JP5028131B2 - Gelling agent - Google Patents

Description

  The present invention relates to a gelling agent and a gel composition using the same.

Conventionally, many substances such as water-soluble polymer compounds and 12-hydroxystearic acid are known as gelling agents for gelling water or nonpolar media, and cosmetics containing these substances as gelling agents are known. It has been reported. [See, for example, Patent Document 1 (cosmetics containing N-acylamino acid derivatives) and Patent Document 2 (cosmetics containing polysaccharide derivatives or salts thereof)]
On the other hand, there are few gelling agents capable of gelling highly polar organic media such as alcohol and polyol, and it is limited to a few substances such as dibenzylidene-D-sorbitol (DSB) and metal soap such as sodium stearate. Yes. This is because the gelling agent is derived from the gelation mechanism in which the gelling agent separates into a microphase without dissolving in the organic medium to form a network. In addition, since alcohol has the property of being able to dissolve low polarity compounds such as hydrocarbons and very high polarity compounds such as water, it is inherently difficult to gel such alcohols. .

  However, DSB capable of gelling alcohol has a problem that it is poor in chemical stability and decomposes to generate odor. Further, in order to thicken or gelate using metal soap, it is necessary to use it at a relatively high concentration. Thus, when the gel-like composition prepared using these gelling agents is blended in cosmetics, there is a problem in that an unpleasant feeling such as a strong sticky feeling or a rough feeling is received during use.

Japanese Patent Laid-Open No. 51-19139 Japanese Patent Laid-Open No. 9-110901

  An object of the present invention is to provide a gelling agent having an excellent gelling ability at a low concentration with respect to a highly polar organic base such as alcohol, and a gel composition containing the gelling agent.

The present invention has found that a cellulose derivative having a specific structure works as an excellent gelling agent at a low concentration with respect to a highly polar organic base.
That is, the present invention provides [1] and [2].
[1] A gelling agent comprising a cellulose derivative having a mass average molecular weight of 100,000 to 1,500,000 comprising a repeating unit represented by the following general formula (1).

(In the formula, R represents a hydrogen atom, a hydroxyalkyl group, and a group selected from the substituents represented by the general formula (2), Q represents an alkanediyl group having 2 to 4 carbon atoms, and a represents Means an average addition mole number and is a number of 0 to 10. R ¹ represents an alkyl group having 16 to 24 carbon atoms which may be substituted with a hydroxyl group, A represents an ether bond or an oxycarbonyl group, E ¹ represents an alkanediyl group having 1 to 6 carbon atoms which may be substituted by a hydroxy group or an oxo group, E ² represents an alkanediyl group having 1 to 6 carbon atoms, and n represents the average number of moles added. And a plurality of R, Q, R ¹ , A, E ¹ , E ² , a and n within and between the repeating units may be the same or different. However, the degree of substitution of the substituent represented by the general formula (2) is 1) a repeating unit 1000 per 50 to 200 represented by.)
[2] A gel composition comprising the gelling agent of [1] and an alcohol.

  The gelling agent of the present invention is capable of gelling a highly polar organic base used in the cosmetics field and the external preparation field at a low concentration, and has an excellent performance that does not impair the touch during use. Have. Moreover, the composition containing the gelling agent and alcohol of the present invention is useful as an excellent gel composition.

<Gelling agent>
The gelling agent of the present invention contains a cellulose derivative having a mass average molecular weight of 100,000 to 1,500,000 consisting of repeating units represented by the following general formula (1).

In the general formula (1), R represents a group selected from a hydrogen atom, a hydroxyalkyl group, and a substituent represented by the general formula (2).
The hydroxyalkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. Examples thereof include a 2-hydroxyethyl group and a 2-hydroxypropyl group, and the 2-hydroxyethyl group is particularly preferable from the viewpoint of availability.
Q represents an alkanediyl group having 2 to 4 carbon atoms, and is preferably an ethylene group or a propane-1,2-diyl group.
a means the average added mole number, and is a number of 0-10, Preferably it is a number of 0-6, From a synthetic viewpoint, Preferably the sum total of three a is 1-3.
From the viewpoint of dispersibility, R is preferably a hydroxyalkyl group and a substituent represented by the general formula (2).

In the general formula (2), R ¹ is a hydroxyl group is an alkyl group with carbon atoms and optionally 16-24 substituted. R ¹ is preferably a linear alkyl group having 16 to 24 carbon atoms, more preferably a linear alkyl group having 16 to 20 carbon atoms, from the viewpoints of gelation performance, solubility, and dispersibility.
A in the general formula (2) is an ether bond or an oxycarbonyl group (for example, —OCO— or —COO—), and is preferably an ether group from the viewpoint of chemical stability.

E ¹ is an alkanediyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group or an oxo group. E ¹ is preferably an alkanediyl group having 2 to 4 carbon atoms having a hydroxy group, and particularly preferably a 2-hydroxypropane-1,2-diyl group, from the viewpoint of ease of synthesis and the like.
E ² is an alkanediyl group having 1 to 6 carbon atoms. E ² is preferably an alkanediyl group having 2 to 4 carbon atoms, and particularly preferably an ethylene group or a propane-1,2-diyl group, from the viewpoint of availability.
n means an average number of added moles and is a number of 0 to 20, and preferably 0 to 10, more preferably 0 to 5, particularly preferably 0 from the viewpoint of gelation performance.
A plurality of R, Q, R ¹ , A, E ¹ , E ² , a and n in the repeating unit and between the repeating units in the general formula (1) may be the same or different.

The degree of substitution of the substituent represented by the general formula (2) is 50 to 200 per 1000 repeating units represented by the general formula (1), and is preferably per 1000 repeating units from the viewpoint of production cost. It is 50-150, More preferably, it is 60-120.
The “degree of substitution” means the average number of substituents per 1000 repeating units (constituent monosaccharides) represented by the general formula (1).
This degree of substitution can be determined by the Zeisel method (DG Anderson., Anal. Chem., 43, 894 (1971)). More specifically, hydrolysis of an ether bond and iodination of a higher alcohol (R ¹ OH) generated by hydrolysis are performed using hydrogen iodide, and the resulting alkyl iodide (R ¹ I) is converted into a gas chromatograph. It can be determined by quantifying by the graph method.

  The cellulose derivative contained in the gelling agent of the present invention has a mass average molecular weight of 100,000 or more, preferably 200,000 or more from the viewpoint of gelation performance, and 1.5000 or less from the viewpoint of dissolution rate. Preferably, it is 1 million or less. The mass average molecular weight (Mw) of the cellulose derivative is measured by a gel permeation chromatography (GPC) method using polystyrene as a standard substance. Details of the method for measuring the mass average molecular weight (Mw) are described in the Examples.

  Moreover, the cellulose derivative used by this invention is represented with the following general formula (3) with respect to the compound without a substituent represented with General formula (2) among the compounds represented with General formula (1). It can be obtained by reacting a polyoxyalkylene agent.

(In the formula, E ³ represents an epoxidized alkyl group having 3 to 6 carbon atoms, a linear or branched halogenated alkyl group having 1 to 6 carbon atoms which may be substituted by a hydroxy group, a carboxy group, and a carbon number. 1 to 6 carboxyalkyl groups or derivatives thereof are shown, and R ¹ , A, E ² , and n are the same as above.
In the general formula (3), among the groups represented by E ³ , the epoxidized alkyl group having 3 to 6 carbon atoms includes 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5- Examples thereof include an epoxypentyl group and a 5,6-epoxyhexyl group. Among these, 2,3-epoxypropyl group is preferable from the viewpoint of synthesis.
The linear or branched alkyl halide group having 1 to 6 carbon atoms that may be substituted by the hydroxy group of E ³ is preferably a linear halogenated alkyl group having 2 to 6 carbon atoms, such as 2-chloroethyl. Group, 3-chloropropyl group, 4-chlorobutyl group, 5-chloropentyl group, 6-chlorohexyl group, 2-bromoethyl group, 2-hydroxy-3-chloropropyl group and the like. Among these, a 2-hydroxy-3-chloropropyl group is preferable from the viewpoint of synthesis.

As the carboxyalkyl group having 1 to 6 carbon atoms E ^3, preferably carboxyalkyl group having 2 to 5 carbon atoms, carboxyethyl group, carboxypropyl group, carboxybutyl group, and carboxymethyl pentyl group.
Examples of the derivatives of the epoxidized alkyl group, halogenated alkyl group, carboxy group, and carboxyalkyl group having 1 to 6 carbon atoms include methyl ester compounds, ethyl ester compounds, acid halides, tosyl compounds, mesyl compounds, anhydrous Such as things. Among these, 2,3-epoxypropyl group and 2-hydroxy-3-chloropropyl group are particularly preferable.
The polyoxyalkylene agent represented by the general formula (3) can be used singly or in combination of two or more, and the amount used is appropriately determined depending on the desired introduction amount of the substituent of the general formula (2). Can be determined.

(Reaction conditions)
The above reaction is preferably carried out in the presence of an alkali, if necessary. Examples of the alkali include hydroxides, carbonates, bicarbonates and the like of Group 1 or Group 2 elements of the periodic table. Of these, sodium hydroxide and potassium hydroxide are preferred.
From the viewpoint of reaction efficiency, the amount of alkali used is preferably 0.01 to 0.5 mole times, particularly 0.1 to 0.2 mole times, with respect to the repeating unit represented by the general formula (1). The range of is preferable.
As the solvent, a lower alcohol having 1 to 6 carbon atoms can be used. From the viewpoint of reaction yield, a lower alcohol having 2 to 4 carbon atoms is preferable, and isopropyl alcohol is particularly preferable. Further, from the viewpoint of increasing the reactivity, a mixed solvent in which 0.1 to 100% by weight, particularly preferably 1 to 50% by weight of water is added to the lower alcohol can be used.
The reaction temperature is preferably 0 to 150 ° C., particularly preferably 30 to 100 ° C., from the viewpoint of reaction efficiency.

After completion of the reaction, it can be neutralized with an acid. As the acid, in addition to inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as acetic acid and succinic acid can be used.
Moreover, after completion | finish of reaction, it can refine | purify in order to remove the polyoxyalkylene agent represented by unreacted general formula (3), the alkali catalyst, and the salt produced | generated by neutralization. Further, the solvent can be distilled off without purification.
The purification method can be appropriately carried out by a method according to the purpose. For example, using a reaction solvent or a mixed solvent of acetone / water and repeating stirring and filtration 2 to 3 times is effective.
The content of the cellulose derivative represented by the general formula (1) is 50 to 100% by mass, preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass in the gelling agent from the viewpoint of gelation performance. %.

<Gel composition>
The gel composition of the present invention comprises the gelling agent of the present invention and an alcohol. A cellulose derivative having a mass average molecular weight of 100,000 to 1,500,000 composed of the repeating unit represented by the general formula (1) is thickened by uniform dispersion in alcohol and exhibits excellent gelling ability.
The alcohol is not particularly limited as long as it can uniformly disperse the cellulose derivative represented by the general formula (1). A wide range of alcohols can be used, from lower monohydric or polyhydric alcohols having 1 to 6 carbon atoms to higher monohydric or polyhydric alcohols having 7 to 18 carbon atoms, and these alcohols can be effectively gelled. . Since the alcohol separated from water can be gelled by a general oil gelling agent, the gelling agent of the present invention is particularly effective for a polar alcohol.
Water can be added to the gel composition of the present invention for the purpose of increasing the dispersibility of the cellulose derivative contained in the gelling agent of the present invention.
The content of the gelling agent can be determined by appropriately adjusting from the viewpoint of the target viscosity and gel strength, but when blended with cosmetics or the like with respect to a mixture with alcohol and / or water. From the viewpoint of usability, it is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, further preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass.
From the viewpoint of dispersibility, the alcohol content is preferably 50 to 99% by mass, more preferably 70 to 99% by mass, still more preferably 75 to 95% by mass, and particularly preferably 80 to 90% in the gel composition. % By mass.
From the viewpoint of dispersibility, the water content is preferably 0 to 50% by mass, more preferably 0 to 15% by mass with respect to the alcohol, and preferably 5 to 20% by mass in the gel composition. Preferably it is 8-15 mass%.

In the case of gelling alcohol or the like, it can be gelled by adding the gelling agent of the present invention to the target alcohol or the like and stirring at room temperature. Further, the method of refluxing a target alcohol or a mixture of alcohol and water to accelerate dispersion and then returning to room temperature is preferable because gelation can be performed in a short time.
A surfactant, a dispersant, a fragrance, a dye, an inorganic salt, and a pH adjuster that are usually used in cosmetics and toiletry products can be appropriately added to the gel composition of the present invention depending on the purpose.
The gelling agent of the present invention and the gel composition containing it can be suitably used for cosmetics, external preparations for skin, toiletry products and the like.

In the following examples, “%” is “% by mass” unless otherwise specified.
In addition, the measuring method of the substitution degree of the substituent represented by General formula (2), and the mass mean molecular weight (Mw) of a cellulose derivative is as follows.
(1) Measurement of the degree of substitution of the substituent represented by formula (2)
It was determined by the Zeisel method (DGAnderson., Anal. Chem., 43, 894 (1971)).
Specifically, 110 mg of adipic acid, an appropriate amount of internal standard substance (hydrocarbon) and 3 g of 55% hydroiodic acid are added to 100 mg of the cellulose derivative, sealed, and stirred at 150 ° C. for 1 hour. After cooling to 60 ° C., 3 g of hexane is added and stirred vigorously. After cooling to 30 ° C. or lower, 1 g of diethyl ether is added and stirred vigorously again. The organic layer was collected, sodium bicarbonate (powder) was added thereto, and the mixture was vigorously stirred. The solution was collected, and alkyl iodide was quantified by gas chromatography.
(2) Measurement of mass average molecular weight (Mw) of cellulose derivative N, N- containing 60 mmol / L phosphoric acid and 50 mmol / L lithium bromide as a solvent using Tosoh Corporation HLC-8120GPC as a column. It measured using polystyrene as a standard substance by GPC method using dimethylformamide, and calculated as a polyoxyethylene (POE) equivalent mass average molecular weight (Mw).

Examples 1-3
(Production of cellulose derivative A)
Into a 1 L four-necked round bottom flask with a reflux condenser, 100 g of hydroxyethyl cellulose (“SE390” manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight 200,000) is added and stirred with isopropyl alcohol (IPA) / water (mass ratio). = 500/15 mixed solvent was added to prepare a slurry. After passing nitrogen for 30 minutes to deoxygenate the system, 52.9 g of stearyl glycidyl ether was added, and 6.1 g of 48% aqueous sodium hydroxide solution was further added and stirred. The flow of nitrogen was stopped, the temperature was raised in a nitrogen atmosphere, and after aging for 9 hours under heating and refluxing at a bath temperature of 85 ° C., the mixture was cooled to near room temperature.
After acetic acid 4.5g was added and neutralized to the obtained solution, IPA 500g was added and it extracted from the flask, acetone 6L was added, and sugar chain aggregation precipitation was performed. After removing the solvent by filtration, the mixture was swelled by stirring overnight in 1 L of ethanol, then 2 L of acetone was added to cause aggregation and precipitation of sugar chains, and the solvent was again removed by filtration. The obtained cake was dried at 60 ° C. under reduced pressure (1.3 kPa) to obtain 92.6 g of a rocky cellulose derivative A. The obtained cellulose derivative A had a POE equivalent mass average molecular weight (Mw) of 240,000, and the degree of substitution of stearyl glycidyl ether was 97.5.

(Production of gel composition)
Cellulose derivative A, IPA (0.9 g) and water (0.1 g) are placed in a 10 mL (inner diameter 18 mm) glass container containing a magnetic stirrer so as to have the ratio shown in Table 1, and stirred on a block heater. While raising the temperature to 70 ° C., the cellulose derivative A was uniformly dispersed. Then, it cooled to 25 degreeC, stirring on a water bath, and was set as the gel-like composition.
(Evaluation of gelling ability)
The gel composition obtained above was allowed to stand for 10 seconds, then the glass container was turned over, and the gelled state was evaluated according to the following criteria. The results are shown in Table 1.
(Evaluation criteria)
5: Even if it falls, it does not deform for 10 seconds or more, maintains its shape, and is sufficiently gelled.
4: Deforms when it falls, but thickens.
3: It deforms when it falls, and it does not thicken.
2: Deforms immediately when it falls, and does not gel unless cooled to 10 ° C.
1: No gelation at all.

Examples 4-6
(Production of cellulose derivative B)
In Example 1, the same operation as in Example 1 was performed except that 126.2 g of the compound represented by the following formula (4) was used instead of 52.9 g of stearyl glycidyl ether.
The resulting solution was neutralized by adding 4.5 g of acetic acid, then taken out from the flask, 2 L of acetone was added, and the operation of solvent removal by aggregation and filtration of sugar chains was repeated three times. The obtained cake was dried at 60 ° C. under reduced pressure (1.3 kPa) to obtain 117.9 g of a light yellow powdery cellulose derivative B. The obtained cellulose derivative B had a POE equivalent mass average molecular weight (Mw) of 240,000, and the degree of substitution of glycidyl ether represented by the following formula (4) was 75.7.

  Production of a gel composition containing cellulose derivative B and evaluation of gelation ability were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 1-3
(Production of cellulose derivative C)
In Example 1, the reaction was carried out using 7.9 g of the compound of the following formula (5) instead of 52.9 g of stearyl glycidyl ether, and the reaction was performed in the same manner as in Example 1 except that the mixture was heated to reflux and then cooled to near room temperature. It was.
The resulting solution was neutralized by adding 4.5 g of acetic acid, extracted from the flask, filtered, and then dispersed by adding 700 g of a mixed solvent of IPA / water = 85/15 and removing the solvent by filtration three times. Repeatedly, the solvent was replaced twice with IPA. The obtained cake was dried at 60 ° C. under reduced pressure (1.3 kPa) to obtain 87.2 g of a light yellow powdery cellulose derivative C. The obtained cellulose derivative C had a POE equivalent mass average molecular weight (Mw) of 240,000, and the degree of substitution of the glycidyl ether represented by the following formula (5) was 9.1.

  Production of a gel-like composition containing cellulose derivative C and evaluation of gelation ability were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 4-6
(Production of cellulose derivative D)
In Comparative Example 1, the same operation as in Comparative Example 1 was carried out except that 6.4 g of stearyl glycidyl ether was used instead of 7.9 g of the compound of formula (5) (yield 92.0 g). The obtained cellulose derivative D had a POE equivalent mass average molecular weight (Mw) of 240,000, and the degree of substitution of stearyl glycidyl ether was 12.5.
Production of a gel composition containing cellulose derivative D and evaluation of gelation ability were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 7-9
(Production of cellulose derivative E)
Comparative Example 3 was carried out in the same manner as Comparative Example 3 except that 3.7 g of lauryl glycidyl ether was used instead of 7.9 g of the compound of formula (5) (yield 91.0 g). The obtained cellulose derivative D had a POE-converted mass average molecular weight (Mw) of 240,000, and the degree of substitution of lauryl glycidyl ether was 11.6.
Production of a gel composition containing cellulose derivative E and evaluation of gelation ability were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 10-12
Sodium stearate, IPA (0.9 g) and water (0.1 g) are placed in a 10 mL (18 mm inner diameter) glass container containing a magnetic stirrer in the proportions shown in Table 1, and stirred on a block heater. The temperature was raised to 70 ° C. while uniformly dispersing. Then, it cooled to 25 degreeC, stirring on a water bath.
The gelation ability was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As is clear from Table 1, it can be seen that the gel agents of the present invention shown in Examples 1 to 6 are capable of gelling alcohol even at a low concentration and exhibit high gelling ability. Therefore, the gelling agent of the present invention and the gel composition containing the same can be suitably used for cosmetics, external preparations for skin, toiletry products and the like.

Claims (4)

A gelling agent comprising a cellulose derivative having a mass average molecular weight of 100,000 to 1,500,000 comprising a repeating unit represented by the following general formula (1).

(In the formula, R represents a hydrogen atom, a hydroxyalkyl group, and a group selected from the substituents represented by the general formula (2), Q represents an alkanediyl group having 2 to 4 carbon atoms, and a represents Means an average addition mole number and is a number of 0 to 10. R ¹ represents an alkyl group having 16 to 24 carbon atoms which may be substituted with a hydroxyl group, A represents an ether bond or an oxycarbonyl group, E ¹ represents an alkanediyl group having 1 to 6 carbon atoms which may be substituted by a hydroxy group or an oxo group, E ² represents an alkanediyl group having 1 to 6 carbon atoms, and n represents the average number of moles added. And a plurality of R, Q, R ¹ , A, E ¹ , E ² , a and n within and between the repeating units may be the same or different. However, the degree of substitution of the substituent represented by the general formula (2) is 1) a repeating unit 1000 per 50 to 200 represented by.)   The gelling agent according to claim 1, wherein the content of the cellulose derivative represented by the general formula (1) is 50 to 100% by mass.   A gel composition comprising the gelling agent according to claim 1 or 2 and an alcohol.   The gel composition according to claim 3, comprising 1 to 50% by mass of a gelling agent and 50 to 99% by mass of alcohol.