JP5462465B2 - Method for producing aqueous gel fragrance composition - Google Patents

Description

The present invention relates to a method for producing an aqueous gel fragrance composition .

  Aqueous gel compositions are used in various fields such as fragrances, deodorants, antibacterial agents, and foods. For example, a fragrance using an aqueous gel composition has the advantage that it is excellent in aroma transpiration and sustainability and is easy to handle.

  As a fragrance | flavor using the conventional aqueous gel composition, what used water as a solvent and used carrageenan etc. as a gelatinizer is known, for example (refer patent documents 1-4).

JP 56-57451 A Japanese Patent Laid-Open No. 10-226749 JP 2001-276203 A JP 2001-279119 A

  However, in Patent Document 1, a carrageenan is dispersed in water, heated to 70 ° C. and dissolved, and then a fragrance is added. In Patent Document 2, copper-type carrageenan is dispersed in water, heated to 80 ° C. to 90 ° C. and dissolved, and then cooled to about 60 ° C. before adding a fragrance. Furthermore, in Patent Documents 3 and 4, hydrophobically modified polyether urethane as a water separation inhibitor is dissolved in a moisturizer by heating at 70 ° C., and carrageenan as a gelling agent is dissolved at 70 ° C. in a solution cooled to room temperature. The fragrance | flavor etc. were added to this at 70 degreeC. That is, in any case, the fragrance was added at a temperature much higher than room temperature, and there was a problem that the fragrance was volatilized or thermally deteriorated during the production process of the aqueous gel fragrance.

  Moreover, when using a fragrance in which a plurality of fragrance components are prepared, only the low boiling point fragrance components are volatilized during the production of the aqueous gel fragrance, and the balance of the fragrance components is lost, making it difficult to obtain a desired fragrance. There was also a problem.

  Then, an object of this invention is to provide the method of manufacturing an aqueous gel-like composition, without exposing the fragrance | flavor etc. which are additives to an aqueous gel-like composition to high temperature.

In order to solve such a problem, the inventors of the present application conducted intensive research, and among the substances used as anti-wetting agents in Patent Documents 3 and 4, n = 1 to 10 represented by the following chemical formula 1 A mixture of the copolymer is used as a gelling agent, and water and a water-soluble alcohol (ethanol, n-propanol, isopropanol, and 3-methoxy-3-methyl-1-butanol are used as a solvent for dissolving the gelling agent. It has been found that by using together with a species or more) , a new property unprecedented is exhibited.
<Chemical formula 1>
_{CH 3 (CH 2) 9 CH} (C 12 H 25) CH 2 -O- (CH 2 CH 2 O) 20 -CONH- (CH 2) 6 -NHCO- [O- (CH 2 CH 2 O) 240 - CONH (CH ₂ ) ₆ NHCO] _n- (OCH ₂ CH ₂ ) ₂₀ -O-CH ₂ (C ₁₂ H ₂₅ ) CH (CH ₂ ) ₉ CH ₃

That is, the gelling agent of the mixture of n = 1 to 10 represented by Formula 1 is selected from water and water-soluble alcohols (ethanol, n-propanol, isopropanol, and 3-methoxy-3-methyl-1-butanol). Found that the fluidity of the solvent in which the gelling agent is dissolved (gelling agent solution) is maintained at room temperature. did. And it discovered that it can gelatinize by adding room temperature water to this gelatinizer solution, and mixing. Based on these findings, the inventors of the present application have made various further studies and completed the present invention.

The method for producing an aqueous gel-like fragrance composition of the present invention has the following chemical formula 1 as a gelling agent.
<Chemical formula 1>
_{CH 3 (CH 2) 9 CH} (C 12 H 25) CH 2 -O- (CH 2 CH 2 O) 20 -CONH- (CH 2) 6 -NHCO- [O- (CH 2 CH 2 O) 240 - CONH (CH ₂ ) ₆ NHCO] _n- (OCH ₂ CH ₂ ) ₂₀ -O-CH ₂ (C ₁₂ H ₂₅ ) CH (CH ₂ ) ₉ CH ₃
A mixture of copolymers represented by n = 1 to 10 and water and a water-soluble alcohol as a solvent for dissolving the gelling agent are mixed at room temperature, and the gelling agent is dissolved in the solvent to obtain a gelling agent solution. A gelling agent dissolving step to be obtained and a gelling step of adding water to the gelling agent solution at room temperature for gelation, and ethanol, n-propanol, isopropanol and 3-methoxy-3-methyl as water-soluble alcohols 1-butanol or one or more selected from butanol is used in the gelling agent dissolution step, between the gelling agent dissolution step and the gelation step, or in the gelation step, aqueous with respect to the gelling agent solution. Additives to the gel composition are added and mixed to uniformly disperse in the gelling agent solution, and at least a volatile substance is added as an additive, and at least a fragrance is added as a volatile substance. As described above , n = 1 or more selected from ethanol, n-propanol, isopropanol, and 3-methoxy-3-methyl-1-butanol is used as the water-soluble alcohol. The gelling agent of the mixture of 1 to 10 copolymers can be dissolved in a solvent mixed with water and a water-soluble alcohol at room temperature, and the flow of the solvent (gelling agent solution) in which this gelling agent is dissolved Sex is maintained at room temperature. Moreover, in the gelling step from the gelling agent dissolving step, the gelling agent solution can always be maintained at room temperature to ensure fluidity. Therefore, in this case, the addition of the additive to the aqueous gel composition may be performed not only between the gelling agent dissolving step and the gelling step or in the gelling agent dissolving step. it can.

Here, in this invention, it is preferable that a gelatinizer contains at least 1.5 mass% with respect to the whole composition.

Further, in the present invention, a water and a water-soluble alcohol as the solvent for dissolving the gelling agent is from 1: 100 to 4: is preferably contained at a mass ratio.

In the present invention, it is particularly preferable to use ethanol as the water-soluble alcohol . And in this invention, when using ethanol, it is preferable to contain 3-10 mass parts of ethanol with respect to 1 mass part of gelatinizers.

In addition, the aqueous gel fragrance composition produced by the production method of the present invention is characterized in that it becomes cloudy when water or water and water-soluble alcohol evaporate and the dissolved state of the gelling agent cannot be maintained. It is what you have.

  In the method for producing an aqueous gel composition according to claim 17, at least a transpiration substance is added as an additive. Furthermore, in the method for producing an aqueous gel composition according to claim 18, at least a fragrance is added as a transpiration substance.

As described above, according to the present invention, the flavoring is the addition of the aqueous gel-like fragrance composition, etc., uniformly dispersed at room temperature in the manufacturing process of the aqueous gel-like fragrance composition, then the additives to high temperature An aqueous gel fragrance composition can be obtained at room temperature without exposure. Therefore, since the additive does not volatilize or deteriorate due to heat, the additive can be dispersed in the aqueous gel composition without impairing the function of the additive.

Moreover, according to the present invention, water or water and water-soluble alcohol evaporate and have an excellent feature that it becomes clouded when the dissolved state of the gelling agent cannot be maintained. Therefore, by adding the transpirable substance as an additive in accordance with the time until the water to be transpirated or all of the water and water-soluble alcohol is evaporated, the composition of the transpirationable substance as an additive is almost completely evaporated. It has the advantage that the object can be clouded and the replacement time can be easily determined visually.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  The aqueous gel composition of the present invention uses a mixture of copolymers of n = 1 to 10 represented by the following chemical formula 1 as a gelling agent, and includes at least the gelling agent, water, and water-soluble alcohols. Yes.

<Chemical formula 1>
_{CH 3 (CH 2) 9 CH} (C 12 H 25) CH 2 -O- (CH 2 CH 2 O) 20 -CONH- (CH 2) 6 -NHCO- [O- (CH 2 CH 2 O) 240 - CONH (CH ₂ ) ₆ NHCO] _n- (OCH ₂ CH ₂ ) ₂₀ -O-CH ₂ (C ₁₂ H ₂₅ ) CH (CH ₂ ) ₉ CH ₃

  The method for producing an aqueous gel composition of the present invention comprises a mixture of n = 1 to 10 copolymers represented by Chemical Formula 1 as a gelling agent and water and water-soluble alcohols as a solvent for dissolving the gelling agent. And a gelling agent dissolving step in which the gelling agent is dissolved in a solvent to obtain a gelling agent solution, and a gelling step in which water is added to the gelling agent solution to gelate, Addition of additives to the aqueous gel-like composition to the gelling agent solution at room temperature between the agent dissolving step and the gelling step, or mixing, and uniformly dispersing in the gelling agent solution I try to let them.

  In the present specification, room temperature refers to a temperature range in which additives to the aqueous gel composition, such as fragrances, are not thermally deteriorated, for example, 5 ° C. to 35 ° C., preferably 20 ° C. to Refers to 35 ° C.

  The copolymer of n = 1 to 10 represented by the chemical formula 1 is a copolymer having a cosmetic ingredient display name (PEG-240 / decyltetradeceth-20 / HDI). The INCI name is PEG-240 / HDI COPOLYMER BIS-DECYLTETRADECET-20-20 ETHER. In the present invention, a mixture of copolymers of n = 1 to 10 represented by Formula 1 is used as a gelling agent. In the following description, this mixture of copolymers will be referred to as PDH copolymer.

  The PDH copolymer can be obtained, for example, as follows. That is, in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer, 131 parts by mass of polyethylene glycol 11000 (PEG, molecular weight of about 11000) and 20 mol of ethylene oxide (EO) of 2-dodecyl-dodecyl alcohol The adduct is charged in 552 parts by mass and dehydrated under reduced pressure (10 mmHg or less) at 90 to 110 ° C. for 3 hours to make the water content of the system 0.03% or less. Next, the mixture was cooled to 80 ° C., 17.9 parts by mass of hexamethylene diisocyanate (HMDI) was added, the mixture was reacted at 80 to 90 ° C. for 2 hours under a nitrogen stream, and it was confirmed that the isocyanate was 0%. A solid to waxy solid reaction product. However, the method for producing the PDH copolymer is merely an example, and is not limited thereto, and other known methods or new methods can be appropriately employed.

  Here, the content of the PDH copolymer is preferably at least 1.5% by mass or more, more preferably 2.0% by mass or more based on the entire aqueous gel composition. When the content of the PDH copolymer is less than 1.5% by mass, the aqueous gel composition may have fluidity. The upper limit of the content of the PDH copolymer is not particularly limited as long as it can be dissolved in a solvent, but not only the cost of the entire aqueous gel composition is improved, but also an aqueous gel fragrance. In some cases, the residue is increased and the appearance is also deteriorated. Therefore, it is sufficient to set the content to 5.0% by mass at the maximum.

  The PDH copolymer can be dissolved using water and water-soluble alcohols as a solvent.

  Here, the mixing ratio of water as a solvent and water-soluble alcohols is preferably 1: 200 to 4: 1 and more preferably 1: 100 to 1: 1 in terms of mass. If the amount of water is less than this range, the PDH copolymer may not be dissolved. If the amount of water exceeds this range, the entire system easily gels when the PDH copolymer is dissolved, loses fluidity, and causes the additive to the aqueous gel composition to be added to the aqueous gel composition. It becomes difficult to disperse uniformly. That is, by setting the mixing ratio of water as a solvent and water-soluble alcohols within the above range, the PDH copolymer is completely dissolved, and the fluidity of the entire system is maintained at room temperature to obtain an aqueous gel composition. It is possible to uniformly disperse the additive in the aqueous gel composition.

  Examples of water-soluble alcohols include water-soluble alcohols and water-soluble diols (water-soluble glycols). Of these, ethanol, n-propanol, isopropanol, 3-methoxy-3-methyl-1-butanol, hexylene glycol, dipropylene glycol, propylene glycol and 2- (2-ethoxyethoxy) ethanol are preferably used. N-propanol, isopropanol, 3-methoxy-3-methyl-1-butanol is more preferable, and ethanol is particularly preferable.

  Ethanol, n-propanol, isopropanol, 3-methoxy-3-methyl-1-butanol, hexylene glycol, dipropylene glycol, propylene glycol and 2- (2-ethoxyethoxy) ethanol are used in combination with water as water-soluble alcohols. Thus, the effect of completely dissolving the PDH copolymer and maintaining the fluidity of the entire system at room temperature can be reliably obtained. Moreover, by using ethanol, n-propanol, isopropanol, 3-methoxy-3-methyl-1-butanol as water-soluble alcohols together with water, the PDH copolymer is completely dissolved at room temperature, and the fluidity of the whole system Can be reliably obtained at room temperature.

  That is, when using ethanol, n-propanol, isopropanol, and 3-methoxy-3-methyl-1-butanol as water-soluble alcohols together with water, the PDH copolymer can be completely dissolved even at room temperature. Even if the additive to the aqueous gel composition is mixed in the stage of dissolving the copolymer, the additive is not exposed to a high temperature in the subsequent steps, and thermal deterioration does not occur. On the other hand, when hexylene glycol, dipropylene glycol, propylene glycol, 2- (2-ethoxyethoxy) ethanol is used in combination with water as a water-soluble alcohol, the PDH copolymer cannot be completely dissolved at room temperature. It is necessary to slightly heat (40 ° C. to 65 ° C.). In this case, when the additive to the aqueous gel composition is mixed at the stage of dissolving the PDH copolymer, the additive may be thermally deteriorated or volatilized. However, the PDH copolymer once dissolved does not precipitate even when cooled to room temperature. Further, the fluidity of the entire system is not lost even when cooled to room temperature. Therefore, after the PDH copolymer is dissolved, the additive is added to the aqueous gel composition after cooling to room temperature, so that the additive does not volatilize or thermally deteriorate.

  In addition to the above effects, ethanol is particularly preferable as a water-soluble alcohol because it is inexpensive, easily available, and very compatible with water.

  In addition, water-soluble alcohols may be contained in additives to the aqueous gel composition, such as fragrances and surfactants. Therefore, it is possible to dissolve the PDH copolymer using water-soluble alcohols contained in the additive.

  Here, when using ethanol as water-soluble alcohols, it is preferable to make ethanol into 3-10 mass parts with respect to 1 mass part of PDH copolymers, and it is more preferable to set it as 4-9 mass parts. More preferably, the content is ˜8 parts by mass. If the amount of ethanol is less than this range, the PDH copolymer may not dissolve. On the other hand, if the amount of ethanol is larger than this range, the aqueous gel-like composition becomes soft, and there is a possibility that a problem may occur in shape retention.

  The solvent in which the PDH copolymer is dissolved (gelator solution) can be gelled by adding water and mixing. The amount of water added when gelling is defined by the amount of water-soluble alcohol used. That is, since the gelation is caused by mixing four times as much water with respect to the mass of the water-soluble alcohols, the mass obtained by subtracting the mass of water used as a solvent from the mass of this water. It can be made to gelatinize by mixing the above water. The water temperature may be room temperature, but gelation is possible even if the temperature is lower than room temperature. As described above, the aqueous gel composition of the present invention contains water having a mass exceeding 4 times the mass of the water-soluble alcohol, but if the amount of water is excessively increased, There is a risk that handling during production may be deteriorated. Therefore, the upper limit value of the amount of water is preferably set to 100 times the amount that does not reduce the handleability during production, for example, 1000 times the maximum of the mass of the water-soluble alcohol. It is more preferable, and it is more preferable to make it 25 times.

  The additive to the aqueous gel composition is a step after cooling the solvent (gelling agent solution) in which the PDH copolymer is dissolved to room temperature when heating is required when dissolving the PDH copolymer, That is, it is added between the gelling agent dissolving step and the gelling step. Or it is also possible to disperse | distribute an additive uniformly by adding an additive with water in a gelatinization process. When the PDH copolymer can be dissolved at room temperature, an additive can be further added in the gelling agent dissolving step. In addition, when adding several additives, you may add all simultaneously in these processes, and may add separately. In addition, when an additive is added, it may be added independently, but once dissolved or dispersed in a solvent or water, the additive is dispersed in a solvent (gelator solution) in which the PDH copolymer is dissolved. You may make it add, after improving property.

  In addition, as an additive to the water-based gel-like composition in the present invention, for example, a fragrance that is a transpiration substance is cited. Moreover, when it is difficult to disperse | distribute a fragrance | flavor alone to an aqueous gel-like composition, it is also possible to use surfactant further as an additive. According to the present invention, since the additive to the aqueous gel-like composition can be produced without being exposed to a high temperature, it is possible to produce an aqueous gel-like fragrance using as an additive a fragrance that easily causes volatilization or thermal degradation. Very suitable. Further, the surfactant added together with the fragrance in order to uniformly disperse the fragrance in the aqueous gel-like composition can exert its function to the maximum without causing thermal deterioration. Furthermore, solubilizing agents and fragrance transpiration control agents that make it easier to dissolve oily components can be used together as additives, maximizing their functions without causing thermal degradation. Can be made.

  In addition, polymers other than PDH copolymers, gelling agents, thickeners, deodorants, pigments, solvents, antioxidants, UV absorbers, preservatives, antibacterial agents, lame and other decorative items, etc. It can be used in combination as an additive as long as the function of the product is not lowered. And since these are not exposed to high temperature in the manufacturing process of an aqueous gel-like composition, thermal deterioration can be prevented and the function can be exhibited to the maximum.

  Furthermore, according to the aqueous gel composition of the present invention, water or water and water-soluble alcohols evaporate and have the property of becoming cloudy when the dissolved state of the gelling agent cannot be maintained. More specifically, when water or water and water-soluble alcohols evaporate and the gelling agent cannot be maintained in a dissolved state, the composition starts to become cloudy. When all is transpired, the entire composition becomes completely cloudy. Therefore, by adding the transpirable substance as an additive in accordance with the time until the water to be transpirated or all the water and water-soluble alcohols are transcribed, the transpirationable substance as an additive is almost completely evaporated. The composition becomes cloudy and the replacement time can be easily confirmed visually. For example, when a fragrance is used as an evaporating substance as an additive to form an aqueous gel fragrance, the fragrance has a function that allows the replacement time to be easily confirmed visually by the cloudiness of the composition. It becomes possible.

  The above-described embodiment is an example of a preferred embodiment of the present invention, but is not limited thereto, and various modifications can be made without departing from the gist of the present invention. For example, in the above-described embodiment, a fragrance is given as an example of an additive for an aqueous gel composition, and the fragrance is used as an fragrance. However, the aqueous gel composition of the present invention is used as an fragrance. It is not limited. That is, the aqueous gel-like composition of the present invention is a deodorant, disinfectant, insect repellent, repellent, attractant, insecticide by appropriately changing the additive to a transpiration substance other than a fragrance. It can also be used as a bactericide, fumigant, acaricide, patch, external preparation and the like. That is, according to the present invention, an aqueous gel-like composition can be produced without the additive being exposed to a high temperature. Therefore, the present invention is not limited to the use of a fragrance as an additive, but is added to the aqueous gel-like composition. Thus, volatilization and thermal deterioration of various known or novel additives used can be prevented, and their functions can be maximized.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, all the compounding quantities of the materials in Tables 1-4 shown below mean the mass%.

Example 1
The concentration of PDH copolymer required for gelation was examined.

  Water heated to 80 ° C. and PDH copolymer were added at a ratio shown in Table 1 and stirred. After confirming uniform cloudiness, the mixture was gradually cooled with stirring. Table 1 shows the state of solidification at each concentration of PDH copolymer.

  From the results shown in Table 1, it was revealed that, as an aqueous gel composition, the PDH copolymer needs to be at least 1.5% by mass based on the total composition.

(Example 2)
A method for producing an aqueous gel composition at room temperature using a PDH copolymer as a gelling agent was studied.

  In this example, the following five production methods (production methods A to E) were examined. The blending ratio is shown in Table 2.

(1) Manufacturing method A
The case where ethanol was used as a water-soluble solvent was examined. Ethanol used in the experiment is a 95 v / v% product purchased from Nippon Alcohol Sales Co., Ltd. (95 v / v% ethanol used in the subsequent experiments is the same product). That is, a small amount of water (4.5 to 4.7 v / v%) and ethanol (95 v / v%) are contained.
First, when PDH copolymer was added to this 95 v / v% ethanol at room temperature and stirred, it was confirmed that it was sufficiently dissolved even at room temperature. On the other hand, when a 99.5 v / v% ethanol product containing almost no water was used, the PDH copolymer could not be completely dissolved. Therefore, it was revealed that the PDH copolymer can be dissolved at room temperature by using a mixture of ethanol and a small amount of water.
Then, it was clarified that gelation is possible by adding PDH copolymer to 95 v / v% ethanol at room temperature, stirring, and adding water thereto at room temperature.
From this result, by using a mixture of ethanol and water, PDH copolymer can be added and dissolved at room temperature, and then water can be added to gel at room temperature. As a result, it was revealed that an aqueous gel composition can be produced.

(2) Manufacturing method B
As a water-soluble solvent, n-propanol (Daicel Chemical Industries, Ltd., purity 99% or more, moisture 0.2 mass% or less), isopropanol (Mitsubishi Corporation Chemical Co., Ltd., purity 99.9% or more, moisture 0.1 mass%) In the following, the case of using 3-methoxy-3-methyl-1-butanol (Kuraray Co., Ltd., purity 99% or more, moisture 0.2% by mass or less) was examined. These contained almost no water, and as such, the PDH copolymer could not be dissolved at room temperature. Therefore, when the same amount of water as the PDH copolymer to be blended was mixed with each of these water-soluble solvents, it was confirmed that the PDH copolymer could be completely dissolved at room temperature.
Gelation is possible by adding the PDH copolymer to a mixture of the same amount of water and the PDH copolymer blended with the water-soluble solvent at room temperature, stirring, and then adding the remaining water to the mixture at room temperature. It became clear that.
From this result, by using n-propanol, isopropanol or 3-methoxy-3-methyl-1-butanol mixed with water, PDH copolymer was added and dissolved at room temperature. Thus, it was revealed that the gelation can be performed by adding water, and the aqueous gel composition can be produced by setting all steps to room temperature.

(3) Manufacturing method C
As a water-soluble solvent, hexylene glycol (Shell Chemicals Japan Co., Ltd., purity 99% or more, moisture 0.2% by mass or less), dipropylene glycol (Shell Eastern Petroleum, purity 99.5% or more, moisture 0.2) Mass% or less), propylene glycol (Dow Chemical Co., Ltd., purity 99% or more, moisture 0.2 mass% or less), 2- (2-ethoxyethoxy) ethanol (Daicel Chemical Industries, Ltd., purity 99% or more, moisture 0 .1 mass% or less) was used. These contained almost no water, and as such, the PDH copolymer could not be dissolved at room temperature. Therefore, although the same amount of water as the PDH copolymer to be blended was mixed with each of these water-soluble solvents, the PDH copolymer could not be completely dissolved at room temperature. Then, when it heated at 40-65 degreeC, it has confirmed that PDH copolymer was completely meltable. After heating and dissolving, the mixture was allowed to cool to room temperature, and it was confirmed that no precipitation of PDH copolymer occurred. And it became clear that gelatinization was possible by adding the remaining water to this at room temperature.
From this result, after using hexylene glycol, dipropylene glycol, propylene glycol, 2- (2-ethoxyethoxy) ethanol mixed with water, after heating it to 40-65 ° C. and dissolving it It was revealed that the solution can be gelated by adding water at room temperature after cooling to room temperature. That is, it was found that if a fragrance or the like was added together with water during gelation, the fragrance or the like could be uniformly dispersed in the aqueous gel composition without being exposed to heat.

(4) Manufacturing method D
About the manufacturing method A examined above, it investigated about actually manufacturing an aqueous | water-based gel-like fragrance | flavor at room temperature. A 95% v / v ethanol product, a fragrance, and a surfactant were mixed in advance, and the PDH copolymer was added thereto at room temperature, followed by stirring and mixing until completely dissolved. Subsequently, propylene glycol and water were sequentially added at room temperature, and mixed with a stirrer at room temperature until uniform. As a result, it was confirmed that the aqueous gel-like fragrance could be produced without degrading the fragrance or the like thermally at all steps at room temperature.

(5) Manufacturing method E
When PDH copolymer was dissolved only with water, addition of a fragrance or the like at room temperature was studied.
First, when PDH copolymer was added to water heated to 80 ° C. and stirred, a uniform cloudy state was obtained. Therefore, it was considered that, similarly to the production method C, if this was allowed to cool to room temperature and then a fragrance or the like was added, it could be uniformly dispersed in the aqueous gel composition without exposing the fragrance or the like to heat. However, when the temperature is lower than the cloud point of 60 to 75 ° C., the viscosity rapidly increases and gelation occurs, and the perfume and the like cannot be uniformly dispersed.
That is, when the PDH copolymer is heated and dissolved only with water, it is necessary to add a fragrance or the like while maintaining the temperature above the cloud point (60 to 75 ° C.), and the fragrance or the like cannot be added at room temperature. It became clear.
In addition, the aqueous gel-like fragrance E obtained in Table 2 was added with PDH copolymer in water heated to 80 ° C., stirred, and after confirming that it became uniform cloudy, the cloud point (60 The temperature is maintained at a temperature of ˜75 ° C. or higher, and a fragrance, a surfactant, ethanol, or propylene glycol is added.

(6) Examination of blending ratio of PDH copolymer and ethanol Next, based on the production method A, the blending ratio of the PDH copolymer and ethanol was examined. Table 2 shows the results.

  From the results shown in Table 2, it was revealed that it is preferable to dissolve 1 part by mass of the PDH copolymer with respect to 3 to 10 parts by mass of ethanol. When the amount of ethanol was less than 3 parts by mass, an amount of PDH copolymer required as a gelling agent could not be dissolved. Moreover, when the quantity of ethanol exceeded 10 mass parts, it turned out that a water-based gel-like composition becomes soft and a problem arises in the point of shape retention property.

(Example 3)
It was investigated whether an aqueous gel composition could be produced at room temperature using a gelling agent other than the PDH copolymer.

  Gelatin gum (manufactured by Dainippon Sumitomo Pharma Co., Ltd.), carrageenan (manufactured by Nitta Gelatin Co., Ltd.), gelatin (manufactured by Nitta Gelatin Co., Ltd.), agar (manufactured by Ina Food Industry Co., Ltd.) as gelling agents other than PDH copolymers Using. According to Table 3, 95 v / v% ethanol was added to the gelling agent and mixed by stirring, and then water was added and mixed until uniform.

  From the results shown in Table 3, it was revealed that it was difficult to produce an aqueous gel composition at room temperature when the gelling agent was other than the PDH copolymer.

Example 4
Various evaluations were performed on an aqueous gel fragrance produced using a gelling agent as a PDH copolymer at room temperature and an aqueous gel fragrance produced using a conventional gelling agent. The results are shown in Table 4.

(1) Manufacture of aqueous gel-like fragrance using PDH copolymer A fragrance and a surfactant are premixed in 95 v / v% ethanol, and the PDH copolymer is added thereto at room temperature until completely dissolved. Stir and mix. Thereafter, propylene glycol and water were sequentially added, mixed at room temperature until uniform with a stirrer, and filled into a predetermined volume of colorless transparent glass.

(2) Production of aqueous gel fragrance using conventional gelling agent Gellan gum, carrageenan, gelatin, and agar were used as conventional gelling agents. First, the gelling agent was dispersed in propylene glycol, water was added and stirred and mixed, the temperature was raised to 90 ° C. or higher, and the mixture was stirred and dissolved for about 2 hours or more to obtain an aqueous gelling agent solution. Moreover, the fragrance | flavor and surfactant were mixed in 95v / v% ethanol, and it heated at 70 degreeC. This was added to an aqueous gelling agent solution, stirred and mixed under heating (60 ° C.), and then filled into a colorless transparent glass container having a predetermined capacity. When gellan gum, carrageenan, gelatin and agar were used, it was impossible to produce an aqueous gel fragrance at room temperature.

  Hereinafter, the aqueous gel fragrance produced as described above was evaluated.

(A) State immediately after production The state immediately after production of the aqueous gel-like fragrance produced above was visually evaluated. In Table 4, ◯ indicates that it was gel-like immediately after production, and x indicates that it was liquid immediately after production. When PDH copolymer, gellan gum and carrageenan were used as gelling agents, they were in a gel state immediately after production, but agar and gelatin were liquid immediately after production and did not gel.

(B) Appearance (transparency)
The appearance (transparency) of the produced aqueous gel fragrance was evaluated. Evaluation evaluated the transparency when putting black paper behind each composition and comparing with the water with which the container was filled. As a result, when the gelling agent was PDH copolymer and carrageenan, it was confirmed that the gelling agent was as colorless and transparent as water. On the other hand, when gellan gum was used as the gelling agent, the transparency was slightly inferior to water and the color was slightly yellowed.

(C) Heat resistance (50 ° C)
Each of the produced fragrances was left to stand in a 50 ° C. constant temperature bath (yamato Incubator 400) for one week, and the state was visually confirmed. As a result, it was confirmed that when the gelling agent was gellan gum or carrageenan, the shape was maintained even when tilted immediately after removal. On the other hand, when the gelling agent was a PDH copolymer, although it had a slight fluidity when tilted immediately after removal, it was at a level that does not cause any particular problems in use.

(D) Restorability (from 70 ° C to room temperature)
Each manufactured fragrance was left in a 70 ° C. constant temperature bath (yamato Incubator 400) for one week, taken out, allowed to cool at room temperature for a day, and confirmed that the fragrance was at room temperature. The state of the fragrance was visually evaluated. As a result, when the gelling agent was PDH copolymer and gellan gum, it was confirmed that the gelling agent was restored to room temperature when returned to room temperature. On the other hand, when carrageenan was used as the gelling agent, it was not completely restored even when it was returned to room temperature.

(E) Water separation evaluation During the heat resistance test in (C), it was visually evaluated whether or not there was a seepage (water separation) of the liquid contained in each fragrance. As a result, when the gelling agent was PDH copolymer, no water separation was observed. On the other hand, when the gelling agent was gellan gum, there was some water separation. In addition, when carrageenan was used as the gelling agent, significant water separation occurred.

(F) Residue evaluation Each fragrance was allowed to stand and evaporate until there was no change in mass, and then the state of the residue was visually evaluated. As a result, when the gelling agent was PDH copolymer, it was confirmed that the residue was white and turbid. On the other hand, when the gelling agent was gellan gum or carrageenan, it was confirmed that the residue was transparent. From this, when PDH copolymer was used as the gelling agent, it was clarified that it also functions as an indicator, assuming that it is time to replace the gel when it becomes cloudy.

From the above results, it was found that by using a PDH copolymer as the gelling agent, it can be produced at room temperature, and the perfume and the like can be uniformly dispersed without being thermally deteriorated. Moreover, by using PDH copolymer as the gelling agent, it is clear that the replacement time is easy to understand due to white turbidity at the end of use, and it is clear that it can produce an aqueous gel-like fragrance far superior to conventional products. It became.

Claims (7)

A method for producing an aqueous gel fragrance composition, wherein a gelling agent is represented by the following chemical formula 1
<Chemical formula 1>
_{CH 3 (CH 2) 9 CH} (C 12 H 25) CH 2 -O- (CH 2 CH 2 O) 20 -CONH- (CH 2) 6 -NHCO- [O- (CH 2 CH 2 O) 240 - CONH (CH ₂ ) ₆ NHCO] _n- (OCH ₂ CH ₂ ) ₂₀ -O-CH ₂ (C ₁₂ H ₂₅ ) CH (CH ₂ ) ₉ CH ₃
A mixture of copolymers represented by n = 1 to 10 and water and a water-soluble alcohol as a solvent for dissolving the gelling agent are mixed at room temperature, and the gelling agent is dissolved in the solvent to form a gelling agent. A gelling agent dissolving step for obtaining a dissolving solution, and a gelling step of adding water to the gelling agent dissolving solution at room temperature for gelation, and the water- soluble alcohol includes ethanol, n-propanol, isopropanol, and 3- Using one or more selected from methoxy-3-methyl-1-butanol, the gelling agent dissolution step, between the gelling agent dissolution step and the gelation step or in the gelation step, An additive to the aqueous gel composition is added to and mixed with the gelling agent solution to uniformly disperse the gelling agent solution, and at least a transpiration substance is added as the additive, Transpiration Method for producing aqueous gel-like fragrance composition characterized by adding at least fragrance as the substance. The method for producing an aqueous gel-like fragrance composition according to claim 1 , wherein at least 1.5% by mass of the gelling agent is used with respect to the entire composition. The method for producing an aqueous gel fragrance composition according to claim 1 or 2 , wherein a mass ratio between the water as the solvent and the water- soluble alcohol is 1: 100 to 4: 1. The method for producing an aqueous gel fragrance composition according to any one of claims 1 to 3 , wherein ethanol is used as the water-soluble alcohol . The manufacturing method of the aqueous | water-based gel-like fragrance | flavor composition as described in any one of Claims 1-4 which uses 3-10 mass parts of said ethanol with respect to 1 mass part of said gelling agents. By the manufacturing method as described in any one of Claims 1-5, when the said water or the said water and the said water-soluble alcohol evaporate, when it becomes impossible to maintain the dissolved state of the said gelatinizer, the aqueous gel form which becomes cloudy A method for producing a fragrance composition. It manufactures with the manufacturing method of the aqueous | water-based gel-like fragrance | flavor composition as described in any one of Claims 1-6, The said water or the said water and the said water-soluble alcohol evaporate, and the dissolved state of the said gelatinizer is maintained. An aqueous gel-like fragrance composition characterized by becoming cloudy when it can no longer be produced.