JP2001316215A - Alum aqueous solution and method for producing the same, viscous alum aqueous solution and method for producing the same, gelled composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alum aqueous solution which can be supplied as a raw material for various uses. SOLUTION: This substantially transparent alum aqueous solution obtained by dissolving alum and urea in a prescribed amount of water, characterized by dissolving the alum in an amount exceeding a limited dissolution concentration for the prescribed amount of the water in the alum aqueous solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alum aqueous solution and a method for producing the same, a viscous alum aqueous solution and a method for producing the same, a gelling composition and a method for producing the same, and more particularly, alum and urea are dissolved in a predetermined amount of water. A substantially transparent alum aqueous solution obtained and a method for producing the same,
The present invention relates to a viscous alum aqueous solution that is made viscous so that a film is formed when applied, a method for producing the same, a gelled composition in which the alum solution is gelled, and a method for producing the same.

[0002]

2. Description of the Related Art Alum has an antiseptic action and an astringent action when applied to the skin, and is therefore used in antiperspirants, acidic lotions, facial cleansers, bath preparations and the like. Further, alum is also used as a mordant for dyes, pigments, sizing agents and the like. As a raw material of alum used for such various uses, if it can be supplied in a liquid state, it is extremely convenient and advantageous in terms of handling of the raw material. However, at room temperature, since the limit solubility concentration of alum in water is low, when the alum aqueous solution is supplied as a raw material for various uses, the concentration of alum dissolved must be kept low in consideration of temperature control during transportation and storage. And transportation costs and storage costs increase. For this reason, conventionally, the raw material of alum used for antiperspirants and the like has been supplied in a solid state.

[0003]

As described above, the raw material of alum supplied in a solid state has lower transportation and storage costs and is easier to manage as compared with a low-concentration alum aqueous solution. However, when an intended product is to be obtained using a solid alum raw material, it is necessary to dissolve the solid alum raw material. Therefore, there is a strong demand for an alum aqueous solution as a raw material. Further, when an alum aqueous solution is used as an antiperspirant or the like, the duration of the medicinal effect such as the antiperspirant effect of the sprayed alum aqueous solution is short, and there is a demand for extending the duration of the medicinal effect. Furthermore, in order to form the alum aqueous solution into a predetermined shape, for example, as proposed by the present inventor in Japanese Patent Application No. Hei 7-152274 (Japanese Patent Application Laid-Open No. 8-231218), a hot alum solution is formed. After filling the container,
It is necessary to cool the hot solution and grow alum crystals in a block shape while sealing the open surface of the hot solution to prevent evaporation of water from the open surface. For this reason, an alum-containing composition that can be easily formed into a predetermined shape is also demanded. Therefore, a first object of the present invention is to provide an alum aqueous solution that can be supplied as a raw material for various uses and a method for producing the same. A second object of the present invention is to provide an alum aqueous solution capable of extending the duration of the medicinal effect of the alum aqueous solution and a method for producing the same. A third object of the present invention is to provide an alum-containing composition that can be easily formed into a predetermined shape and a method for producing the same.

[0004]

Means for Solving the Problems As a result of repeated studies to solve the first problem, the present inventor has found that, with an alum aqueous solution in which alum and urea are dissolved in water, the amount of alum dissolved is reduced. The present inventors have found that a stable alum aqueous solution can be obtained even when the concentration exceeds the limit dissolution concentration in water, and have reached the first present invention. That is, a first aspect of the present invention is a substantially transparent alum aqueous solution obtained by dissolving alum and urea in a predetermined amount of water, wherein the alum aqueous solution contains a limit to the predetermined amount of water. An alum aqueous solution characterized in that alum in an amount exceeding the dissolution concentration is dissolved. Further, the first present invention provides a method for producing a substantially transparent alum aqueous solution comprising alum and urea dissolved in a predetermined amount of water,
After heating and dissolving an alum in an amount exceeding the critical dissolution concentration in the predetermined amount of water in the water to form a heating solution, adding a predetermined amount of urea to the heating solution, and dissolving the urea when the urea is dissolved. A method for producing an alum aqueous solution, wherein the solution is immediately cooled.

Further, the inventor of the present invention has conducted various studies to solve the second problem. As a result, when the alum aqueous solution is applied to the skin, it contains a urea adduct formed by the reaction between alum and urea. It has been found that the duration of the medicinal effect of alum can be prolonged by forming a film that can be formed, and the present invention has reached the second invention. That is, the second present invention is a substantially transparent viscous alum aqueous solution obtained by dissolving alum and urea in a predetermined amount of water, and when the alum aqueous solution is applied, the alum and urea are mixed. A viscous alum aqueous solution characterized in that a water-soluble polymer is dissolved in the alum aqueous solution so as to form a film containing a urea adduct formed by the reaction. Further, the second invention is characterized in that when producing a substantially transparent viscous alum aqueous solution comprising alum and urea dissolved in a predetermined amount of water, the alum is heated and dissolved in the predetermined amount of water. After the heating solution,
When a predetermined amount of urea is added to and dissolved in the heated solution,
Immediately cooling the heated solution to obtain an alum aqueous solution,
Next, when the resulting alum aqueous solution is applied, a water-soluble polymer is dissolved in the alum aqueous solution so that a film containing a urea adduct generated by the reaction of alum and urea is formed. It is also a method for producing a viscous alum aqueous solution characterized by viscous treatment.

Further, as a result of the present inventor's study to solve the above third problem, as an alum-containing composition which can be easily formed into a predetermined shape, alum, urea and a predetermined amount of water are dissolved. It was found that by using the gelled composition composed of
Of the present invention. That is, the third invention is a substantially transparent gelling composition obtained by dissolving alum and urea in a predetermined amount of water, wherein the gelling composition contains the alum and the urea. A gel composition characterized in that a water-soluble polymer soluble in an alum aqueous solution obtained by dissolving urea in a predetermined amount of water is added. Further, the third invention provides a method for producing a substantially transparent gelled composition obtained by dissolving alum and urea in a predetermined amount of water, wherein the alum, urea and the water-soluble polymer are used. A method for producing a gelling composition characterized in that a transparent alum aqueous solution dissolved in a predetermined amount of water is obtained, and then the alum aqueous solution is frozen in a frozen atmosphere and then gelled by thawing. is there.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The alum aqueous solution according to the first invention is a substantially transparent alum aqueous solution in which alum, water and urea are dissolved. As the alum, alum conventionally used can be used, and specifically, aluminum potassium sulfate [A
1K (SO ₄ ) ₂ .12H ₂ O], aluminum ammonium sulfate [AlNH ₄ (SO ₄ ) ₂ .12H ₂ O], or sodium aluminum sulfate [NaAlNH ₄ (SO ₄ ) _2]
[12H ₂ O] can be suitably used. The amount of the alum to be dissolved can be an amount that exceeds the limit dissolved concentration of the alum in the water to be dissolved. As described above, the alum can be dissolved in an amount exceeding the limit concentration of alum dissolved in water, because urea is dissolved in the alum aqueous solution. This is shown in [Table 1] and [Table 2] below. This [Table 1] is a table in which the concentration (solubilization limit concentration) at which aluminum potassium sulfate (potash) can be dissolved in an alum aqueous solution is investigated by changing the temperature of the aqueous solution and the urea concentration. Also,
[Table 2] is a table in which the concentration at which aluminum ammonium sulfate (ammonium alum) can be dissolved in an alum aqueous solution (solubility limit concentration) was measured by changing the temperature of the aqueous solution and the urea concentration.

[Table 1]

[Table 2] The concentrations shown in [Table 1] and [Table 2] are concentrations with respect to the obtained alum aqueous solution.

The following Tables 3 and 4 are tables for measuring the specific gravity and viscosity at 20 ° C. of the alum aqueous solution shown in Tables 1 and 2. The concentrations shown in [Table 3] and [Table 4] are also the concentrations with respect to the obtained alum aqueous solution.

[Table 3]

[Table 4] As is clear from [Table 1] to [Table 4], the amount of alum dissolved in water by dissolving urea is determined by the limiting dissolution concentration in water (the solubilizing limit concentration when the amount of urea added is 0% by weight). Can be exceeded. Further, the obtained alum aqueous solution is substantially transparent, and its viscosity is within a range in which the alum aqueous solution can be easily handled.

FIG. 1 shows an alum aqueous solution obtained by changing the amount of alum and urea added, stored in an atmosphere of 20 ° C. for one month. In FIG. 1, the vertical axis shows the alum concentration as the Alum concentration, and the horizontal axis shows the urea concentration.
Shown as Urea concentration. Each of these concentrations is a concentration with respect to the alum aqueous solution. In FIG. 1, region 1
Is a region in which the amount of urea dissolved is smaller than the amount of alum dissolved, and alum crystals precipitate during storage.
On the other hand, region 2 is a region in which the amount of urea dissolved is larger than the amount of alum dissolved, and needle crystals precipitate during storage. The needle crystals precipitated in this region 2 were subjected to macro-Kjeldahl method for nitrogen determination, aluminum oxide concentration analysis, and differential thermal analysis. As a result, the needle crystals were found to be urea adduct formed by the reaction between alum and urea. Is determined. The boundary between the region 1 and the region 2 is such that the urea concentration is 4
Around 0% by weight. In contrast to the region 1 and the region 2, the region 3 is a region in which excess urea is dissolved with respect to the amount of alum dissolved, and is a region in which the added urea is decomposed. In this region, to dissolve excess urea,
This is a region where excess urea is decomposed when urea is added to and dissolved in a heating solution obtained by heating and dissolving alum and water.
Such decomposition tends to occur when urea having a urea concentration exceeding 50% by weight is added. Also in this region 3, precipitation of needle-like crystals is observed during storage.

On the other hand, a region 4 is a region where a transparent alum aqueous solution composed of alum, urea and water can be stably held for one month under an atmosphere of 20 ° C. This area 4
Is a region where the urea concentration is 50% by weight or less, and preferably 5 to 50% by weight. In such a region 4, as the urea concentration increases, the solubilization limit concentration of the alum in the alum aqueous solution increases, and the urea concentration becomes 30 to 45.
The solubilization limit concentration reaches a peak at% by weight. Like this
By dissolving urea, the amount of alum exceeding the limit solubility concentration of alum in water can be dissolved because in the areas 2 and 3 where the amount of urea dissolved is large, alum reacts with urea to form urea adducts. It is considered that this is caused by the reaction between alum and urea in the alum aqueous solution to form a urea adduct from the precipitation of the acicular crystals.

[0011] Such an alum aqueous solution is prepared by heating and dissolving a predetermined amount of water and an amount of alum exceeding the limit dissolution concentration in water to form a heating solution, and then adding a predetermined amount of urea to the heating solution. When the dissolved urea is dissolved in the heated solution, it can be obtained by immediately cooling the heated solution. Generally, when alum, urea and water are heated, a precipitate of aluminum hydroxide is generated by a uniform precipitation reaction. That is, when urea is added to an acidic sample solution containing aluminum ions and heated to 90 to 100 ° C.,
The hydrolysis of urea produces ammonium hydroxide in the solution and the aluminum hydroxide precipitates. Also, when the alum aqueous solution of alum and water is heated for a long time,
Produces basic salts, producing a cloudy precipitate. In this regard, in the present invention, urea is added to a heated solution of alum and water, and when the urea is dissolved, cooling is performed immediately so that the heating time of the urea is as short as possible, so that the urea is heated. Decomposition is suppressed as much as possible. Here, in order to immediately cool the heating solution in which urea is dissolved, replenish the amount of water scattered with steam or the like during heating, and add room temperature water to adjust the alum concentration or the like to a predetermined concentration. Alternatively, it can be carried out by adjusting the concentration of alum in the heating solution to be slightly higher than a predetermined value, and immediately adding an insufficient amount of water when the urea added to the heating solution is dissolved.

In order to dissolve a large amount of alum in water, it is advantageous to increase the dissolution temperature. However, urea is added to a high-temperature heated solution, and the alum dissolved by adding urea is dissolved. The cooling time for cooling the heated solution also increases. For this reason, there is a tendency that ammonium hydroxide is generated in the solution by the hydrolysis of urea, and a hydroxide of aluminum is generated to easily cause cloudy precipitation. If this tendency is observed, the molar ratio of urea / alum should be 40
The following adjustment is preferable because the formation of a basic salt can be suppressed. When ammonium alum is used, the temperature at which the alum aqueous solution is adjusted is set to 110 ° C.
By keeping it below, the generation of the basic salt can be suppressed.

[0013] In the alum aqueous solution thus obtained, an amount of alum exceeding the limit dissolution concentration of alum in the water contained in the aqueous solution is dissolved, but the amount of alum exceeds the limit of solubilization of the alum aqueous solution. By adding a solubilizing agent that can increase the amount of dissolution, an alum aqueous solution in which a large amount of alum is dissolved can be obtained. As such a solubilizer, a water-soluble polymer or a sodium salt can be used. As the water-soluble polymer, a water-soluble cellulose having a hydrophilic group or a carboxyvinyl polymer can be used. Examples of the water-soluble cellulose having a hydrophilic group include hydroxyethyl cellulose and methyl cellulose. And carboxymethylcellulose. The amount of the water-soluble polymer added as the solubilizer is preferably 0.05 to 0.5% by weight based on the alum aqueous solution. In addition, sodium sulfate can be used as a sodium salt as a solubilizing agent, and its addition amount is preferably 0.1 to 10% by weight based on the alum aqueous solution.

By the way, in the alum aqueous solution, as shown in [Table 1] and [Table 2], the solubilization limit concentration of the alum aqueous solution decreases as the solution temperature becomes lower.
For this reason, when storing alum aqueous solution in winter,
Crystals and the like may be precipitated in the alum aqueous solution.
In order to eliminate such a possibility that crystals and the like are precipitated in the alum aqueous solution, it is preferable to add a low-temperature stabilizer that lowers the freezing point temperature or the crystal precipitation starting temperature of the alum aqueous solution. As such a low-temperature stabilizer, a sugar alcohol can be used. Examples of the sugar alcohol include glycerin, sorbitol, xylitol, mannitol, and galactitol.
And xylitol can be suitably used. The amount of the low-temperature stabilizer to be added is 1 to the alum aqueous solution.
It is preferably 50% by weight, particularly preferably 5 to 30% by weight. Here, when the amount of the low-temperature stabilizer is less than 1% by weight, a substantial effect of storage stability accompanying a decrease in temperature tends to be hardly exerted. On the other hand, when the amount of the low-temperature stabilizer is 50
If the amount exceeds 10% by weight, the contents of urea and alum in the alum aqueous solution decrease, and when the alum aqueous solution is applied to the skin, a sticky feeling tends to accompany.

[0015] The obtained alum aqueous solution exhibits a stable storage property in a state where the alum exceeding the limit dissolution concentration in water is dissolved. The results of measuring the pH value of the alum aqueous solution stored in an atmosphere at 20 ° C. are shown in the following [Table 5], [Table 6] and [Table 7]. In Tables 1 to 7, KA indicates aluminum potassium sulfate (potash) and AA indicates aluminum ammonium sulfate (ammonium alum). Further, Urea indicates urea. In addition, the alum aqueous solution of [Table 7] is a sorbitol (Sorbito) as a low-temperature stabilizer.
An alum aqueous solution to which l) was added was used.

[Table 5]

[Table 6]

[Table 7]

As is clear from Tables 1 to 7, an alum aqueous solution in which alum and urea are dissolved in a predetermined amount of water is long in a state in which alum exceeding the limit dissolution concentration in water is dissolved. Exhibits storage stability over time. Therefore, such alum aqueous solution can be supplied as a raw material for various uses such as antiperspirants. The alum aqueous solution supplied as a raw material can be adjusted to a concentration suitable for the intended use by diluting it with water or the like, and the step of dissolving solid (powder) alum can be omitted. Here, when diluting the alum aqueous solution, a solvent other than water can be used. For example, an alum aqueous solution dissolves in ethanol, isopanol, and glycerin and propylene glycol as cosmetic raw materials to form a transparent solution. The alum solution dissolves in the dimethylsiloxane methylsiloxane copolymer used as the silicone for cosmetics, but becomes a slightly cloudy solution. However, this level of slight cloudiness is not a problematic level. The alum aqueous solution contains a urea component. Conventionally, urea has pharmacological actions such as moisturizing action and antibacterial action, and is used as a therapeutic agent for atopic skin eczema, keratosis, ichthyosis, etc. It is widely used in the medical field and has no effect on the human body.

Since the alum is dissolved in the alum aqueous solution described so far, it exerts a medicinal effect such as antiperspirant by being applied to the skin, but the medicinal effect has a short duration, and the medicinal effect lasts for a short time. An extension of time is required. The extension of the duration of such a medicinal effect is such that when an alum aqueous solution is applied, a film containing a urea adduct generated by the reaction between alum and urea is formed,
This is possible by dissolving a water-soluble polymer in an alum aqueous solution to make it viscous. As the water-soluble polymer, any polymer having compatibility with the alum aqueous solution may be used, but a polyhydric alcohol can be suitably used. Such polyhydric alcohols include polyvinyl alcohol,
Hydroxyethyl cellulose, hydroxypropyl cellulose and the like can be mentioned. The amount of the water-soluble polymer to be added is preferably 1 to 15% by weight based on the alum aqueous solution. 15% by weight of water-soluble polymer
When the value exceeds, it is difficult to dissolve the water-soluble polymer, and the solution obtained by dissolving the water-soluble polymer tends to have a high viscosity and its handling tends to be difficult. On the other hand, when the added amount of the water-soluble polymer is less than 0.1% by weight, the film formed after coating tends to be insufficient. Here, the polyvinyl alcohol used as the water-soluble polymer is C
It is known to form a complex with u, Al, Ti and the like to make them insoluble. However, even if polyvinyl alcohol is added to an alum aqueous solution in which alum as an aluminum compound is dissolved, a transparent viscous solution can be formed without insolubilization.

[0018] Such a viscous alum aqueous solution is
After heating and dissolving alum in a predetermined amount of water to form a heating solution, when a predetermined amount of urea is added and dissolved in the heating solution, the heating solution is immediately cooled to obtain an alum aqueous solution. Then, a predetermined amount of a water-soluble polymer such as polyvinyl alcohol is dissolved in this alum aqueous solution to obtain a viscous solution. Here, when adding the water-soluble polymer to the alum aqueous solution, a uniform viscous solution can be easily obtained by previously dissolving the water-soluble polymer in water or the like to form an aqueous solution. After immersing the slide glass in the obtained viscous alum aqueous solution, taking out and air-drying, a white film is formed on the slide glass. Observation of this white film with a microscope confirmed that crystals of the urea adduct were distributed on the film.
The amount of the alum dissolved in the viscous alum aqueous solution may be equal to or less than the limit dissolution concentration of the alum in the contained water, but the amount of the alum dissolved in the contained water exceeds the limit dissolved concentration of the alum, so that the viscous alum aqueous solution is applied. This is preferable because a sufficient amount of alum can be applied. When this viscous alum aqueous solution is applied to the skin, the water content of the alum aqueous solution applied at body temperature or the like evaporates, and a film containing a urea adduct formed by the reaction between alum and urea is formed. For this reason,
The urea adduct is not washed away by sweat or the like, can exist on the skin for a long time, and can maintain the medicinal effects such as antiperspirant. In addition, the above-mentioned solubilizing agent and / or
Alternatively, a low-temperature stabilizer may be added.

Since the alum aqueous solution described above is liquid, it is difficult to form it into a predetermined shape. In this respect, according to the substantially transparent gelled composition obtained by adding and dissolving a water-soluble polymer to an alum aqueous solution obtained by dissolving alum and urea in a predetermined amount of water, easily. It can be formed into a predetermined shape. As the water-soluble polymer, polyvinyl alcohol having a saponification degree of 97 mol% or more and an average polymerization degree of 1000 or more can be suitably used. Such a polyvinyl alcohol is, for example, a polyvinyl alcohol having a degree of saponification of less than 97 mol% and an average degree of polymerization of less than 1,000, hydroxyethyl cellulose-
, Hydroxypropyl cellulose and the like. The amount of such water-soluble polymer added is
The content is preferably 1 to 15% by weight based on the gelling composition. When the amount of the water-soluble polymer added is less than 1% by weight based on the gelled composition, the composition tends to be difficult to gel, while when it exceeds 15% by weight, the gelled composition contains The alum and urea contents tend to be too low. Such a gelled composition is first alum,
A clear alum aqueous solution in which urea and a water-soluble polymer are dissolved in a predetermined amount of water is obtained. Next, the alum aqueous solution can be obtained by freezing in a frozen atmosphere, followed by thawing and gelling. Here, it is preferable to previously dissolve the water-soluble polymer in water or the like to prepare an aqueous solution in order to obtain a transparent alum aqueous solution. In addition, the above-mentioned solubilizer and / or low-temperature stabilizer may be added to the gelled composition.

By the way, conventionally, urea gradually decomposes in an aqueous solution to generate carbon dioxide gas and ammonia. In this regard, the gelled composition according to the present invention is stably present as an urea adduct generated by the reaction between alum and urea. Therefore, the medicinal effects of alum and urea can be exhibited. In addition, the gelled composition has water incorporated into the polymer molecules in the gelled composition,
It does not dry easily and has moderate viscosity and fluidity,
It also has storage stability. For this reason, the gelled composition can be easily formed into a predetermined shape as compared with a case where a liquid alum aqueous solution is poured into a forming container and formed.

[0021]

The present invention will be described in more detail with reference to the following examples. Example 1 After adding 27 g of water to 60 g of alum and heating and dissolving, 63 g of urea was added and dissolved by stirring. After confirming that the urea was dissolved, water was added to the heated solution to adjust the weight to 150 g in order to immediately supply evaporated water and the like. When this water was added, the temperature of the heated solution dropped, but was further allowed to cool to room temperature. The resulting alum aqueous solution was a clear aqueous solution. This alum solution
It was stored for one month in a 20 ° C. incubator while checking for crystal precipitation every two days. No crystal precipitation was observed during storage, and the state of a clear aqueous solution was maintained. This alum aqueous solution had a specific gravity of 1.372 g / ml and a viscosity of 19 cps. In addition, p
H was 4.2.

Here, an alum aqueous solution was obtained in the same manner as described above except that 52.5 g of potassium alum, 15 g of water, and 82.5 g of urea were used. When this alum aqueous solution was allowed to stand under an atmosphere at room temperature for 2 days, colorless needle-like crystals were precipitated in the alum aqueous solution. The aluminum oxide concentration of the needle-like crystals was 2.04% (19.0% by weight in terms of potassium alum), and the converted value of urea determined from the quantitative value of nitrogen by the macro Kjeldahl method was 68.9% by weight. Was. For this reason, it is inferred that the needle-like crystals are urea adducts formed by the reaction between alum and urea.

Example 2 10 g of water was added to 75 g of ammonium alum and dissolved by heating, and 66 g of urea was added and dissolved by stirring.
After confirming that the urea has dissolved, immediately add water to the heated solution to adjust the weight to replenish the evaporated water and the like.
The weight was 50 g. When this water was added, the temperature of the heated solution dropped, but was further allowed to cool to room temperature. The resulting alum aqueous solution was a clear aqueous solution. The alum aqueous solution was stored in an incubator at 20 ° C. for one month while checking for crystal precipitation every two days. No crystal precipitation was observed during storage, and the state of a clear aqueous solution was maintained.
This alum aqueous solution had a specific gravity of 1.406 g / ml and a viscosity of 65 cps. The pH of the alum aqueous solution was 4.2.

Here, ammonium alum is used for 37.
5 g, 30 g of water and 82.5 g of urea,
An alum aqueous solution was obtained in the same manner as above. When this alum aqueous solution was allowed to stand for one day in a room temperature atmosphere, colorless needle-like crystals were precipitated in the alum aqueous solution. FIG. 2 shows a chart of X-ray diffraction of this needle-like crystal. Although the main peak of the chart shown in FIG. 2 substantially coincides with the peak of urea, the intensity of the main peak gradually decreases as the amount of alum added increases. Also, the peak intensity at 2θ = 35.4 ° gradually decreases as the amount of alum added increases. For this reason, it is inferred from X-ray diffraction that the acicular crystals are urea adducts formed by the reaction of alum and urea.

Example 3 An alum aqueous solution was obtained in the same procedure as in Example 1.
At this time, urea 30% by weight, potash alum 20-50
0.5% by weight of a water-soluble cellulose shown in the following [Table 8] was added to the aqueous solution of alum adjusted to% by weight and dissolved by heating. After cooling, each level of the alum aqueous solution obtained by removing the undissolved portion of the water-soluble cellulose was divided into three, and each was stored at room temperature for 12 months. The results of investigating the start of crystal precipitation in this alum aqueous solution are shown in [Table 8]. In Table 8, the description "not precipitated" indicates that no crystal was precipitated during storage.

[Table 8] As is clear from Table 8, at the level where water-soluble cellulose is added, the solubility limit at which alum can be dissolved can be increased as compared with the level where water-soluble cellulose is not added. it can.

Example 4 An alum aqueous solution was obtained in the same operation procedure as in Example 1.
At this time, 30 to 35% by weight of urea, 25% of alum
To an aqueous solution of alum adjusted to ~ 35% by weight, anhydrous sodium sulfate shown in the following [Table 9] was added in a molar amount 0.5 times the amount of potassium alum and dissolved by heating. Each level of the alum aqueous solution obtained by cooling was divided into three, and each was stored in a 5 ° C. incubator for one month. The results of investigating the start time of crystal precipitation in this alum aqueous solution are shown in [Table 9].
Shown in In Table 9, the description “not precipitated” indicates that no crystal was precipitated during storage.

[Table 9] As is clear from Table 9, the level at which anhydrous sodium sulfate was added can increase the solubilization limit concentration at which alum could be dissolved, as compared to the level at which anhydrous sodium sulfate was not added.

Example 5 An alum aqueous solution was obtained in the same manner as in Example 1. The composition of this alum aqueous solution is 40% by weight of urea, 20% by weight of alum, and 40% by weight of water. Sorbitol was added to the alum aqueous solution. The amount of sorbitol added is 4.8 to 23.0% by weight based on the alum aqueous solution containing sorbitol. The freezing point of each aqueous solution was measured, and the results are shown in [Table 10].

[Table 10] As is clear from Table 10, the level at which sorbitol was added shows that the freezing point is lower and the stability at low temperatures is higher than the level at which sorbitol is not added. I understand.

Example 6 An alum aqueous solution was obtained in the same manner as in Example 1. The composition of this alum aqueous solution is 10% by weight of urea, 10% by weight of alum, and 80% by weight of water. Xylitol was added to the alum aqueous solution. The amount of xylitol added is 4.8 to 23.0% by weight based on the xylitol-containing alum aqueous solution. The freezing point of each aqueous solution was measured, and the results are shown in [Table 11].

[Table 11] As is clear from Table 11, the level at which xylitol was added was lower than the level at which xylitol was not added, and the freezing point was lowered and the stability at low temperatures was increased.

Example 7 An alum aqueous solution was obtained in the same manner as in Example 1. The composition of this alum aqueous solution is 10% by weight of urea, 10% by weight of alum, and 80% by weight of water. One such aqueous solution of alum and commercially available polyvinyl alcohol (Kurarepovar 217, saponification degree: 88.0 ± 1.0 mol%)
A 0% by weight aqueous solution was mixed at a weight ratio of 1: 1 to obtain a transparent and viscous viscous alum aqueous solution. The cover glass was immersed in this viscous alum aqueous solution, and the cover glass taken out was air-dried, whereby a white film was formed on the slide glass. Observation of this white film with an optical microscope having a magnification of 400 times revealed that urea adduct crystals were densely distributed on the film. The size of this crystal was about 5 μm.

Example 8 An alum aqueous solution was obtained in the same manner as in Example 1. The composition of this alum aqueous solution is 10% by weight of urea, 10% by weight of alum, and 80% by weight of water. Such an alum aqueous solution and commercially available hydroxypropyl cellulose (100
The mixture was mixed with a 2% by weight aqueous solution (0 to 4000 cps) at a weight ratio of 1: 1 to obtain a transparent and viscous viscous alum aqueous solution. The cover glass was immersed in this viscous alum aqueous solution, and the cover glass taken out was air-dried, whereby a white film was formed on the slide glass. Observation of this white film with an optical microscope having a magnification of 400 times revealed that crystals of the urea adduct were distributed on the film.

Example 9 After an alum aqueous solution was obtained in the same manner as in Example 1, glycerin was added and melted. The composition of the glycerin-containing alum aqueous solution is 30.8% by weight of urea, 15.4% by weight of alum, 30.8% by weight of water, and 2% by weight of glycerin.
3% by weight. Further, a glycerin-containing alum aqueous solution and a commercially available polyvinyl alcohol (Kurarepovar 11)
A 10% by weight aqueous solution of 7) was mixed at a weight ratio of 1: 1 to obtain a transparent and viscous viscous alum aqueous solution. After cooling and freezing this viscous liquid in a -15 ° C freezer, it was transferred to an incubator at 30 ° C and thawed. As a result, a transparent gel was obtained. Spread a part of this gel on a slide glass,
Observation with an optical microscope having a magnification of 400 times confirmed that crystals of the urea adduct were distributed. Here, when the mixing ratio between the glycerin-containing alum aqueous solution and a commercially available 10% by weight aqueous solution of polyvinyl alcohol (Kurarepovar 117) was set to 19: 1 (weight ratio), the obtained viscous alum aqueous solution was obtained by After cooling in a freezer at 15 ° C. for 4 days, it remained a transparent and viscous viscous liquid without freezing.

Example 10 An alum aqueous solution was obtained in the same manner as in Example 9. The composition of the alum aqueous solution is 30.8% by weight of urea, 15.4% by weight of alum, 30.8% by weight of water, and 23% by weight of glycerin. The glycerin-containing alum aqueous solution and a commercially available polyvinyl alcohol (Kurarepovar 117, saponification degree: 98.5 ± 0.5 mol%)
A 0% by weight aqueous solution was mixed at a weight ratio of 4: 1 to obtain a transparent and viscous viscous alum aqueous solution. The cover glass was immersed in this viscous alum aqueous solution, and the cover glass taken out was air-dried, whereby a white film was formed on the slide glass. Observation of this white film with an optical microscope having a magnification of 400 times revealed that crystals of the urea adduct were distributed on the film.

Example 11 In Example 9, the composition of the glycerin-containing alum aqueous solution was 30.8% by weight of urea, potassium alum.
4% by weight, 30.8% by weight of water, 23% by weight of glycerin, and a commercially available polyvinyl alcohol (Kurarepobar 117) was replaced by a commercially available polyvinyl alcohol (Kurarepobar).
217), to obtain a viscous alum aqueous solution in the same manner as in Example 9. This viscous alum aqueous solution was cooled and frozen in a freezer at -15 ° C, then transferred to a 30 ° C incubator and thawed three times, but was not gelled but remained transparent and viscous. . However, when the cover glass was immersed in this viscous alum aqueous solution and the cover glass taken out was air-dried, a white film was formed on the slide glass. Observation of this white film with an optical microscope having a magnification of 400 times revealed that crystals of the urea adduct were distributed on the film.

Example 12 An alum aqueous solution was obtained in the same manner as in Example 1. The composition of this alum aqueous solution is 10% by weight of urea, 10% by weight of alum, and 80% by weight of water. 2 of such an alum aqueous solution and a commercially available polyvinyl alcohol (Kurarepovar 217, saponification degree: 88.0 ± 1.0 mol%)
A 0% by weight aqueous solution was mixed at a weight ratio of 1: 3 to obtain a transparent and viscous viscous alum aqueous solution. The obtained viscous alum aqueous solution is cooled and frozen in a freezer at -15 ° C, then transferred to an incubator at 30 ° C and thawed.
Repeated several times, the mixture did not gel and remained a viscous liquid which was transparent and viscous. However, when the cover glass was immersed in this viscous alum aqueous solution and the cover glass taken out was air-dried, a white film was formed on the slide glass. Observation of this white film with an optical microscope having a magnification of 400 times revealed that crystals of the urea adduct were distributed on the film.

[0035]

According to the present invention, it is possible to provide an alum aqueous solution in which an amount of alum having a good preservability and exceeding a limiting dissolution concentration in contained water is dissolved, and various uses such as an antiperspirant using the alum. Can be supplied as raw material.
As a result, steps such as dissolution of the solid raw material can be omitted in the manufacturing process for various uses. Since the urea component is stably present in such an alum aqueous solution, it is possible to provide cosmetics, bath agents, and the like having both the moisturizing action of urea and the astringent action of alum. In addition, when applied to the skin, a film containing alum and urea can be formed, so that the duration of the medicinal effect exerted by alum and urea can be extended as compared with the related art. Furthermore, since a gel containing alum and urea can be produced, the gel can be applied to various uses such as cosmetics and the like, which have the medicinal effects of alum and urea.

[Brief description of the drawings]

FIG. 1 is a diagram showing a state in which an alum aqueous solution obtained by changing the amounts of alum and urea added is stored in an atmosphere at 20 ° C. for one month.

FIG. 2 is an X-ray diffraction chart of a colorless needle-like crystal precipitated in an alum aqueous solution that has been left under an atmosphere at room temperature.

[Explanation of symbols]

1 A region where alum crystals precipitate during storage 2 A region where needle-like crystals composed of urea adducts precipitate during storage 3 A region where added urea is decomposed 4 A transparent alum aqueous solution composed of alum, urea and water Area that can be held stably for 1 month in an atmosphere of 20 ° C.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) A61K 7/50 A61K 7/50

Claims (26)

[Claims] 1. A substantially transparent alum aqueous solution obtained by dissolving alum and urea in a predetermined amount of water, wherein the alum aqueous solution has a concentration exceeding the limit solubility for the predetermined amount of water. An alum aqueous solution, wherein an amount of alum is dissolved. 2. The alum aqueous solution according to claim 1, wherein the alum aqueous solution contains a urea adduct formed by reacting alum with urea. 3. The alum aqueous solution according to claim 1, wherein the alum aqueous solution contains a solubilizing agent capable of increasing the amount of the alum dissolved above the solubilization limit concentration of the alum aqueous solution. 4. The alum aqueous solution according to claim 3, wherein the solubilizing agent is a water-soluble polymer or a sodium salt. 5. The alum aqueous solution according to claim 1, wherein the alum aqueous solution contains a low-temperature stabilizer that lowers the freezing point temperature or the crystallization start temperature of the alum aqueous solution. 6. The alum aqueous solution according to claim 5, wherein the low-temperature stabilizer is a sugar alcohol. 7. The aqueous solution of alum according to claim 1, wherein the amount of urea is 5 to 50% by weight based on the aqueous solution of alum. 8. A method for producing a substantially transparent aqueous solution of alum comprising alum and urea dissolved in a predetermined amount of water, comprising the steps of: A method for producing an alum aqueous solution, comprising: adding a predetermined amount of urea to the heating solution after heating and dissolving the heating solution into the heating solution; and immediately cooling the heating solution when the urea is dissolved in the heating solution. . 9. The method for producing an alum aqueous solution according to claim 8, wherein a solubilizing agent capable of increasing the amount of alum dissolved in the alum aqueous solution to a concentration exceeding the solubilization limit concentration is dissolved in the alum aqueous solution. 10. The method according to claim 9, wherein a water-soluble polymer or a sodium salt is used as the solubilizing agent. 11. The method for producing an alum aqueous solution according to claim 9 or 10, wherein a low-temperature stabilizer that lowers the freezing point temperature or the crystallization starting temperature of the alum aqueous solution is dissolved in the alum aqueous solution. 12. The method according to claim 11, wherein a sugar alcohol is used as the low-temperature stabilizer. 13. A substantially transparent viscous alum aqueous solution obtained by dissolving alum and urea in a predetermined amount of water, wherein the alum and urea react with each other when the alum aqueous solution is applied. A viscous alum aqueous solution, wherein a water-soluble polymer is dissolved in the alum aqueous solution so as to form a film containing the urea adduct. 14. The viscous alum aqueous solution according to claim 13, wherein the water-soluble polymer is a polyhydric alcohol. 15. The viscous alum aqueous solution according to claim 13 or claim 14, wherein the amount of the alum dissolved exceeds a limit solubility concentration in a predetermined amount of water to be dissolved. 16. When producing a substantially transparent viscous alum aqueous solution comprising alum and urea dissolved in a predetermined amount of water, the alum is heated and dissolved in the predetermined amount of water to form a heated solution. Thereafter, when a predetermined amount of urea was added to and dissolved in the heated solution, the heated solution was immediately cooled to obtain an alum aqueous solution, and then when the resulting alum aqueous solution was applied, the alum and urea reacted. A method for producing a viscous alum aqueous solution, comprising: dissolving a water-soluble polymer in the alum aqueous solution so as to form a film containing the urea adduct formed by the above method. 17. The method for producing a viscous alum aqueous solution according to claim 16, wherein a polyhydric alcohol is used as the water-soluble polymer. 18. The method for producing a viscous alum aqueous solution according to claim 16 or 17, wherein the amount of the alum to be dissolved exceeds a limit solubility concentration in a predetermined amount of water to be dissolved. 19. A substantially transparent gelling composition obtained by dissolving alum and urea in a predetermined amount of water, wherein the alum and urea are contained in the gelling composition. A gel composition comprising a soluble aqueous polymer added to an alum aqueous solution obtained by being dissolved in a fixed amount of water. 20. The gelled composition according to claim 19, wherein the amount of the alum dissolved exceeds a limit solubility concentration in a predetermined amount of water to be dissolved. 21. The gelled composition according to claim 19, wherein the water-soluble polymer is a polyhydric alcohol. 22. The gelling composition according to claim 19, wherein the water-soluble polymer is a polyvinyl alcohol having a degree of saponification of 97 mol% or more and an average degree of polymerization of 1000 or more. 23. When producing a substantially transparent gelled composition obtained by dissolving alum and urea in a predetermined amount of water, the alum, urea and water-soluble polymer are mixed in a predetermined amount of water. A method for producing a gelled composition, comprising: obtaining a transparent alum aqueous solution dissolved in water; then, freezing the alum aqueous solution in a freezing atmosphere and then thawing to gel. 24. The method according to claim 23, wherein a polyhydric alcohol is used as the water-soluble polymer. 25. A water-soluble polymer having a degree of saponification of 97.
The method for producing a gelled composition according to claim 23 or claim 24, wherein polyvinyl alcohol having a mol% or more and an average degree of polymerization of 1000 or more is used. 26. The method for producing a gelled composition according to any one of claims 23 to 25, wherein the dissolved amount of the alum is a dissolved amount exceeding a limit solubility concentration in a predetermined amount of water to be dissolved.