JP2016183313A - Alcoholic gel composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for obtaining a gel with high practical utility without requiring means such as heating, while using alcohol as material for gelation.SOLUTION: An alcoholic gel composition comprises hydroxypropylated guar gum, a water-soluble cellulose compound, alcohol and water.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to an alcohol-based gel composition, and more particularly, an alcohol-based gel composition that forms a stable gel and does not have a special odor or the like while using alcohol as a main solvent, and its production Regarding the law.

  Conventionally, aqueous gel compositions obtained by gelling aqueous solutions with gelling agents have been widely used in various fields. For example, forms such as fragrances, deodorants and insecticides that gradually release active ingredients. A formulation is provided.

  A gel containing alcohol as a main solvent is also known. This gel has a lower freezing point than a gel containing water as a main solvent, and can obtain an antifreeze effect in a low temperature environment. However, there are few reports of practical techniques for gelling this. For example, in order to increase the viscosity of a lower alcohol, a method of increasing the viscosity by adding an alkali to a lower alcohol in which a carboxyvinyl polymer is dissolved, or an absorption A method of increasing the viscosity using an alcoholic polymer was known.

  However, it is difficult to control the appearance of gels obtained by these conventional thickening methods, and even when gel-like ones are obtained, it is necessary to prepare gels with abundant elasticity. There was a problem that was difficult.

  Further, in the former thickening method in which alkali is added, ammonia is usually used as an alkali, and there is a problem that odor is generated when the amount of alkali used is increased.

  In recent years, as a method for obtaining a lower alcohol gel while eliminating the above disadvantages, a modified guar gum obtained by chemically modifying a guar gum, which is a polysaccharide, is used, and a gel that is easily elastic even at room temperature without heating. The technique to obtain is reported (patent document 1).

  The technology of this Patent Document 1 is to thicken the modified guagum by adding an acid to the modified guagum. However, the active ingredient in the lower alcohol solution is decomposed by the acid or forms a salt and volatilizes. If it disappears, it cannot be used, and further technological development is required.

JP 2002-212298 A

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a technique for obtaining a highly practical gel without using a means such as heating while using alcohol as a substance for gelation. To do.

  The inventors of the present invention have been researching about the technology for gelling alcohol, and using a combination of hydroxypropylated guar gum and a water-soluble cellulose compound as a polymer component for gelation, The inventors have found that by adding an appropriate amount of water, a stable and practical alcohol-based gel can be obtained without using an alkali or acid, and the present invention has been completed.

  That is, the present invention is an alcohol gel composition containing hydroxypropylated guar gum, a water-soluble cellulose compound, alcohol and water.

  The present invention also provides a method for producing an alcohol-based gel composition characterized by adding water to a mixture of hydroxypropylated guar gum, a water-soluble cellulose compound and an alcohol.

  According to the present invention, a practical and practical alcohol-based gel composition can be obtained even at room temperature. And since this gel composition shrink | contracts by volatilization of alcohol or a water | moisture content, when it is set as the composition of the type which volatilizes a component, the end point is clear.

The figure which showed the gel formation test typically. In the figure, a is the position of the upper end of the prepared gel, and b is the position of the front end of the gel after 5 minutes have passed since the gel was laid down side by side.

  In the present specification, the alcohol-based gel composition means a gel-like composition using a solvent in which a part of the solvent, for example, 0.1 to 50% is water and the other part is alcohol. To do. In addition, “gel” means a state in which fluidity is lost due to high viscosity and the appearance is generally called gel. For example, a gel with a total amount of 50 g is prepared in a 100 ml beaker, and the gel after preparation in the beaker is prepared. It means that the distance from the position of the top end of the gel surface after 5 minutes have passed since the gel was laid down side by side with the beaker from 0 mm to 45 mm.

  The alcohol-based gel composition of the present invention is composed of hydroxypropylated guar gum and a water-soluble cellulose compound, alcohol and water as a solvent, and if necessary, an aroma component, a deodorizing component, an insecticidal / bactericidal component It contains active ingredients such as.

  Hydroxypropylated guar gum (hereinafter referred to as “HP guar gum”) used in the present invention is a reaction of propylene oxide to guar gum obtained by purifying the endosperm portion of Guar seed, which is a leguminous plant. Can be obtained.

  This HP guar gum can be obtained by addition reaction of guar gum and propylene oxide using sodium hydroxide, potassium hydroxide or the like as a catalyst according to a conventionally known method. For example, “JAGUAR HP series” (Solvay) It can also be used as it is.

  Further, the degree of substitution of HP-modified guar gum, that is, the average number of hydroxypropyl groups present per glucose ring unit of cellulose is preferably 0.4 or more, more preferably 1.2 or more. If the degree of substitution is less than this, the gelation effect may be insufficient.

On the other hand, examples of water-soluble cellulose compounds used in the present invention include C _1-4 alkyl celluloses such as methyl cellulose and ethyl cellulose; for example, hydroxy C _2-4 alkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; Cellulose (for example, hydroxy C _2-4 alkyl C _1-4 alkyl cellulose such as hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose, etc.).

  Among these, preferred examples are hydroxypropylmethylcellulose (hereinafter abbreviated as “HPMC”) and hydroxyethylcellulose (hereinafter abbreviated as “HEC”) because of its high affinity with alcohol and good dispersibility. Is mentioned.

Among these, HPMC is a nonionic water-soluble cellulose ether obtained by treating cellulose with caustic soda and then reacting with an etherifying agent such as methyl chloride, propylene oxide or ethylene oxide. By substituting a part with a methyl group or a hydroxypropyl group (—CH ₂ CHOHCH ₃ ), the hydrogen bond is eliminated and water-solubility is achieved. For example, since it is commercially available as “Metroze” (manufactured by Shin-Etsu Chemical Co., Ltd.), it can be used as it is.

  In the present invention, when HPMC is used as the water-soluble cellulose compound, the degree of substitution, that is, the average number of hydroxyl groups substituted with methoxyl groups present per glucose ring unit of cellulose is preferably 1.0 to 2. 5 and more preferably in the range of 1.5 to 2.5. The number of moles of substitution, that is, the average number of moles of hydroxypropoxy group added per glucose ring unit of cellulose is preferably in the range of 0.05 to 0.40, more preferably 0.10 to 0.30. Further, the viscosity of the 2% aqueous solution is preferably 2000 to 10,000 mPa · s.

On the other hand, HEC is a nonionic water-soluble cellulose ether obtained by treating cellulose with caustic soda and then reacting with ethylene oxide, and part of the hydrogen atoms of the hydroxyl group of cellulose is a hydroxyethyl group (—CH ₂ CH ₂ By substituting with OH), the hydrogen bond disappears and becomes water-soluble. For example, since it is marketed as “HEC Daicel” (manufactured by Daicel Finechem Co., Ltd.), it can be used as it is.

  In the present invention, when HEC is used as the water-soluble cellulose compound, the degree of substitution, that is, the average number of hydroxyl groups substituted with hydroxyethyl groups present per cellulose glucose ring unit is preferably 0.5 to 2. 0.0, more preferably in the range of 0.8 to 1.5. The number of substituted moles, that is, the average number of moles of hydroxyethyl groups added per glucose ring unit of cellulose is preferably in the range of 1.0 to 3.0, more preferably 1.5 to 2.8. Further, the viscosity of the 2% aqueous solution is preferably 2000 to 10,000 mPa · s.

（式中、ｎは１ないし３の自然数を示す） Furthermore, the alcohol gelled in the present invention is preferably a lower alcohol having 5 or less carbon atoms or an aromatic alcohol represented by the following formula (1).

(Where n represents a natural number of 1 to 3)

  Specific examples of alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and pentanol. And phenoxyethanol.

  The alcohol-based gel composition of the present invention (hereinafter referred to as “gel composition”) is produced by adding and dispersing HP guar gum and a water-soluble cellulose compound in alcohol, then adding water and stirring to homogenize. Is done. In this method, at the stage where HP-modified guar gum and a water-soluble cellulose compound are added to the alcohol, the dispersion is highly fluid, but by adding water, the water-soluble cellulose dissolves in the water, and the entire composition Gels.

  In the production of the gel composition, the HP-modified guar gum is used in an amount of about 0.1 to 20% by mass (hereinafter abbreviated as “%”), preferably about 1 to 15%, based on the total composition. The functional cellulose compound is used in an amount of about 0.1 to 20%, preferably about 0.5 to 10%.

  The amount of water in the solvent to be gelled is about 1 to 30%, preferably about 5 to 20%, and the balance is alcohol.

  The gel composition can be produced by adding water in the solvent at room temperature (about 25 ° C.) without any special heating or the like, particularly gelling acid, alkali, or other components. There is no need to add for the start.

  In addition, in the above solvent components such as alcohol or water, an effective component such as an aroma component, a deodorizing component, an insecticidal / insecticidal component, a bactericidal component, a pigment component or the like is added and gelled, thereby forming a gel A fragrance, a gel-like deodorant, a gel-like insecticide, a gel-like insecticide, a gel-like fungicide and the like can be easily obtained.

  The active ingredient to be used is not particularly limited, but, for example, aromatic components such as fragrances and essential oils, aluminum sulfate, ammonium chloride, alum, copper sulfate, zinc sulfide, zinc stearate, aluminum stearate, titanium oxide zinc oxide , Flavonoid compounds, catechins, polyphenols, cyclodextrins, zeolites, layered zinc aluminosilicates, activated carbon, Bincho charcoal and other deodorant ingredients, empentrin, transfluthrin, allethrin, phenothrin, methfluthrin, profluthrin, paradichlorobenzene, naphthalene, camphor, 2 -Phenoxyethanol, chili powder, burdock powder, insecticidal / insecticidal / bactericidal components such as cuminaldehyde, emulsifying / dispersing components such as surfactants, pH adjusting components such as acids and alkalis, pigment components such as synthetic pigments and natural pigments, etc. Cited .

  The gel composition of the present invention thus obtained can be gelled by using HP-modified guar gum and water-soluble cellulose which are easy to handle with high concentration of alcohol without heating. Therefore, as compared with the case of using a gelling agent that requires heat treatment, a gel composition can be obtained without reducing the volatile active ingredient due to denaturation and volatilization during the gel preparation process.

  It is also possible to prevent dangers such as explosion and fire due to overheating of alcohol during the preparation process. Furthermore, it becomes possible to give an insecticidal effect and an antifreeze effect in a low temperature environment by blending alcohol at a high concentration of 50% or more.

  From the above properties, the gel composition of the present invention can be advantageously used as a volatile fragrance, a deodorant, an insecticide / insecticide, a bactericide and the like.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.

Example 1
Preparation of gel composition:
According to the composition shown in Table 1, a gel composition was prepared at room temperature by the following method.

[Composition]

[Production method]
At room temperature, 95% ethanol was taken into a plastic 100 ml beaker, and HPMC or HEC was added thereto as HP-modified guar gum and a water-soluble cellulose compound to obtain a suspension. While this suspension was stirred with a stirrer, ion exchange water was added to cause gelation to obtain a gel composition.

Example 2
Evaluation of physical properties of gel composition:
About the gel composition obtained in Example 1, the physical property was evaluated by the following evaluation criteria. The results are shown in Table 2.

[ Evaluation of the physical properties ]
(1) Stirrability The following criteria evaluated from the stirring state at the time of gel manufacture.
○: After addition of ion-exchanged water, the solution was gelled after stirring uniformly. ×: No gelation even after 20 minutes after addition of ion-exchanged water.

(2) Gel forming property After stopping stirring for gel formation, the gel moving distance was measured as shown in Fig. 1 for a 100 ml beaker that was allowed to stand at room temperature for 20 minutes, and the gel forming property was evaluated from this value. . That is, the distance (movement distance) from the position of the top end of the gel (a in the figure) to the position of the tip of the gel surface (b in the figure) after 5 minutes have passed since the gel was laid down side by side with the beaker ) Was measured and evaluated according to the following criteria.
◎; Traveling distance when lying down for 5 minutes is less than 10 mm ○; Moving distance when lying down for 5 minutes is 10 to 45 mm
×: Liquid

(3) Shrinkability due to volatilization The following criteria evaluated whether the gel volatilizes and the gel shrinks in a similar shape compared to the shape immediately after formation: ◎; Gel contracts in a similar shape ○; Gel Shrinks but shape is indefinite (part of the residue remains on the wall)
×: Volumetric shrinkage is small and shrinkage is difficult to understand-; No gel was formed, so evaluation is not possible

[Physical properties]

  As is clear from this result, by using ethanol and water as a solvent and using HP-modified guar gum in combination with HPMC or HEC which is a water-soluble cellulose compound, it is excellent in stirring property, gel forming property, and shrinkage property after volatilization. A gel composition could be formed.

Example 3
Preparation of gel composition and evaluation of physical properties (1):
The gel composition of the present invention was prepared using HPMC having different physical properties, and the physical properties were evaluated. As in Example 2, the stirring property and gel forming property were evaluated in the same manner as in Example 2. The composition of the gel composition is shown in Table 3, and the physical properties are shown in Table 4.

[Composition]

[ Evaluation of the physical properties ]
(4) Water separation The water separation after the prepared gel was allowed to stand overnight was evaluated according to the following criteria. ◎; No water separation was observed at all ○; Slight water separation was observed ×; A large amount of water separation was observed

[Physical properties]

  As is clear from this result, when HPMC was used, a good gel composition could be formed.

Example 4
Preparation of gel composition and evaluation of physical properties (2):
Using phenoxyethanol as the hydrophilic alcohol, a gel composition was prepared in the same manner as in Example 1, and the evaluation of stirring property, gel forming property and water separation was evaluated by the same method as in the previous example. The composition of the gel composition is shown in Table 5, and the physical properties are shown in Table 6.

[Composition]

[Physical properties]

  As is clear from this result, even when phenoxyethanol was used as the hydrophilic alcohol, a good gel could be obtained by the combined use of HP guar gum and HPMC.

Example 5
Preparation of gel composition and evaluation of physical properties (3):
Preparation of a gel composition was attempted in the same manner as in Example 1 using HP-modified guar gum and HPMC having a lower substitution degree than the HP-modified guar gum used in Examples 1 to 4. Table 7 shows the composition and gel-forming properties of the gel composition.

この結果から明らかなように、ＨＰＭＣを用いない場合には低置換ＨＰ化グアガムをアルコールに分散することが困難であり、２層に分離してしまうが、ＨＰＭＣを併用することでゲル化させることが可能となった。 [Composition and physical properties]

As is clear from this result, when HPMC is not used, it is difficult to disperse the low-substituted HP guar gum in alcohol, and it is separated into two layers. However, gelation can be achieved by using HPMC together. Became possible.

Example 6
Preparation of gel composition and evaluation of physical properties (4):
Preparation of a gel composition was attempted in the same manner as in Example 1, using HP-modified guar gum having the same low substitution degree as that used in Example 5 and HEC having a different viscosity. Table 8 shows the composition and gel-forming properties of the gel composition.

[Composition and physical properties]

  As is clear from this result, even when HP-modified guar gum having a low degree of substitution was used, an excellent gel composition could be formed using HEC having different viscosities.

Preparation Example Gel deodorant, gel fragrance, and gel insect repellent were prepared according to the composition shown in Table 9 below. In any case, uniform stirring was possible, good gel-forming property was exhibited, and there was little water separation from the gel, and a highly useful preparation was obtained in which the gel contracted into a similar shape as the solvent evaporated.

  The alcohol-based gel composition obtained according to the present invention is less colored, and the gel shrinks due to the volatilization of lower alcohol and water. Therefore, the end point is clear when the composition is a type that volatilizes components. It is something that is practical.

Therefore, in preparing the alcohol-based gel composition of the present invention, for example, an effective component such as an aroma component, a deodorizing component, an insecticidal / bactericidal component, a pigment component, or the like is added to the solvent component and gelled. Gel-like fragrances, gel-like deodorants, gel-like insecticides and gel-like fungicides can be easily obtained.

Claims (5)

  An alcohol-based gel composition containing hydroxypropylated guar gum, a water-soluble cellulose compound, alcohol and water. The water-soluble cellulose compound is one or more of C _1-4 alkyl cellulose, hydroxy C _2-4 alkyl cellulose, and hydroxy C _2-4 alkyl C _1-4 alkyl cellulose. Alcohol-based gel composition.   The alcohol-based gel composition according to claim 1, wherein the water-soluble cellulose compound is hydroxypropylmethylcellulose and / or hydroxyethylcellulose. The alcohol is a lower alcohol having 5 or less carbon atoms, or the following formula (1)

(Where n represents a natural number of 1 to 3)
The alcohol-based gel composition according to any one of claims 1 to 3, which is an aromatic alcohol represented by the formula: A method for producing an alcohol-based gel composition, comprising adding water to a mixture of hydroxypropylated guar gum, a water-soluble cellulose compound and alcohol.

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