JPS62737B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a gel-like substance using dibenzalsorbitol (hereinafter abbreviated as DBS). More specifically, the present invention relates to a method for producing a gel-like substance using a mixed solution of a polar organic solvent and a metal compound soluble in the organic solvent as a DBS solvent. As is well known, DBS has the ability to gel various organic compounds. This gelation is performed by dissolving DBS at a high temperature and then lowering the temperature of the solution, taking advantage of the fact that the solubility of DBS increases significantly as the temperature increases. However, in this method, when using a low boiling point organic solvent, it is not possible to heat it to a high temperature, so the solubility of DBS is low.
A gel-like substance with good shape retention cannot be obtained. Furthermore, the syneresis rate is high and the stability of the gel-like substance is poor. For example, a gel-like substance cannot be obtained with methyl alcohol, and when using isopropyl alcohol, the solubility of DBS is quite low even at the boiling point of isopropyl alcohol, and the dissolution operation is difficult, so only a gel-like substance with low strength can be obtained. As a solution to this problem, it is known to add a good solvent for DBS. dimethylformamide, dimethylsulfoxide, hexamethylsulfolamide,
DBS dissolves well in solvents such as N-methylpyrrolidone and sulfolane even at fairly low temperatures, so by adding a small amount of this, the solubility of DBS can be improved even in poor DBS solvents such as isopropyl alcohol. This makes it possible to produce gel-like substances. Furthermore, by increasing the amount of these good solvents, it becomes possible to prevent the precipitation of DBS even if water or a hydrocarbon compound, etc., which are non-solvents for DBS, are added. However, these good solvents are highly toxic to the human body or extremely expensive. Furthermore, the physical properties of the resulting gel are poor, and gel-like substances produced by DBS using these good solvents are unsuitable for many uses. Furthermore, in Japanese Patent Publication No. 52-20037, hydroxypropyl methylcellulose or cellulose in which a portion of hydroxypropyl methylcellulose has been replaced with hydroxypropoxy groups and water are added to a solution of DBS in alcohol, heated, and cooled to completely dissolve alcohols. A transparent gelation method is described, and although water is an essential component in this method, the resulting gel-like material is flexible, so it is not possible to obtain a gel-like material with sufficient strength. As a result of various studies to find a suitable solvent for DBS, the present inventors discovered the surprising fact that even a poor solvent for DBS can be transformed into a good solvent for DBS by adding a specific metal compound to it. Based on this knowledge, we have completed the present invention. That is, in the present invention, a liquid mixture containing DBS, a polar organic solvent, and at least one metal compound selected from chlorides, bromides, iodides, and nitrates of lithium, calcium, and magnesium as essential components is dissolved by heating, and then cooled. The present invention provides a method for producing a gel-like substance, which is characterized by solidifying it. DBS used in the present invention is a compound easily obtained by a condensation reaction between benzaldehyde and sorbitol. This DBS includes alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, methoxy, ethoxy,
It may be nuclear-substituted with an alkoxy group such as propoxy, butoxy, isobutoxy, or a halogen group, and in the present invention, these can be used alone or in combination of two or more. Examples of the polar organic solvent used in the present invention include various polar organic solvents such as alcohols, esters, ketones, ethers, and amides. If the method of the present invention is applied to a solvent that has a high boiling point and dissolves DBS well at high temperatures, or a good solvent for DBS, the solubility of DBS will further increase.
Although a large amount of non-solvent can be added, the present invention uses a poor solvent system for DBS with a boiling point of about 50 to 140 °C and a solubility of DBS of about 5 g/100 g of solvent at the boiling point or around 100 °C. It is particularly effective in gelation. Examples of such poor solvents include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, methyl cellosolve, cellosolve, butyl cellosolve,
Butanediol methyl ether, ethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, tetrahydrofuran, 1,4-dioxane,
Examples include 1,3-dioxane.
Particularly effective are alcohols having 1 to 4 carbon atoms and monoalkyl ethers of ethylene glycol, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, These are sec-butyl alcohol, tert-butyl alcohol, ethylene glycol methyl ether, and ethylene glycol ethyl ether. These polar organic solvents can be used alone or in a mixture of two or more. The metal compounds of the present invention added to the above polar organic solvent are chlorides, bromides, iodides, and nitrates of lithium, calcium, and magnesium, all of which are soluble in the above polar organic solvent.
Specific examples include lithium chloride, lithium bromide, lithium nitrate, calcium chloride, calcium bromide, calcium iodide, calcium nitrate, magnesium chloride, magnesium bromide, magnesium iodide, and magnesium nitrate. Among these metal compounds, lithium chloride, calcium chloride, calcium bromide, calcium nitrate,
Magnesium chloride and the like are preferred. Particularly preferred is calcium chloride, which is effective in small amounts, is inexpensive, and has low toxicity. Note that metal compounds soluble in organic solvents such as tin, titanium, iron, nickel, and cobalt are not preferred because they slightly decompose DBS. The above metal compounds can be used alone or in a mixture of two or more. In the present invention, the mixing ratio of DBS, polar organic solvent and metal compound can be varied over a wide range.
However, since DBS and metal compounds remain as non-volatile components in the gel-like substance, it is not preferable to use them in large quantities. In consideration of the physical properties, cost, etc. of the gel-like material, it is usually preferable to prepare the DBS in 1 to 5 parts by weight and the metal compound in 0.5 to 10 parts by weight in 100 parts by weight of the gel-like material. If a metal compound is not used at this time, the solubility of DBS in the polar organic solvent will not be sufficient, making it impossible to obtain a strong gel-like substance. When preparing the gel-like substance of the present invention, the above-mentioned
Besides DBS, polar organic solvents and metal compounds,
One or more types of water and hydrocarbon compounds, which are non-solvents for DBS, can be added. By mixing a non-solvent, it becomes possible to incorporate a substance that is insoluble in the polar organic solvent and soluble in the non-solvent into the gel-like substance. Furthermore, by adding a non-solvent, it becomes easy to adjust the gelation temperature of the mixed solution of DBS, a polar organic solvent, and a metal compound, and the price of the gel material can be further reduced. In particular, when mixed with water, the combustibility of the gel-like substance, which is flammable, can be reduced, and the safety in storage and use of the gel-like substance can be improved. The non-solvent is preferably water and/or an aliphatic hydrocarbon compound, and examples of the aliphatic hydrocarbon compound include benzine, kerosene, liquid paraffin, vaseline, terpenes, squalene, squalane, etc. More than one species is used in combination. When such non-solvents are mixed, the amount that can be mixed can be increased by raising the mixing temperature, but the mixing temperature is appropriately determined in relation to the boiling point. The gel-like substance of the present invention is produced by mixing the above-mentioned components, heating and melting the mixture, and then cooling the mixture. Although there are no particular restrictions on the order in which the components are mixed, DBS, a polar organic solvent, and a metal compound are usually placed in a container equipped with a stirrer, a reflux device, a thermometer, and a sample inlet, and the temperature is raised while stirring.
Dissolve the DBS completely while keeping it at reflux or 80-100 °C, add the amount of non-solvent below the DBS precipitates as required, pour the solution into the mold and cool. The difference between the dissolution temperature and the gelation temperature can be adjusted by the solubility of DBS (determined by the solvent composition, amount of non-solvent, temperature, etc.), but a temperature of about 5 to 20°C is suitable for handling. For cooling, it is sufficient to simply let it cool to room temperature, but in order to improve productivity, it may be cooled rapidly. At the same time as DBS precipitates, a gel-like substance is generated. Moreover, in the present invention, in addition to the above-mentioned components,
It is possible to add active ingredients, soluble polymers, fillers, humectants, surfactants, colorants, etc. Active ingredients include medicinal ingredients, fragrances, cosmetics, etc. Specifically, they include deodorants, fragrances, anti-inflammatory/analgesic agents,
Examples include insect repellents, agents for A. aeruginosa syndrome, hemostatic agents, anti-itch agents, disinfectants, and agents for preventing rough skin. Soluble polymers include methylcellulose, ethylcellulose, hydroxyethylcellulose,
Examples include hydroxypropylcellulose, porvinylpyrrolidone, polyethylene glycol, and acrylic acid copolymers. Furthermore, polyvinyl acetate, ethyl cellulose, etc. can also be used as a non-solvent when adding a hydrocarbon compound. As the filler, kaolin, clay, bentonite, talc, calcium carbonate, zinc white, silica, wheat flour, corn starch, etc. can be used. Humectants include ethylene glycol, propylene glycol, glycerin, and low molecular weight polyethylene glycol, and surfactants include mono- and di-fatty acid esters of glycerin, ethylene oxide-propylene oxide copolymers, and polyethylene glycol mono-fatty acid esters. Can be mentioned. According to the present invention, a gel-like material with a low syneresis rate and high strength can be produced using a polar organic solvent, regardless of whether the gel-like material contains water or not, and is useful as a solid fuel. It is. Furthermore, by adding an active ingredient, it can be used as, for example, a solid deodorant and fragrance, a solid insect repellent, and a stick painkiller. Next, the present invention will be explained with reference to Examples. In addition,
As DBS, Gelol D, a trade name manufactured by Shin Nihon Rika Co., Ltd., was used. The compressive strength of gel material is 3cm
ψ×4cm gel-like substance is 4cm/
It was compressed at a speed of min and its fracture strength was determined. Example 1 Metal compound 3 in Table 1 was added to 50 g of ethyl alcohol.
g and 2.5 g of DBS were added, and the temperature was raised to 75°C. When hot, water was added until just before DBS precipitated, and the mixture was cooled to produce a gel-like substance. The results are shown in Table 1.

[Table] Substance weight loss (%)
From this example, by adding a metal compound, it becomes possible to mix with water, which is a non-solvent of DBS.
Moreover, it can be seen that the compressive strength of the gel-like substance is improved. In addition, the syneresis rate is small and it becomes stable as a gel-like substance. Example 2 Using calcium chloride, ethyl alcohol and/or cellosolve, Example 1 was prepared using the formulation shown in Table 2.
A gel-like substance was prepared in the same manner as above. The results are in Table 2
Shown below.

[Table] As in Example 1, the miscible amount of water was increased, and the compressive strength and syneresis rate were improved. Example 3 2.5 g of DBS and 3 g of calcium chloride were added to 50 g of the organic solvent shown in Table 3, and dissolved at elevated temperatures to determine the miscible amount of water when heated. Next, in the same order, a predetermined amount of water was added to a solution of DBS and calcium chloride while it was hot, and the mixture was cooled to produce a gel-like substance. The compressive strength and syneresis rate of the gel material obtained were measured. The results are shown in Table 3.

[Table] As in Example 1, the miscible amount of water was increased, and the compressive strength and syneresis rate were improved. Example 4 A predetermined amount of water was added when hot to a solution of 50 g of ethyl alcohol, 2.5 g of DBS, 1 g of the soluble polymer shown in Table 4, and calcium chloride in the amount shown in Table 4, and the solution was cooled to produce a gel-like substance. The results are shown in Table 4.

[Table]

[Table]
In Comparative Examples Nos. 1 and 4, the gel-like substances obtained were soft and did not have sufficient strength to measure compressive strength. Furthermore, Comparative Examples Nos. 2, 3, 5 and 6 did not have sufficient compressive strength and syneresis rate compared to Examples Nos. 1 to 6. Example 5 30g of ethyl alcohol, 10g of cellosolve
Add 1.5 g of DBS and 3 g of calcium chloride, dissolve by heating, and when hot, add 50 g of water, 3 g of commercially available lemon flavor, and 0.2 g of nonionic surfactant, and stir well.
The mixture was poured into a container and allowed to cool to room temperature to obtain a gel-like substance. There is no fragrance separation and it can be used as a solid fragrance that releases fragrance gradually. Example 6 Add 1.2 g of DBS and 1.5 g of calcium chloride to 50 g of ethyl alcohol, dissolve by heating, and add 30 g of water when heated.
g, methyl salicylate 1.0g, thymol 0.5g, 1
- 0.5 g of menthol was added, stirred well, poured into a container, and allowed to cool to room temperature to obtain a stick-like gel-like substance. When applied to the skin, it is moderately abrasive and can be used as an anti-inflammatory analgesic with an excellent feel. Example 7 Add 1.5 g of DBS and 2 g of calcium chloride to 50 g of ethyl alcohol and dissolve by heating. When hot, add 40 g of water, 2 g of N·N-diethyltoluamide, and 3 g of propylene glycol, stir well, and pour into a container. The mixture was allowed to cool to room temperature to obtain a gel-like substance. It can be used as a mosquito repellent and can be applied to the skin or left to evaporate. Example 8 10g of ethyl alcohol and 30g of cellosolve
Add 1.2 g of DBS, 1.5 g of calcium chloride, and 0.5 g of methyl cellulose and dissolve by heating. When heated, 5 g of liquid paraffin, 3 g of propylene glycol, d1-
Camphor 1g, allantoin 0.2g, vitamin E
0.2 g of acetic ester was added, stirred well, poured into a container, and allowed to cool to room temperature to obtain a gel-like substance. It can be suitably used as a stick-like skin roughness preventive agent.

Claims (1)

[Claims] 1. A mixed solution containing dibenzalsorbitol, a polar organic solvent, and at least one metal compound selected from chlorides, bromides, iodides, and nitrates of lithium, calcium, and magnesium as essential components is dissolved by heating. A method for producing a gel-like substance, the method comprising: cooling and solidifying the substance. 2. The method for producing a gel-like substance according to claim 1, wherein the polar organic solvent is at least one selected from alcohols, esters, ketones, and ethers having a boiling point of 50 to 140°C. 3 The polar organic solvent is methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, t-butyl alcohol, sec-butyl alcohol, ethylene glycol methyl ether, and ethylene glycol ethyl The method for producing a gel-like substance according to claim 1, wherein the gel-like substance is at least one selected from ethers. 4. The method for producing a gel-like substance according to claim 1, wherein the metal compound is at least one selected from lithium chloride, calcium chloride, calcium bromide, calcium nitrate, and magnesium chloride.