JPH11140010A - Orthophthalaldehyde stabilized composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having high stability of orthophthalaldehyde in high concentration, manifesting reduced degradation, polymerization and discoloring and being liquid at normal temperature by including predetermined amounts of water and water soluble aliphatic alcohol to orthophthalaldehyde. SOLUTION: The composition comprises (A) 100 pts.wt. of orthophthalaldehyde, (B) 1-300 pts.wt. of water, preferably at pH of 4-8, (C) 1-500 pts.wt. of water soluble aliphatic alcohol(e.g.; polyethylene glycol 200, ethylene glycol monomethyl ether and the like). The prescribed composition is preferably prepared by directly adding water and a water soluble aliphatic alcohol to the synthesized orthophthalaldehyde in a melt state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an orthophthalaldehyde-stabilized composition useful as a raw material for disinfectants and non-medical antibacterial and algicidal agents. More specifically, an orthophthalaldehyde-stabilized solution that can be stably stored for a long period of time with reduced decomposition and coloration even at a high concentration, and has reduced storage and heat decomposition and reduced discoloration, has high storability, and is easy to melt. And a solvent and the like to prepare a liquid preparation.

[0002]

2. Description of the Related Art Orthophthalaldehyde has excellent bactericidal activity and is therefore useful as a raw material for disinfectants and non-medical antibacterial and algicidal agents, and is industrially supplied in various production methods and product forms. ing. For example, as industrial scale product forms, there are crystalline powder and solid orthophthalaldehyde which is obtained by directly distilling and purifying a distilled and purified fraction into a packaging container and solidifying by cooling. However, in the case of orthophthalaldehyde of this powder, the solubility in the antibacterial and algae target is not sufficient at the time of use, and it is irritating and corrosive. There are problems such as things.

For this reason, it is preferable that these orthophthalaldehydes are prepared and supplied in a high-concentration solution in advance. However, the melting point of orthophthalaldehyde is about 56 ° C., and the solubility in water at room temperature is about Since it is as low as 5% by weight, an organic solvent is usually used when preparing a solution. For example, JP-A-63-313705, JP-A-6-2
No. 3,368 and JP-A-7-116669 describe the use of alcohols (methanol, ethanol), glycols, esters, ketones, and aromatic hydrocarbons. However, orthophthalaldehyde is unstable in a high-concentration solution, and there is a problem in that a solution using the above organic solvent is decomposed and polymerized during storage.

[0004] On the other hand, for example, Japanese Patent Application Laid-Open No. Hei 8-302594 discloses a method in which a polymer is dissolved in propylene carbonate to improve stability.
Orthophthalaldehyde concentrated solutions are described.
However, the orthophthalaldehyde solution using such an aprotic solvent, which was pale yellow at the time of solution preparation, is easily colored brown by long-term storage at room temperature or heating, and is used for disinfection and antibacterial and algal use. There is a problem that causes adverse effects and a decrease in product value.

[0005] On the other hand, the above-mentioned solid orthophthalaldehyde has a higher stability of components than a solution. Therefore, if stored as it is, there is little decrease in the component content due to decomposition and polymerization, and there is no influence on the human body due to dusting. Therefore, it is easy to handle during storage and transportation, and it is less costly than powdery or liquid.However, in order to prepare it into a liquid for use, it is necessary to melt it, take out a predetermined amount from the packaging container, and mix it with a solvent etc. There is a problem in workability at this time. In other words, when a liquid preparation is industrially prepared using solid orthophthalaldehyde, the melting point is about 56 ° C. when the orthophthalaldehyde is transferred from a container to another container or a pot (or when subdivided). It is necessary to heat and melt as described above, to be able to be taken out of the container and mixed with a solvent or the like. However, it takes a long time to completely melt.
In addition, if the package is directly externally heated at the time of this heating, the pale yellow orthophthalaldehyde will be colored brown or black. (Powdered orthophthalaldehyde also has the property of being colored when it is heated and melted as it is.) The same coloring occurs when solid aprotic aldehyde is heated with an aprotic solvent added thereto. Solid orthophthalaldehyde to which an aliphatic alcohol having is added is hardly colored by heating and melting,
There was a problem that the decomposition and polymerization of the components of orthophthalaldehyde were remarkable.

[0006]

Accordingly, the present invention provides
An object of the present invention is to provide an orthophthalaldehyde-stabilized composition which is highly stable at a high concentration, has low decomposition, polymerization and coloring over time, and is liquid at room temperature. Further, the present invention can be taken out of the container without causing decomposition upon heating and melting, polymerization and coloring,
Another object of the present invention is to provide a solid orthophthalaldehyde-stabilized composition which can be completely melted in a short time and easily prepared into a liquid preparation or the like.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and as a result, when water and a water-soluble aliphatic alcohol are used in combination in a predetermined ratio as a solvent, a high-concentration orthophthalaldehyde solution can be obtained. The present inventors have found that the above-mentioned object can be achieved without coloring due to a stable period, and the present invention has been accomplished based on this finding. That is, the present invention
(1) Orthophthalaldehyde, a predetermined amount of water and a water-soluble aliphatic alcohol are contained in the orthophthalaldehyde-stabilizing composition, (2) 100 parts by weight of orthophthalaldehyde is water 1 to 300
The orthophthalaldehyde-stabilized composition according to (1), wherein the composition contains 1 part by weight and 1 to 500 parts by weight of a water-soluble aliphatic alcohol. (3) Ortho according to (1), wherein the solution is 1 to 300 parts by weight of water and 50 to 500 parts by weight of a water-soluble aliphatic alcohol based on 100 parts by weight of orthophthalaldehyde. Phthalaldehyde stabilizing composition, (4) 1 to 20 parts by weight of water and 1 to 20 parts by weight of a water-soluble aliphatic alcohol with respect to 100 parts by weight of orthophthalaldehyde, being a solid substance And (5) 100 parts by weight of orthophthalaldehyde are dispersed in 5 to 50 parts by weight of water and 5 to 50 parts by weight of a water-soluble aliphatic alcohol. An object of the present invention is to provide an orthophthalaldehyde-stabilized composition according to the above (1).

[0008]

DETAILED DESCRIPTION OF THE INVENTION The orthophthalaldehyde composition of the present invention is characterized by comprising orthophthalaldehyde, water and a water-soluble aliphatic alcohol. The composition of the present invention comprises 1 to 300 parts by weight of water, preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and 1 to 500 parts by weight of a water-soluble aliphatic alcohol based on 100 parts by weight of orthophthalaldehyde. Parts, preferably 1 to 200
Parts by weight, more preferably 1 to 100 parts by weight. If the amount of water is too large (the amount of the water-soluble aliphatic alcohol is too small), it may be difficult to rapidly dissolve the composition in the antibacterial and algal target. When the amount of the water-soluble aliphatic alcohol is too large (the amount of water is too small), the stability of the orthophthalaldehyde component in the composition is reduced. The composition of the present invention comprises:
The orthophthalaldehyde component is stable for a long 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 compositions of the present invention include solids, solutions,
Dispersions (such as suspensions) are included. When the composition of the present invention is a solution, the composition contains 1 to 300 parts by weight of water and 50 to 500 parts by weight of a water-soluble aliphatic alcohol based on 100 parts by weight of orthophthalaldehyde. From the viewpoints of production cost, stability of orthophthalaldehyde in solution, transportation, storage, etc., 50 to 100 parts by weight of water, 100 parts by weight of orthophthalaldehyde, water-soluble aliphatic alcohol 7
The amount is preferably 0 to 200 parts by weight, more preferably 60 to 80 parts by weight of water and 100 to 150 parts by weight of a water-soluble aliphatic alcohol. When the composition of the present invention is a solid, the composition contains 1 to 20 parts by weight of water and 1 to 20 parts by weight of a water-soluble aliphatic alcohol based on 100 parts by weight of orthophthalaldehyde. 1 to 10 parts by weight of water and 1 to 10 parts by weight of water-soluble aliphatic alcohol are preferable for 100 parts by weight of orthophthalaldehyde in terms of shortening of melting time, stability of the composition, transportation, storage, handling and production cost. And 2 to 5 parts by weight of water and 2 to 5 parts by weight of a water-soluble aliphatic alcohol. In the composition of the present invention, the shape of the solid is not limited as long as it is not in the form of a powder, and may be any shape such as a block, a column (tablet), and a flat plate. When the composition of the present invention is a dispersion (preferably a suspension), it contains 5 to 50 parts by weight of water and 5 to 50 parts by weight of a water-soluble aliphatic alcohol with respect to 100 parts by weight of orthophthalaldehyde. Become. In terms of stability, handling, transportation, and storage of the composition, 100 parts by weight of orthophthalaldehyde and water 8
-40 parts by weight, and 8-40 parts by weight of a water-soluble aliphatic alcohol, more preferably 10-20 parts by weight of water and 10-20 parts by weight of a water-soluble aliphatic alcohol.

The composition of the present invention can be prepared by directly mixing the above-mentioned water and water-soluble aliphatic alcohol with an industrially synthesized molten orthophthalaldehyde. In this case, the orthophthalaldehyde solidified in the packaging container can be added and mixed immediately before the melting operation. The melting and mixing temperature is not less than the melting point of orthophthalaldehyde (about 56 ° C), preferably 60 to 100 ° C, more preferably 70 to 80 ° C. it can. Further, water and a water-soluble aliphatic alcohol can be added to powdered orthophthalaldehyde and melted and mixed in the same manner as a solid one, and the shape of orthophthalaldehyde used as a raw material is not particularly limited. By adding water and a water-soluble aliphatic alcohol at the time of melting and mixing, coloring of orthophthalaldehyde by heating can be prevented. When the composition of the present invention is used as a dispersion, it is obtained by adding a mixed liquid of water and a water-soluble aliphatic alcohol and orthophthalaldehyde having a solubility equal to or higher than the solubility. The form of orthophthalaldehyde used at this time is not limited to powder (crystal), but can be obtained by directly adding a distillate of industrially purified orthophthalaldehyde and mechanically stirring it while gradually cooling it. Can be.

In the present invention, tap water, ion-exchanged water, distilled water and the like can be used without particular limitation, and water having a pH of 4 to 8 is usually used.

The water-soluble aliphatic alcohol that can be used in the present invention includes, for example, glycol solvents,
Glycol ether solvents, alcohol solvents and the like can be mentioned, and one kind may be used alone or two or more kinds may be mixed, and they can be arbitrarily selected and used. The composition of the present invention is a solution, in that it is preferably a homogeneous and low-viscosity solution when directly injected into an antibacterial and algal target, etc., and has a low viscosity as a water-soluble aliphatic alcohol, And it is preferable to use those that are sufficiently miscible with water, but using a water-soluble aliphatic alcohol having high viscosity or low compatibility with water does not affect the stability or prevention of coloring of the composition of the present invention. .
In addition, chain alcohols are generally known to have reduced compatibility with water as the molecular weight increases, but in the present invention, glycol-based solvents, glycol ether-based solvents, lower alcohols and the like By using a mixed solvent combined with another solvent having high compatibility with water as the water-soluble aliphatic alcohol, such a solvent having low compatibility with water can also be used favorably. The same applies to the viscosity. When used in combination with another solvent having a low viscosity, a solvent having a high viscosity can be favorably used. Thus, the use of two or more solvents in combination does not affect the stability of the composition of the present invention or the prevention of coloring.

The following are specific examples of the solvent that can be used in the present invention, but the present invention is not limited thereto. As the glycol solvent, a glycol having 2 to 5 carbon atoms or a polymer thereof is preferable. For example, ethylene glycol, diethylene glycol, tetraethylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, propylene glycol,
Dipropylene glycol, polypropylene glycol 4
00, polypropylene glycol 700, polypropylene glycol 1000, 1,3-propanediol,
1,3-butanediol, 1,4-butanediol,
2,3-butanediol and 1,5-pentanediol can be used.

As the glycol ether-based solvent, a monoether of a glycol having 2 to 9 carbon atoms and a lower alkyl or aryl is preferable, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether. Isopropyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether , Propylene Monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether.

The alcohol solvent preferably has 1 to 8 carbon atoms, may be cyclic or chain, and may be linear or branched. Further, the cyclic alcohol may have a hetero atom. Specifically, for example, methanol, ethanol, 1-propanol, 2-
Propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methyl-2-propanol,
-Pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, isopentyl alcohol, 2,2-dimethyl-1- Propanol, 1
-Hexanol, 2-methyl-1-pentanol, 4-
Methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, furfuryl alcohol, tetrahydrofurfuryl Alcohol.

In the present invention, as the water-soluble aliphatic alcohol, at least one selected from polyethylene glycol 200, polypropylene glycol 400, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether is used. , Composition stability and viscosity, composition (concentration)
This is preferred from the viewpoints of flexibility, solvent cost, and low volatility.

The orthophthalaldehyde-stabilized composition of the present invention has high long-term storage stability, and can prevent the decomposition, polymerization and coloring of the orthophthalaldehyde component during the heating and melting operation. Furthermore, in the solid orthophthalaldehyde-stabilized composition of the present invention, the time required for complete melting can be reduced, work efficiency can be greatly improved, and work safety can be ensured. In addition, when preparing a liquid preparation using the solid composition of the present invention, the present invention does not re-solidify even when the above-mentioned water and water-soluble aliphatic alcohol are further added, melted and mixed, and cooled to room temperature. Can be a stable orthophthalaldehyde high concentration solution.

[0017]

Next, the present invention will be described in more detail with reference to examples. Examples 1 to 38, Comparative Examples 1 to 13 Orthophthalaldehyde, water and each organic solvent were mixed and stirred at the compounding ratios shown in Tables 1 to 6 to form a solution (Examples 1 to 2).
8, Comparative Examples 1 to 8) or solid (Examples 29 to 38, Comparative Examples 9 to 13) orthophthalaldehyde compositions were obtained. In Examples 1 to 28 and Comparative Examples 1 to 8, powdered orthophthalaldehyde (manufactured by Union Carbide) was used. For Examples 29 to 33 and Comparative Examples 9 to 11, a fraction obtained by distilling and purifying orthophthalaldehyde was used. Example 3
4 to 38 and Comparative Examples 12 and 13 are packed in 100
8 wrapped in a liter polyethylene-coated iron drum
Solid orthophthalaldehyde (manufactured by Ihara Nikkei Chemical Co., Ltd.) packed with 0 kg was used.

The following measurements and tests were performed on each of the obtained orthophthalaldehyde compositions. The results are shown in Tables 1 to 6.
It was shown to. Examples 1 to 28 and Comparative Examples 1 to 8 (orthophthalaldehyde solution) 50 g of each of the orthophthalaldehyde solutions obtained in Examples 1 to 28 and Comparative Examples 1 to 8 were taken in a glass container, sealed and sealed at 50 ° C. For 6 weeks. The remaining orthophthalaldehyde was analyzed by gas chromatography to determine the orthophthalaldehyde residual ratio. In addition, each sample 5
Take 0 g in a glass container, stopper tightly and place in an 80 ° C thermostat.
After standing for a week, the degree of coloring of each sample was visually measured as the Gardner color number. (The Gardner color number of the orthophthalaldehyde solution immediately after preparation is 4.) The results are shown in Tables 1 to 4. About Examples 29-33 and Comparative Examples 9-11 (orthophthalaldehyde solids) 20 g each of the orthophthalaldehyde solids obtained in Examples 29-33 and Comparative Examples 9-11 were taken in a glass container,
The container was sealed and left in a constant temperature bath at 80 ° C. for one week. The remaining orthophthalaldehyde was analyzed by gas chromatography to determine the orthophthalaldehyde residual ratio. Also, 1
The degree of coloring of each sample after standing for a week was visually measured as the Gardner color number. (The ortho-phthalaldehyde solid immediately after preparation has a Gardner color number of 7.) The results are shown in Table 5. Examples 34 to 38 and Comparative Examples 12 and 13 (Orthophthalaldehyde Solids) The orthophthalaldehyde solids obtained in Examples 34 to 38 and Comparative Examples 12 and 13 were heated at 75 ° C. in an air bath heating system together with the container. And the number of days until the solid orthophthalaldehyde completely melted and the residual amount of orthophthalaldehyde at the end of melting were measured. The coloring degree of the melted orthophthalaldehyde was visually measured as the Gardner color number. The results are shown in Table 6.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4]

[0023]

[Table 5]

[0024]

[Table 6]

From the results shown in Tables 1 to 4, the orthophthalaldehyde solutions of the present invention of Examples 1 to 28 have a high residual ratio of orthophthalaldehyde even after standing at 50 ° C. for 6 weeks, and have no coloring. It can be seen that even a solution having a high concentration of 40% by weight is a solution that is stable and can be stored for a long time. On the other hand, Comparative Examples 1, 3, using only water-soluble aliphatic alcohol as the solvent,
In Nos. 5 and 7, the residual ratio of orthophthalaldehyde is extremely low, and coloring is also observed. In Comparative Examples 2, 4, 6, and 8, in which only the aprotic solvent was used, although the residual rate of orthophthalaldehyde was high, the coloring of the solution was remarkable. Examples 22 to 28 in Table 4 are examples in which a mixed solvent of ethylene glycol monomethyl ether and 1-octanol was used as a water-soluble aliphatic alcohol. In addition, from the results in Table 5, the solid orthophthalaldehyde compositions of the present invention obtained in Examples 29 to 33 are not significantly reduced in the amount of the orthophthalaldehyde component due to storage and have no coloring. In Comparative Example 9 using only orthophthalaldehyde and Comparative Example 10 using only water, the residual rate of orthophthalaldehyde was low and coloring was remarkable. Comparative Example 11 using only ethylene glycol monomethyl ether has a remarkably low orthophthalaldehyde residual ratio. Furthermore, as is clear from Table 6, the solid orthophthalaldehyde compositions of the present invention obtained in Examples 34 to 38 have no decomposition of orthophthalaldehyde due to heat melting, and almost no coloring during heat melting. Absent.
Also, the number of days until complete melting is greatly reduced to 3 days, compared to 7 days for Comparative Example 12 using only orthophthalaldehyde.

[0026]

The orthophthalaldehyde-stabilized composition of the present invention has a composition in which the content of the orthophthalaldehyde component in the composition is not decomposed or degraded by long-term storage or heat-melting operation, and is not affected by aging or heating. There is almost no coloring. Therefore, it can be stably stored for a long time in a shape that is easy to handle, and the commercial value does not decrease due to coloring. Further, according to the solid orthophthalaldehyde-stabilized composition of the present invention, the time required for heating and melting can be shortened, the working efficiency can be improved, and dusting can be prevented to ensure work safety. Furthermore, the orthophthalaldehyde-stabilized composition in the form of a solution of the present invention is stable for a long period of time even at a high concentration, has no adverse effect on the human body due to dusting, is extremely easy to prepare and dilute with other components, and is easy to handle. It is possible to supply in a form having excellent properties.

Claims (5)

[Claims] 1. A stabilized orthophthalaldehyde composition comprising a predetermined amount of water and a water-soluble aliphatic alcohol with respect to orthophthalaldehyde. 2. The stable orthophthalaldehyde according to claim 1, wherein 1 to 300 parts by weight of water and 1 to 500 parts by weight of a water-soluble aliphatic alcohol are contained per 100 parts by weight of orthophthalaldehyde. Composition. 3. The solution according to claim 1, wherein 1 to 300 parts by weight of water and 50 to 500 parts by weight of a water-soluble aliphatic alcohol are contained with respect to 100 parts by weight of orthophthalaldehyde. Orthophthalaldehyde stabilized composition. 4. 1 to 20 parts by weight of water and 1 part by weight of water-soluble aliphatic alcohol per 100 parts by weight of orthophthalaldehyde
2. The composition for stabilizing orthophthalaldehyde according to claim 1, wherein the composition is a solid. 5. A mixture of 100 parts by weight of orthophthalaldehyde and 5 to 50 parts by weight of water and 5 to 50 parts of a water-soluble aliphatic alcohol.
The orthophthalaldehyde-stabilized composition according to claim 1, wherein the composition is dispersed in parts by weight.