic acid and adipic acid, which are the raw materials for these peracids, It is disadvantageous in terms of production efficiency because solubility is low and efficient formation of peracid is not performed.
Also, since only a low concentration of peracid solution can be obtained, it is disadvantageous in distribution and the like. For the production of these peracids, acid anhydrides such as succinic anhydride or adipic anhydride are mainly used. Is used as a raw material.

[0004] However, aqueous solutions of peracid derived from these anhydrides can generate high concentrations of peracid, but as the peracid decomposes, hardly soluble host acid crystals are precipitated when cooled. It has problems from the viewpoints of stability and safety over time and safety, and also has the economic reason that the raw material anhydride is relatively expensive. Is almost never used.

[0005] 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 they are scarce and expensive, general use is more difficult in terms of raw material availability and economics.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a perdicarboxylic acid-containing aqueous solution derived from such an odorless, low-solubility dicarboxylic acid, which is disadvantageous due to a change with time, or a disadvantage in production efficiency and distribution. For general sterilization, bleaching, and washing with excellent stability or performance and economic efficiency, which has improved the effect and economical issues 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 The present inventors have conducted intensive studies on these problems and as a result, mixed water-soluble glutaric acid with succinic acid and adipic acid having low water solubility,
The aqueous solution of the complex dicarboxylic acid in which these odorless dicarboxylic acids are dissolved can dissolve succinic acid and adipic acid having low water solubility at a higher concentration in the existing water, and the aqueous solution of the complex dicarboxylic acid can be dissolved in the aqueous solution of the complex dicarboxylic acid. By adding and reacting with hydrogen oxide, the perdicarboxylic acid is efficiently formed even when the use ratio of glutaric acid is reduced, which can improve economical problems, and the resulting specific concentration composition can be improved. The dicarboxylic acid-containing aqueous solution was found to be excellent in the effect of its use, and it was difficult to cause crystal precipitation during storage, thereby improving the problems of the odorless perdicarboxylic acid-containing aqueous solution derived from a single dicarboxylic acid. It is found that an aqueous solution containing perdicarboxylic acid can be obtained which is more excellent in stability, safety, performance and economy. This has led to the completion of the out of the present invention.

[0008] That is, the present invention provides a dicarboxylic acid containing glutaric acid and succinic acid, which is obtained by reacting hydrogen peroxide with (1) a percarboxylic acid (in terms of monopercarboxylic acid) of 0.05 to 1.0 mol. / Kg solution, (2) 0.2 to 2.2 mol / Kg of total dicarboxylic acids excluding perdicarboxylic acid
Solution, (3) a hydrogen peroxide solution of 1.0 to 12.0 mol / Kg,
(4) The stabilizer is contained at a concentration of 0.01 to 3.0% by weight,
And a succinic acid (including persuccinic acid) concentration of 0.1 to 0.7
Succinic acid (including persuccinic acid) per mole of glutaric acid (including perglutaric acid) in the range of mol / Kg solution
(1) a percarboxylic acid-containing aqueous solution containing a molar ratio of 0.1 to 2.0, and a complex dicarboxylic acid containing succinic acid and adipic acid and hydrogen peroxide reacted with hydrogen peroxide. 0.05 to 1.0 mol / Kg solution of dicarboxylic acid (in terms of monoperdicarboxylic acid), (2) 0.2 to 2.2 mol / Kg of total dicarboxylic acids excluding perdicarboxylic acid
Solution, (3) a hydrogen peroxide solution of 1.0 to 12.0 mol / Kg,
(4) The stabilizer is contained at a concentration of 0.01 to 3.0% by weight, and 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 respective perdicarboxylic acids) to 1 mol of glutaric acid (including perglutaric acid) is as follows.
The present invention relates to a perdicarboxylic acid-containing aqueous solution contained at a ratio of 0.1 to 2.0, and a method for producing them.

The aqueous solution containing perdicarboxylic acid of the present invention contains glutaric acid as an essential component, uses succinic acid and adipic acid in combination, and dissolves these dicarboxylic acids in water to obtain a predetermined concentration and ratio of dicarboxylic acid. Aqueous solution, the aqueous solution is further processed and purified by an ion exchange resin or the like,
After removing the heavy metals contained, a hydrogen peroxide solution is added in the co-presence of a stabilizer, and the mixture is reacted to prepare the solution. However, if necessary, the solution can be further diluted with deionized water to a desired concentration. .

The aqueous solution of the complex dicarboxylic acid used in the present invention basically uses 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 in water at a ratio, but crude dicarboxylic acids in the form of a mixture of these dicarboxylic acids in a fixed ratio or a non-constant ratio are easily available, and industrially, these are used as raw materials to form a composite. It is advantageous to prepare an aqueous dicarboxylic acid solution. In this case, once dissolved in water and then cooled, the unnecessary portion of the low-soluble dicarboxylic acid is crystallized and separated and removed, or a mixed dicarboxylic acid is suspended in water to dissolve the insoluble portion. The concentration or ratio of each dicarboxylic acid is adjusted by a method of separating and removing the dicarboxylic acid or a method of mixing and using a mixed dicarboxylic acid and a single dicarboxylic acid to prepare a desired aqueous solution of a complex dicarboxylic acid. In addition, if particularly desired, anhydrides of these dicarboxylic acids can be used, and they can be dissolved in water and hydrated.

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

[0012]

[Table 1]

The concentration of dicarboxylic acid in the aqueous solution of complex dicarboxylic acid is related to the composition of the final aqueous solution containing percarboxylic acid, and the ratio of hydrogen peroxide to dicarboxylic acid added during the reaction or the amount of hydrogen peroxide used is Since the concentration or the like is selected, it cannot be specified unconditionally, but in general, the operability of purification operation of the aqueous solution of dicarboxylic acid with an ion exchange resin or a chelate resin, the removal efficiency of heavy metals, or the intended excess From the efficiency of dicarboxylic acid formation, the solution is subjected to treatment with an ion exchange resin as a 2 to 6 mol / Kg solution, preferably 3 to 5 mol / Kg solution as a dicarboxylic acid concentration.

The dicarboxylic acid used as a raw material usually contains a trace amount of heavy metal as an impurity, and coexists during the reaction between the dicarboxylic acid and hydrogen peroxide, thereby inhibiting the formation of the dicarboxylic acid, and If the concentration of perdicarboxylic acid is not obtained, or if it is present in the final perdicarboxylic acid-containing aqueous solution, the decomposition of perdicarboxylic acid or hydrogen peroxide is promoted, and the storage stability is reduced.
In order to cause practical problems, for the purpose of removing these metal ions, dicarboxylic acids are converted to an aqueous solution and then treated with an ion exchange resin or a chelate resin, and iron, copper, nickel, chromium, Reduce the total heavy metal ion concentration of manganese and zinc to 2 mg / Kg solution or less. As the ion exchange resin here, a generally known strong acidic cation exchange resin having a sulfonic acid group as an ion exchange functional group can be suitably used, and the chelate resin has an iminodiacetic acid group, or Further, a polyamine type generally known chelate resin can be used. The removal of metals in the aqueous solution of dicarboxylic acid can be carried out with a cation exchange resin or a chelate resin to roughly remove the target metal. If stabilization is desired, an even better storage stability can be obtained by further using an anion exchange resin before the treatment with the cation exchange resin to remove trace metals in the anion state.

The treatment of the raw material dicarboxylic acid aqueous solution with an ion exchange resin or a chelate resin may be carried out by a general method such as a method of suspending the resin in the aqueous solution of dicarboxylic acid and separating by filtration, or a method of passing 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 at the time of treatment, the concentration of the dicarboxylic acid in the treatment solution is set to be equal to or less than the saturation concentration at the treatment temperature, and the concentration of the heavy metals is 2.0 mg / kg. Hereinafter, it is desirably provided 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 regenerated with an aqueous solution of a mineral acid such as dilute sulfuric acid and recycled.

The production of perdicarboxylic acid in the present invention is as follows:
A mixed dicarboxylic acid aqueous solution purified by the above method and a hydrogen peroxide aqueous solution are mixed in the presence of a stabilizer, and the mixture is reacted under stirring.If desired, deionized water is added during the reaction. 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 of 0 to 30 ° C. for a long time, but it is not efficient for industrial production.
To 80 ° C., preferably 40 to 60 ° C., and if necessary, if necessary, a reaction solution using an acidic substance such as sulfuric acid, phosphoric acid, condensed phosphoric acid, or phosphonic acid as a catalyst. The reaction time can be further reduced by adding 1 to 10 g per kg.

In order to allow a high reaction temperature during the reaction, it is necessary that the reaction solution is highly stabilized. If the raw material dicarboxylic acid aqueous solution is insufficiently purified, or if the amount of the stabilizer is small, If it is not enough,
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,
The reaction is preferably carried out for 4 to 50 hours.However, when the final concentration of perdicarboxylic acid is low, such as when the reaction solution is diluted to a final composition after the reaction, the reaction time may be reduced. As a result, it is possible to shorten the time without being restricted by the time required to reach the equilibrium composition.

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 solution, but the dicarboxylic acid concentration in the reaction solution is kept constant. In this case, as the ratio of hydrogen peroxide to dicarboxylic acid increases, the ratio or concentration of generated perdicarboxylic acid increases, and although it is efficient in terms of perdicarboxylic acid generation, the concentration of hydrogen peroxide is simultaneously increased. Therefore, it is not preferable to use an excessively large amount because the increase in the peroxide concentration increases the potential danger in handling or storing the final composition liquid. Also, it is not efficient to use a ratio lower than necessary in that the production rate of perdicarboxylic acid is reduced,
In the present invention, the molar ratio of hydrogen peroxide to dicarboxylic acid is from 0.2 to 15, preferably from 0.5 to 10. The concentration of hydrogen peroxide to be used is usually 10 to 70% by weight from the viewpoint of handling or danger, but when a high concentration of perdicarboxylic acid is desired to be produced, the concentration of hydrogen peroxide may be reduced in terms of production efficiency. It is advantageous to use higher concentrations.

The stabilizers added during the reaction include:
Organic phosphonic acids such as aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid) and pyridinecarboxylic acids such as picolinic acid, dipicolinic acid and quinolinic acid. Suitable and 0.01 to the reaction mixture.
The reaction is carried out by adding at a ratio of .about.3.0 wt%, preferably 0.05-1.0 wt%.

The aqueous solution containing perdicarboxylic acid obtained by the reaction is used as it is as a final composition solution or, if desired, water or dicarboxylic acids from which heavy metals have been removed are added.
An aqueous solution within a predetermined concentration range. The aqueous solution of percarboxylic acid containing dicarboxylic acids, hydrogen peroxide,
The composition of water eventually changes to its equilibrium composition, and the higher the concentration of dicarboxylic acids, the higher the concentration of perdicarboxylic acid is allowed, but if it is higher than necessary, crystals will precipitate when cooled. Etc. are likely to occur,
If the concentration is too low, the concentration of the dicarboxylic acid will be unnecessarily lowered, so that the dicarboxylic acids except for the dicarboxylic acid are 0.2 to 2.2 mol / Kg solution, preferably 0.1 to 0.2 mol / Kg.
Make a 3-1.8 mol / Kg solution. Also, with respect to 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 and dicarboxylic acid increases, the potential danger of the aqueous solution increases, Since their use is restricted, a 1.0 to 12 mol / Kg solution as 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 contain the solution in the range of 0.05 to 1.0 mol / Kg solution, preferably in the range of 0.10 to 0.8 mol / Kg solution.

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

The aqueous solution of a percarboxylic acid of the present invention may contain a surfactant, if desired, as long as the object of the present invention is not hindered.
Additives such as fragrances and coloring agents can be added and contained.

[0023]

The perdicarboxylic acid aqueous solution according to the present invention comprises:
Compared to the method using only low-soluble dicarboxylic acids such as succinic acid and adipic acid, it is not only efficient in that the obtained perdicarboxylic acid concentration can be made higher, but also these low-soluble It is more practical because it has improved stability over time, such as the difficulty of precipitating crystalline dicarboxylic acid, and it is more effective than the percarboxylic acid solution obtained from glutaric acid alone. The disadvantages of each perdicarboxylic acid-containing aqueous solution derived from a single dicarboxylic acid have been 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 or economy.

[0024]

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 to 50 ° C., stirred and dissolved, and succinic acid mixed with these dicarboxylic acids 0.5 to 0.8 mol / kg, adipic acid 0.1-0.3
Aqueous solution containing mol / Kg and glutaric acid at a concentration of 0.6 to 2.9 mol / Kg was prepared, and then these solutions were filled with polystyrenesulfonic acid type strongly acidic cation exchange resin (manufactured by Orcano, Amperite IR-124). The mixture was passed at 30 ° C. at an SV ratio of 4 to 6 to prepare a composite dicarboxylic acid aqueous solution having a heavy metal content of 1.0 mg / Kg solution or less. Further, a 60% by weight aqueous solution of hydrogen peroxide and a 60% by weight aqueous solution of 1-hydroxyethylidene-1,1-diphosphonic acid as a stabilizer were added to these solutions, and the initial concentrations of the respective components were set to the values shown in Table 2, and 50%. The reaction was carried out at 72 ° C for 72 hours. Table 2 shows the results of observing the concentrations of percarboxylic acid and hydrogen peroxide in the obtained reaction solution, and the presence or absence of crystal precipitation when these compositions were allowed to stand at 2-3 ° C. for 4 days.

Example 4 0.7 mol / kg of succinic acid and 0.9 mol / kg of glutaric acid in the same manner as in Examples 1 to 3 except that succinic acid and glutaric acid were used.
After preparing an aqueous solution containing at a concentration of, and similarly treating with an ion exchange resin, adding a hydrogen peroxide solution and a stabilizer to the initial concentration 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 and 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. In addition, a 60% by weight aqueous solution of hydrogen peroxide and 1-hydroxyethylidene-1,1-
A 60% by weight aqueous solution of diphosphonic acid was added to adjust the initial concentration of each component to 0.45 mol / K for succinic acid and hydrogen peroxide, respectively.
g, 4.2 mol / Kg, and 0.56 mol / Kg, 4.5 mol / Kg were prepared and reacted in the same manner as in Examples 1 to 3 to obtain an equilibrium solution, and the resulting persuccinic acid was analyzed. Then, the solution was stored at 2-3 ° C., and the state of crystal precipitation was observed. The results are as shown in Table 2, where the concentration of percarboxylic acid produced was low, and the precipitation of crystals was observed in several days despite the fact that the total succinic acid concentration was the same or low as in Examples 1 to 3. Was done.

Comparative Example 3 Succinic acid was replaced with adipic acid, a solution having an adipic acid concentration of 0.18 mol / Kg was prepared, and treated in the same manner as in Comparative Example 1 to have an initial concentration of 0.13 mol / kg for adipic acid and hydrogen peroxide, respectively. A solution of Kg, 4.31 mol / Kg was prepared, and
After the reaction was carried out in the same manner as in Example 3 to obtain an equilibrium solution, the produced peradipic acid was analyzed. Then, the solution was stored at 2-3 ° C., and the state of crystal precipitation was observed. The results are as shown in Table 2, where the concentration of the produced percarboxylic acid was low, and the precipitation of crystals was observed in several days despite the low concentration of total adipic acid as in Examples 1-2. .

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 so that 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, it was 0.11 mol / Kg as shown in Table 2.

Example 5 A crude dicarboxylic acid containing succinic acid, glutaric acid, and adipic acid in a ratio of 25% by weight, 64% by weight, and 11% by weight, respectively, was used as a raw material. The solution was cooled to 0 to 3 ° C, and the precipitated crystals were separated by filtration, and succinic acid, glutaric acid, and adipic acid were separated by 0.76 mol / Kg, respectively. A composite dicarboxylic acid solution containing 2.71 mol / Kg and 0.15 mol / Kg was prepared. Next, this solution was mixed with a polystyrenesulfonic acid-type strongly acidic cation exchange resin (manufactured by Orcano, Amperlite IR).
-124) at room temperature at an SV ratio of 5 to 8 to reduce the heavy metal content to 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 the concentration of Cu, Mn, and Zn was 0.04 mg / Kg or less, respectively, and subjected to the reaction with hydrogen peroxide. The reaction was performed with 100 parts by weight of a resin-treated complex dicarboxylic acid solution and a 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, 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)
At a concentration of 0.12% by weight while heating at 50 ° C. while stirring for 72 hours. The solution after the reaction contained 0.78 mol / Kg of dicarboxylic 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 concentrations, The molar ratio of the dicarboxylic acid was 0.35. This solution was stored at 0 to 3 ° C. for 4 days, but no precipitation of crystals was observed.
Peroxide residual ratio after storage for 95 days is 95.
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. The mixture was heated to 50 ° C and dissolved by stirring to prepare a composite 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. Next, this solution was cooled at room temperature to an acrylic strong basic anion exchange resin (manufactured by Orcano, Amperlite IRA-45).
8) was passed through a column filled with polystyrenesulfonic acid type strongly acidic cation exchange resin (manufactured by Orcano, Amperite IR-124) at an SV ratio of 5 at an SV ratio of 10 After removing heavy metals in the dicarboxylic acid solution (the total concentration of Fe, Cu, Ni, Mn, Zn, and Cr in the treatment solution is 0.6 mg / Kg
Solution, Cu, Mn, and Zn were each 0.04 mg / Kg or less), 100 parts by weight of a 12.6% by weight aqueous hydrogen peroxide solution per 100 parts by weight of this solution, and 1-hydroxyethylidene-1,1 as a stabilizer. -Mix with 0.50 parts by weight of a 60% by weight aqueous solution of diphosphonic acid, and adjust the initial concentrations of succinic acid, glutaric acid, adipic acid and hydrogen peroxide to 0.51 mol / Kg, 1.10 respectively.
Mol / Kg, 0.16 mol / Kg and 1.85 mol / Kg, and a stabilizer (pure) at a concentration of 0.15% by weight at 50 ° C.
The reaction was carried out for 72 hours while stirring while heating. The solution after the reaction contained 0.18 mol / kg of dicarboxylic 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 concentrations, The molar ratio of dicarboxylic acid was 0.61. When this solution was stored at 0 to 3 ° C for 4 days, no precipitation of crystals was observed, and the residual ratio of the peroxide component when stored at 50 ° C for 7 days was 97.9%.

Comparative Example 5 Heavy metals Fe, Cu, N prepared by dissolving a crude dicarboxylic acid in water
The same reaction as in Example 5 was performed for the composite dicarboxylic acid solution containing i, Mn, Zn, and Cr at a total concentration of 2.8 mg / Kg, except that the heavy metal removal treatment with the cation exchange resin was not performed. The solution after the reaction contains 0.25 mol / K of dicarboxylic acid.
Only contained at a concentration of g.

Example 7 A crude dicarboxylic acid containing succinic acid, glutaric acid, and adipic acid in a ratio of 25% by weight, 64% by weight, and 11% by weight, respectively, was used. Plus 50
C. and dissolved by stirring. Succinic acid, glutaric acid and adipic acid contained 1.02 mol / Kg, 2.20 mol / Kg, 0.3
A complex dicarboxylic acid solution containing 4 mol / Kg was prepared. Then, this solution was subjected to a polystyrenesulfonic acid-type strongly acidic cation exchange resin (manufactured by Orcano, Amperlite 200) at room temperature.
The mixture was passed through a column packed with C) at an SV ratio of 5 to remove heavy metals in the composite dicarboxylic acid solution. Then, 200 parts by weight of 60% by weight hydrogen peroxide and 98% by weight of 98% by weight concentrated sulfuric acid were added to 100 parts by weight of this solution. 2 parts by weight, 1-hydroxyethylidene-1,1 as stabilizer
1 part by weight of a 60% by weight diphosphonic acid aqueous solution and 0.5 part by weight of dipicolinic acid were mixed, and the mixture was reacted at 50 ° C. for 3 hours while stirring. Water 4 per 100 parts by weight of the reaction solution
0 parts by weight were added, and a solution containing 0.61 mol / kg of dicarboxylic acid, 0.23 mol / kg of dicarboxylic acid excluding perdicarboxylic acid, and 7.67 mol / kg of hydrogen peroxide was prepared. After 24 hours, an equilibrium composition solution was obtained in which the component compositions changed to 0.45 mol / Kg, 0.39 mol / Kg, and 7.81 mol / Kg, respectively, after 24 hours. The peroxide component residual ratio of the equilibrium composition solution when stored at 50 ° C. for 7 days is 98.8%.
The concentrations of succinic acid (including persuccinic acid), glutaric acid (including perglutaric acid), and adipic acid (including peradipic acid) in the solution are 0.24 mol / Kg, 0.51 mol / Kg, respectively.
The mole ratio of other dicarboxylic acids to glutaric acid was 0.08 mol / Kg, and was 0.63. In addition, this solution is
After storage at a low temperature of 4 ° C. for 4 days, no precipitation of crystals was observed.

Example 8 A crude dicarboxylic acid containing succinic acid, glutaric acid, and adipic acid at a ratio of 25% by weight, 64% by weight, and 11% by weight, respectively, was used as a raw material. Plus 50
C. and dissolved by stirring. Succinic acid, glutaric acid and adipic acid contained 1.02 mol / Kg, 2.20 mol / Kg, 0.3
A complex dicarboxylic acid solution containing 4 mol / Kg was prepared. Then, this solution was subjected to a polystyrenesulfonic acid-type strongly acidic cation exchange resin (manufactured by Orcano, Amperlite 200) at room temperature.
The mixture was passed through a column packed with C) at an SV ratio of 5 to remove heavy metals from the composite dicarboxylic acid solution. Then, 40 parts by weight of 60% by weight hydrogen peroxide and 98% by weight of concentrated sulfuric acid were added to 100 parts by weight of the solution.
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 0.1 parts by weight of dipicolinic acid.
Five parts by weight were added and mixed, and the mixture was reacted for 2 hours while stirring at a temperature of 50 ° C. After diluting 100 parts by weight of this solution with 140 parts by weight of water and leaving it at room temperature, one week later, 0.13 mol / Kg of dicarboxylic acid and 0.91 mol / Kg of dicarboxylic acid excluding perdicarboxylic acid were added. Hydrogen is 1.93 mol / Kg
Was obtained. 50 of equilibrium composition solution
Percentage of peroxide component after storage at 7 ℃ for 9 days is 99.1%. Succinic acid (including persuccinic acid), glutaric acid (including perglutaric acid), adipic acid (peradipine) (Including acid) were 0.30 mol / Kg, 0.64 mol / Kg, 0.10 mol / Kg, respectively, and the molar ratio of other dicarboxylic acids to glutaric acid was 0.63. 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 aqueous solution obtained in Examples 1, 4 and 5 and the aqueous solution obtained in Comparative Example 4 were tested for bactericidal activity by the following method. The results are shown in Table 3. [Test Method] Using a sewage treatment plant sewage as a test stock solution, a perdicarboxylic acid-containing aqueous solution was added to this fixed amount so that the perdicarboxylic acid concentration became a predetermined concentration, and the solution was stirred and contacted at room temperature for 60 minutes. Was calculated according to the coliform bacteria (plate culture method using desoxycholate medium) in the sewage test method (sewerage method), and the same method was used for the stock test solution without adding a perdicarboxylic acid-containing aqueous solution. The number of Escherichia coli in the undiluted solution was calculated, and the bactericidal effect of the perdicarboxylic acid-containing aqueous solution was displayed as a survival rate value obtained by the following formula. Viability = (the number of bacteria in the treated solution with the addition of the aqueous solution containing perdicarboxylic acid) x 100 / (the number of bacteria in the stock solution) The aqueous solution containing perdicarboxylic acid from the complex dicarboxylic acid is an aqueous solution containing perdicarboxylic acid derived only from glutaric acid The bactericidal action per mole of perdicarboxylic acid was better than that.

[0037]

[Table 3]

Example 10 and Comparative Example 7 Using the aqueous solution containing perdicarboxylic acid prepared in Example 6 and the aqueous solution containing perdicarboxylic acid prepared only from glutaric acid, the minimum bactericidal concentration against Escherichia coli was measured by the following method. Was. As shown in Table 4, the aqueous solution containing perdicarboxylic acid according to the present invention exhibited a bactericidal action at a lower concentration than the aqueous solution containing perdicarboxylic acid derived only from glutaric acid, as shown in Table 4. [Test Method] A perdicarboxylic acid-containing aqueous solution was diluted with distilled water, and 0.1 ml of a growing Escherichia coli solution adjusted to about 10 ⁷ cells / ml in 10 ml of a diluted test solution so that the concentration of perdicarboxylic acid became a predetermined concentration. Was added and contacted for 30 minutes, and 0.1 ml of the mixture was inoculated into 10 ml of Brain Heart Infusion medium,
After culturing at 48 ° C for 48 hours, the presence or absence of Escherichia coli proliferation was determined based on the occurrence of turbidity.

[0039]

[Table 4]

Example 11 and Comparative Example 8 The aqueous solution containing perdicarboxylic acid prepared in Example 6 and the aqueous solution containing perdicarboxylic acid prepared only from glutaric acid were used, and the bleaching solution was diluted with water and the pH was adjusted. 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 aqueous solution containing perdicarboxylic acid to dilute the solution, and an aqueous solution of sodium hydroxide was added to adjust the pH to a predetermined value. Was prepared. Using a bleaching liquid amount 50 times the weight of the stained cloth, a black tea-stained cloth was immersed in the bleaching solution and bleached at 40 ° C. for 30 minutes.
After washing, drying and ironing the bleached cloth,
The reflectance was measured by a color difference meter, and the bleaching rate was calculated from the following equation. Bleaching rate (%) = (BA) × 100 / (CA), 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 black tea staining. Represents the reflectance.

[0042]

[Table 5]

──────────────────────────────────────────────────の Continuing on the front page (51) Int.Cl. ⁷ identification code FI D06L 3/02 D06L 3/02 (58) Investigated field (Int.Cl. ⁷ , DB name) C07C 409/24 A01N 37/16 C02F 1/50 532 C11D 7/38 D06L 1/12 D06L 3/02

Claims (3)

(57) [Claims] 1. A compound obtained by reacting a complex dicarboxylic acid containing glutaric acid and succinic acid with hydrogen peroxide, and (1) perdicarboxylic acid (in terms of monoperdicarboxylic acid)
0.05 to 1.0 mol / Kg solution, (2) 0.2% of total dicarboxylic acids excluding perdicarboxylic acid
2.22.2 mol / Kg solution, (3) 1.0-12.0 mol / Kg solution of hydrogen peroxide, (4) succinic acid (including persuccinic acid) concentration containing stabilizer at a concentration of 0.01-3.0% by weight Is in the range of 0.1 to 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 to 2.0. Containing aqueous solution. 2. A compound obtained by reacting glutaric acid, a complex dicarboxylic acid containing succinic acid and adipic acid with hydrogen peroxide, and (1) perdicarboxylic acid (in terms of monoperdicarboxylic acid)
0.05 to 1.0 mol / Kg solution, (2) 0.2% of total dicarboxylic acids excluding perdicarboxylic acid
2.22.2 mol / Kg solution, (3) 1.0-12.0 mol / Kg solution of hydrogen peroxide, (4) succinic acid (including persuccinic acid) concentration containing stabilizer at a concentration of 0.01-3.0% by weight Is 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 respective perdicarboxylic acids) to 1 mol of glutaric acid (including perglutaric acid) is as follows.
Perdicarboxylic acid-containing aqueous solution contained at a ratio of 0.1 to 2.0. 3. An aqueous solution of a complex dicarboxylic acid obtained by dissolving dicarboxylic acids 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 aqueous solution of the complex dicarboxylic acid is reacted with hydrogen peroxide in the presence of a stabilizer.