JP2000178222A - Orthophthalaldehyde stabilized composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of controlling reduction in component content and discoloration with time or by heating for a long period of time even in a high-concentration solution, neither freezing nor solidifying even under refrigeration conditions, useful as a disinfectant, etc., by adding a specific solvent and water to orthophthalaldehyde. SOLUTION: This composition is obtained by adding (B) at least one kind of solvent selected from (i) N,N-dimethylacetamide and (ii) γ-butyrolactone and (C) water to (A) orthophthalaldehyde. Preferably 50-250 pts.wt. of the component i and 1-150 pts.wt. of the component C or 50-200 pts.wt. of the component, ii and 1-150 pts.wt. of the component C are added to 100 pts.wt. of the component A. Preferably a solvent such as N-dimethylformamide may be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an orthophthalaldehyde-stabilized composition useful as a raw material for disinfectants and non-medical germicidal preservatives, and a method for producing the same. More specifically, the present invention relates to an orthophthalaldehyde-stabilized composition in which decomposition and polymerization of an active ingredient and coloring of a solution during long-term storage are suppressed, and the composition does not freeze and solidify even under refrigeration conditions, and a method for producing the same.

[0002]

2. Description of the Related Art Orthophthalaldehyde is useful as a raw material for disinfectants and non-medical germicidal preservatives due to its excellent bactericidal and preservative efficacy, and is industrially supplied in various production methods and product forms. ing. For example, as a product form on an industrial scale, crystalline powder or flake-like small pieces, or as a product form with a lower production cost, a distillate-purified fraction is directly poured into a packaging container and solidified by cooling and solidification. and so on.

The melting point of orthophthalaldehyde is about 56 ° C.
Therefore, in the case of crystalline powder or flake-like small pieces, blocking tends to occur during distribution and storage at room temperature, and in many cases, some kind of pulverizing work is required when used. In addition to complicating the work process due to this pulverizing work, orthophthalaldehyde is irritating and corrosive. Is also not preferred.

[0004] In addition, the above-mentioned orthophthalaldehyde solid must be heated and melted when it is taken out of the packaging container, and at this time, the yellow orthophthalaldehyde turns black-brown. At the same time as this coloring, polymerization,
A considerable decrease in the content of components due to oxidation, decomposition and the like also occurs. Furthermore, since ortho-phthalaldehyde does not have high water solubility, these solids and raw powders of crystalline powders are not rapidly dispersed and dissolved in water-based germicidal and antiseptic objects, and their effects cannot be fully exerted.

[0005] For this reason, it is preferable that orthophthalaldehyde is dissolved in a water-soluble solvent in advance and supplied to consumers as a liquefied product. Particularly, from the viewpoint of cost, it is desired to supply a product prepared as a high-concentration liquid product. Since the solubility of orthophthalaldehyde in water around room temperature is as low as about 5% or less, when preparing an orthophthalaldehyde solution of 5% or more, or when preparing a mixture with other germicidal and preservative components, It is common to use various organic solvents and surfactants (JP-A-6-2643).
No. 97, No. 7-116669, No. 8-302594
Nos. 9-25205 and 9-194419).

[0006] For example, in Japanese Patent Application Laid-Open No. 8-302594, propylene carbonate is used as a main solvent, and aromatic hydrocarbon,
A slime controlling agent for papermaking has been proposed in which solvents such as esters, alcohols, glycols, and dimethylacetamide are mixed in a weight ratio of not more than half with respect to propylene carbonate as a main solvent.

However, propylene carbonate,
N-methyl-2-pyrrolidinone, 1,3-dimethylimidazolidinone, N, N-dimethylacetamide, N, N
Orthophthalaldehyde composition using an aprotic polar solvent such as dimethylformamide, γ-butyrolactone, or methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, ethylene glycol Orthophthalaldehyde compositions using a solvent having no hydroxyl group in its molecular structure, such as diacetate and diethylene glycol diethyl ether, are less likely to cause a decrease in the component content, but are light yellow immediately after preparation, but have been heated. In addition, there is a problem that the product is colored blackish brown or black due to long-term storage, and the commercial value is greatly impaired. At the same time, a high-concentration composition containing 40% by weight or more of orthophthalaldehyde easily freezes and solidifies under refrigerated conditions, and once frozen and solidified, does not redissolve at about room temperature. Therefore, use and storage in severe winters or cold regions Was difficult.

Also, glycol solvents (eg, ethylene glycol, diethylene glycol, polyethylene glycol 200, propylene glycol, dipropylene glycol, etc.) or glycol ether solvents (eg, methyl carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, etc.) Ethyl cellosolve,
When a solvent having a hydroxyl group in its molecular structure, such as butyl cellosolve or dipropylene glycol monomethyl ether, is used, coloring due to heating or long-term storage is unlikely to occur, and it is difficult to freeze and solidify under refrigerated conditions. However, there is a problem that the interaction between orthophthalaldehyde and these solvents causes a reduction in the component content.

[0009]

Accordingly, the present invention provides
Even in the case of a high-concentration solution, a decrease in the component content and coloring due to aging or heating are suppressed for a long period of time, and an orthophthalaldehyde stabilized composition that does not freeze and solidify even under refrigerated conditions,
And a method for producing the composition.

[0010]

Means for Solving the Problems The present inventors have made intensive studies in view of the above-mentioned problems, and have found that N, N-dimethylacetamide, γ-
Aprotic polar solvents such as butyrolactone, propylene carbonate, N-methyl-2-pyrrolidinone, 1,3-dimethylimidazolidinone, N, N-dimethylformamide, or methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate; Orthophthalaldehyde compositions containing a solvent that does not have a hydroxyl group in the molecular structure, such as carbitol acetate, butyl carbitol acetate, ethylene glycol diacetate, diethylene glycol diethyl ether, and water, are colored by heating or long-term storage. Have a tendency to be reduced. However, even if the above-mentioned aprotic solvent or a solvent having no hydroxyl group is used together with water, depending on the type of the solvent, coloring of the solution is not sufficiently prevented, or freezing and solidification under refrigeration conditions are likely to occur. As a result of further research, it has been found that the above object can be achieved by mixing N, N-dimethylacetamide or γ-butyrolactone and water in a predetermined ratio and using the same, and based on this finding, the present invention has been achieved. I've reached the point.
That is, the present invention provides (1) an orthophthalaldehyde-stabilized composition comprising: o-phthalaldehyde containing at least one solvent selected from N, N-dimethylacetamide and γ-butyrolactone; and water. (2) N, N-dimethylacetamide 50 to 250 parts by weight based on 100 parts by weight of orthophthalaldehyde
Orthophthalaldehyde stabilizing composition, characterized in that it contains 1 to 150 parts by weight of water and 1 to 150 parts by weight of water,
(3) With respect to 100 parts by weight of orthophthalaldehyde, γ
-Butyrolactone 50 to 200 parts by weight and water 1 to 120
And (4) at least one selected from a predetermined amount of N, N-dimethylacetamide and γ-butyrolactone with respect to orthophthalaldehyde. An object of the present invention is to provide a method for producing an orthophthalaldehyde-stabilized composition characterized by containing a solvent and water.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The orthophthalaldehyde composition of the present invention comprises orthophthalaldehyde, water, and N, N
-At least one solvent selected from dimethylacetamide and γ-butyrolactone. The composition of the present invention is characterized in that the orthophthalaldehyde component is stable for a long period of time even at a high concentration. In the present invention, a high concentration generally means a case where the composition contains 20% by weight or more of orthophthalaldehyde. The composition of the present invention is usually provided as a highly concentrated solution.

There is no particular limitation on the orthophthalaldehyde as a raw material that can be used in the present invention, and a predetermined amount of N, N-dimethylacetamide and a predetermined amount are directly added to the orthophthalaldehyde in a molten state immediately after industrial synthesis. It is the simplest to prepare at least one solvent selected from γ-butyrolactone and water to prepare the orthophthalaldehyde-stabilized composition of the present invention.
A stable composition can also be prepared using orthophthalaldehyde having a product shape such as a flake-shaped piece or a solid.

In the present invention, water is industrial water, tap water,
Ion exchange water, distilled water and the like can be used without particular limitation, and tap water having a pH of 5 to 7 is usually used.

In the present invention, at least one selected from N, N-dimethylacetamide and γ-butyrolactone is used as the solvent. When N, N-dimethylacetamide is used in the present invention, it is usually 50 to 250 parts by weight, preferably 50 to 150 parts by weight, more preferably 70 to 12 parts by weight, per 100 parts by weight of orthophthalaldehyde.
0 parts by weight. At this time, water is usually 1 to 150 parts by weight, preferably 5 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of orthophthalaldehyde. When γ-butyrolactone is used in the present invention, it is usually 50 to 200 parts by weight, preferably 50 to 15 parts by weight, per 100 parts by weight of orthophthalaldehyde.
0 parts by weight, more preferably 70 to 120 parts by weight. At this time, water is usually 1 to 120 parts by weight, preferably 5 to 10 parts by weight based on 100 parts by weight of orthophthalaldehyde.
0 parts by weight, more preferably 5 to 50 parts by weight.

In the present invention, in addition to water and the above-mentioned solvents, other solvents may be used in combination without impairing the object of the present invention. Examples of such solvents include the following. . N, N-dimethylformamide, N-
Amide compounds such as methylacetamide and N-methylformamide. ε-caprolactam, N-methyl-2-
Lactam compounds such as pyrrolidinone and 2-pyrrolidinone. Cellosolve acetate, carbitol acetate,
Ester compounds such as ethylene glycol diacetate. Ether compounds such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether.

In order to further improve the dispersibility and solubility of the composition in a water-based bactericidal and antiseptic object, the present invention employs various surfactants or an interface such as benzalkonium chloride or didecyldimethylammonium chloride. A quaternary ammonium salt, a quaternary phosphonium salt or the like having an activating effect can be appropriately blended. As long as the composition is used in a commonly used amount, the properties of the composition of the present invention are not impaired by these compositions.

[0017]

According to the present invention, it is possible to provide orthophthalaldehyde useful as a bactericidal preservative in the form of a high-concentration solution that can be handled safely and easily without fear of dusting. The orthophthalaldehyde-stabilized composition of the present invention has high long-term storage stability, suppresses a decrease in component content and coloration of a solution due to decomposition and polymerization over a long period of time, and is excellent in dispersion and solubility in an aqueous sterilization and preservation target. . Furthermore, the composition does not freeze and solidify even under refrigeration conditions, and can be used and stored well even at low temperatures.

[0018]

Next, the present invention will be described in more detail with reference to examples. Examples 1 to 24, Comparative Examples 1 to 24 Orthophthalaldehyde (hereinafter referred to as OPA), water and each organic solvent were mixed and stirred at the compounding ratios shown in Tables 1 to 8 to obtain a solution OPA composition. . The composition in the table is OP
A, parts by weight based on 100 parts by weight of the organic solvent and water in total. The OPA used was OP-100SF (trade name, manufactured by KI Kasei Co., Ltd., flake-like pieces having a purity of 99% or more). As N, N-dimethylacetamide (hereinafter, referred to as DMAC), a commercial product of industrial grade manufactured by DuPont, γ-butyrolactone (hereinafter, G)
As BL), a commercial product of industrial grade manufactured by Mitsubishi Chemical Corporation was used.

The following measurements and tests were performed on each of the obtained orthophthalaldehyde compositions. Tables 1 to 8 show the results.
It was shown to. (Thermal Stability Test) 50 g of each of the OPA composition samples obtained in the Examples and Comparative Examples were placed in glass containers, sealed, and allowed to stand in a thermostat adjusted to 50 ° C. Six weeks later, the OPA content in the sample was measured by gas chromatography to determine the OPA residual rate. The coloring degree of each sample at this time was visually measured as the Gardner color number, and is shown in Tables 1 to 8 together with the Gardner color number immediately after preparation.

(Refrigeration Stability Test) Samples of the OPA compositions obtained in the Examples and Comparative Examples were each taken in a glass container in an amount of 50 g, sealed, and allowed to stand in a freezer adjusted to -10 ° C. One week later, the OPA composition is visually frozen or
The presence or absence of PA crystal precipitation was observed. When no freezing or crystal precipitation was observed, a small amount of OPA seed crystal was added, and the mixture was rapidly stirred and allowed to stand for another week. Similarly, the presence or absence of freezing and crystal precipitation was visually observed. (Those which were kept in a solution state without freezing and crystal precipitation were shown as "liquid" in the table.)

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

[0028]

[Table 8]

From the results shown in Tables 1 to 8, the OPA-stabilized compositions of the present invention of Examples 1 to 24 have a high OPA residual ratio even after being left at 50 ° C. for 6 weeks, and have almost no coloring. Also,
Even if left at -10 ° C for 2 weeks, it does not freeze and maintains a liquid state with almost no crystal precipitation. Stable and long-term storage is possible even at a high concentration of 40% by weight.
It turns out that it can be used. On the other hand, in Comparative Examples 1 to 12 in which water was not used, freezing and solidification occurred in refrigeration or 5
When left at 0 ° C. for 6 weeks, the OPA residual ratio is either low. In addition, in Examples 1 to 24, the number of Gardner colors hardly changed even after standing at 50 ° C. for 6 weeks, whereas in Comparative Examples 1 to 12, coloring was observed. In Comparative Example 13 where the amount of water used was too small, coloring of the solution occurred, and in Comparative Example 14 where too much water was used, crystals were precipitated by refrigeration. Among Comparative Examples 15 to 24 in which solvents other than DMAC and GBL were used together with water, Comparative Examples 15 to 17 in which an aprotic polar solvent was used were frozen and solidified by refrigeration, and coloring occurred. Also in Comparative Examples 18 and 19 using a solvent having no hydroxyl group, freeze-solidification and coloring occurred. In Comparative Examples 20 to 24 using the glycol-based solvent, either coloring or freeze-solidification occurs, or the component content decreases.

Claims (4)

[Claims] Claims: 1. An orthophthalaldehyde with respect to N, N
-An orthophthalaldehyde-stabilized composition comprising at least one solvent selected from dimethylacetamide and γ-butyrolactone and water. 2. A stabilized orthophthalaldehyde composition comprising 50 to 250 parts by weight of N, N-dimethylacetamide and 1 to 150 parts by weight of water based on 100 parts by weight of orthophthalaldehyde. 3. 50 parts to 200 parts by weight of γ-butyrolactone and 100 parts by weight of water based on 100 parts by weight of orthophthalaldehyde.
A composition for stabilizing orthophthalaldehyde, characterized by containing about 120 parts by weight. 4. A composition for stabilizing orthophthalaldehyde, characterized by comprising a predetermined amount of at least one solvent selected from N, N-dimethylacetamide and γ-butyrolactone and water with respect to orthophthalaldehyde. Production method.