JP6726466B2 - Process for producing hydroxyalkyl cyclodextrin alkenyl succinic acid ester mixture, composition containing mixture containing hydroxyalkyl cyclodextrin alkenyl succinic acid ester, and water-based cosmetic - Google Patents

Description

The present invention relates to a water-based cosmetic composition containing a mixture of hydroxyalkyl cyclodextrins alkenyl succinic acid ester, which has good affinity for hair and skin, gives a good feeling of use and a finished feeling, and has an odor of smell and tobacco. The present invention relates to a cosmetic composition having a deodorizing effect.

In recent years, natural products or their derivatives tend to be widely used as base materials for cosmetics because they are harmless to the human body, have affinity for hair and skin, and have excellent properties. Examples thereof include hydrolyzed proteins, lanolin, lipids, vitamins, cellulose, guar gum, polysaccharides such as starch, and derivatives thereof. For example, a hair setting composition using aminated starch, which is a tertiary aminoalkyl ether of starch and contains 25 to 50% by weight of amylose and 75 to 50% by weight of amylopectin, is disclosed (Patent Document 1). .. Alternatively, it is described that a water-soluble cationic nitrogen-containing polymer is used in shampoos and hair cosmetics (Patent Document 2). In addition, cosmetics using a surfactant made from a linear saccharide such as dextrin or trehalose are described as having low irritation. (Patent Documents 3 and 4)
Furthermore, regarding the removal of odors caused by tobacco, sweat and aging, it is better to include various odorous substances by the technique of inclusion and removal than the method of attaching fragrances (perfumes and colognes) to eliminate the odor. The method of reducing odor has been emphasized from the viewpoint of odor etiquette in recent years.

From the above viewpoints, the raw materials that have been conventionally used for removing odors include protective colloids, cyclodextrins, polyphenols typified by catechins, etc. Due to the increasing demands, satisfactory raw materials cannot be obtained from these conventionally used raw materials. For example, a cleansing cosmetic containing a normal surfactant, represented by shampoos and facial cleansers, can remove odorous substances by washing body parts, but it is a source of odor (nonenal, Aldehydes, ammonia, etc.) are released into a narrow atmosphere such as a bathroom, which may cause "discomfort when washing hair". Further, since odorous substances cannot be removed only by washing with an activator, addition of cyclodextrins is also used, but the feeling such as foaming may change.

U.S. Pat. No. 3,186,911 Japanese Patent Publication No. 47-20635 Japanese Patent No. 3352722 Japanese Patent No. 5427033

Therefore, the present inventors have obtained hydroxyalkylcyclodextrins alkenylsuccinates obtained by reacting cyclodextrins with 1,2-alkylene oxide or 1-halogeno-2-hydroxyalkane and then reacting them with alkenylsuccinic anhydride. By using a mixture containing an acid ester for cosmetics, not only the texture after washing and the feel of the hair are improved, but also odorous substances adsorbed on the hair and scalp are removed and included in various lives, The inventors have found that it is possible to reduce an unpleasant odor during washing and makeup, and have completed the present invention.

As described above, the present invention improves texture and hair feel after washing by using an aqueous cosmetic composition containing a hydroxyalkyl cyclodextrin alkenyl succinic acid ester, and further removes and packs odorous substances. The most important feature is that the unpleasant odor during washing and makeup can be reduced by contact.

That is, the present invention is a hydroxyalkyl cyclodextrin alkenyl succinic acid obtained by reacting cyclodextrins with 1,2-alkylene oxide or 1-halogeno-2-hydroxyalkane and then reacting with alkenyl succinic anhydride. The present invention relates to a method for producing a mixture containing an ester, a composition containing the mixture, and a water-based cosmetic.

The cyclodextrin used as a starting material in the present invention is a dextrin in which bound glucose has a cyclic structure, and α-(6 glucose), β-(7), γ-(8 Individual) cyclodextrin. In addition, dextrins having other cyclic structures (eg, cyclic tetrasaccharide, cycloamylose, cluster dextrin, cyclodextran, branched cyclodextrins typified by maltosyl cyclodextrin, methylated cyclodextrin, etc. can also be used as starting materials. Cyclodextrins have a cyclic structure, and since the inside is hydrophobic and the outside is hydrophilic, it has the function of including odorous substances inside.

In the present invention, the method for producing hydroxyalkyl cyclodextrins is obtained by reacting the above cyclodextrins with an etherifying agent such as 1,2-alkylene oxide or 1-halogeno-2-hydroxyalkane. Is. As the 1,2-alkylene oxide, it is preferable to use ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide or the like. As the 1-halogeno-2-hydroxyalkane, it is preferable to use ethylene chlorohydrin, 1-halogeno-2-hydroxypropane, 1-halogeno-2-hydroxybutane and the like. 1,2-Alkylene oxide or 1-halogeno-2-hydroxyalkane is a compound that withdraws a hydrogen atom from the hydroxyl group of starch and binds to dextrins by an ether bond, or improves the water solubility of cyclodextrins, The purpose is to improve the stability of the aqueous solution after esterification.

In the present invention, the MS value of the hydroxyalkyl cyclodextrins is preferably 1 or more. Here, the MS value means the number of moles of hydroxyalkyl groups bonded (added) to 1 mole of cyclodextrins. For example, the MS value is 2 when 2 mol of hydroxyalkyl group is bonded to 1 mol of β-cyclodextrin (hereinafter referred to as β-CD). However, one or two or more hydroxyalkyl groups bound to β-CD and one to which no hydroxyalkyl group is bound are mixed, and the MS value is shown as an average value thereof.

Cyclodextrins have different solubilities depending on the type. Therefore, it is possible to react with highly soluble substances such as β-CD (solubility is about 2% at 25°C) so as to increase the MS value. preferable. However, for very highly soluble ones, such as cluster dextrins, the MS value need not be very high.

When the hydroxyalkyl cyclodextrin is hydroxyethyl cyclodextrin or hydroxypropyl cyclodextrin, the MS value can be measured according to "Pharmaceutical Additives Standard 2013" It is carried out in accordance with the "hydroxypropyl starch hydroxypropoxyl group quantification method (gas chromatography method)" described on pages 533 to 534. In addition, in the case of a substance other than hydroxyethyl cyclodextrin or hydroxypropyl cyclodextrin, it is carried out according to these descriptions.

In the present invention, alkenyl succinic anhydride is used as a reaction reagent for esterification to react with the above-mentioned hydroxyalkyl cyclodextrins. The alkenyl succinic anhydride is C2-20 alkenyl succinic anhydride, more preferably C8-18 alkenyl succinic anhydride (eg, octenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride). , Hexadecenyl succinic anhydride, octadecenyl succinic anhydride, etc.).

In the present invention, as a method for producing a hydroxyalkyl cyclodextrin alkenyl succinic acid ester, a hydroxyalkyl cyclodextrin dissolved in water is reacted with alkenyl succinic anhydride in the presence of an alkali catalyst. The esterification reaction may be carried out by hydroxyalkylation using an etherifying agent such as 1,2-alkylene oxide or 1-halogeno-2-hydroxyalkane, neutralization, purification and drying, followed by re-dissolution.

The esterification reaction can be carried out by stirring at 10 to 50°C while maintaining the pH at 6 to 9. Examples of the alkali catalyst used include alkali metal or alkaline earth metal hydroxides (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.), alkali metal or alkaline earth metal carbonates (eg, sodium carbonate). , Potassium carbonate, lithium carbonate, etc.), alkali metal or alkaline earth metal alkoxides (eg, sodium methoxide, sodium ethoxide, potassium methoxide, etc.), ammonia, mono-, di- or trialkyl having a C1-6 alkyl group. Amines (eg, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, isobutylamine, secondary butylamine, tertiary butylamine, amylamine, secondary amylamine, tertiary Amylamine, hexylamine, etc.), di- or trialcoholamines having an alcoholic hydroxyl group (eg, triethanolamine, triisopropanolamine, diethanolamine, etc.) and the like.

The hydroxyalkyl cyclodextrin alkenyl succinic acid ester produced by the present invention is one in which an alkenyl succinic anhydride is subjected to a ring-opening reaction by the above catalyst to form an ester bond as a one-side ester. The other carboxyl group is neutralized by the catalyst used and the ester is obtained as a solution of a salt of an alkali metal, alkaline earth metal or amine. The addition amount of the alkenyl succinic anhydride to the hydroxyalkyl cyclodextrin can be appropriately selected.

In the "hydroxyalkyl cyclodextrins" produced by the above method, some of them contain a hydroxyalkyl group and some do not. Therefore, when a hydroxyalkyl cyclodextrin is reacted with an alkenyl succinic anhydride in a solution, a) "a hydroxyalkyl cyclodextrin alkenyl succinic acid ester" which is both hydroxyalkylated and alkenyl succinic acid ester, and b ) 4 types of “hydroxyalkyl cyclodextrins” or “alkenyl succinylated cyclodextrins”, which are only alkenyl succinic acid esterified or hydroxyalkylated, and c) “cyclodextrins” having no substituents. The by-product alkenyl succinic anhydride becomes a mixture containing unreacted alkenyl succinic acid salt which remains ring-opened. From the above, the mixture produced by the production method of the present invention will be referred to as "hydroxyalkyl cyclodextrin alkenyl succinic acid ester mixture".

The hydroxyalkyl cyclodextrin alkenyl succinic acid ester mixture produced according to the present invention is commonly used in conventional forms of water-based cosmetics such as hair care products such as shampoos and treatments, skin care products represented by facial cleansers and toothpaste. It is compounded by. Other components in the water-based cosmetic composition of the present invention are not particularly limited, and include common water-based cosmetic carriers, diluents or additives [eg, various surfactants, oily substances (eg, long-chain fatty acid esters, hydrocarbons, etc. Etc.), hydrolyzed proteins, lanolin, lipids, fragrances, pigments, hydrotropes, etc.] can be used. In addition, vitamins and other nutritionally or pharmaceutically active ingredients may be added.

When the hydroxyalkyl cyclodextrin alkenyl succinic acid ester produced by the present invention is blended in a hair care product, the blending amount thereof is preferably 0.1 to 20 mass% with respect to the total amount of the cosmetic. When this ester is blended in a skin care product such as a face wash, the blending amount thereof is preferably 0.5 to 30% by weight based on the total amount of the cosmetic.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
<Example 1>
In a reactor equipped with a cooling/refluxing tube, 2 parts of sodium hydroxide was added to 100 parts by mass of water (hereinafter referred to as "parts") to dissolve, 100 parts of β-CD was dispersed, and propylene oxide (hereinafter referred to as "etherification agent") , PO) is added in an amount described in Table 1 and subjected to an etherification reaction at 40° C. for 24 hours, and then 60 parts of octenyl succinic anhydride (hereinafter referred to as OSA) is added to 40° C. The pH was adjusted to 7.3 with a 25% aqueous solution of sodium hydroxide while stirring and mixing at, and the reaction was carried out for 3 hours. After the reaction, the final concentration was adjusted to 50% to obtain hydroxypropyl cyclodextrin octenyl succinic acid ester mixtures (hereinafter referred to as HPCD-OSA mixtures) 1 to 7. Table 1 shows the amount of PO added, the MS before the OSA reaction, the foamability and stability of the aqueous solution. The foamability and stability were evaluated by the following methods.

Foaming property: The appearance of bubbles was evaluated after shaking a glass bottle containing 1/2 volume of a mixture diluted to a concentration of 0.5% up and down 50 times. (A: Good foaming, forming a firm foam. O: Good foaming, but disappears with time. X: Poor foaming, disappears immediately.)
Stability: A mixture having a final concentration of 50% was placed in a tightly stoppered glass bottle and allowed to stand in an air bath heated to 50° C. for 1 month, and it was judged whether coloring or precipitation occurred. (∘: Coloring does not change much at the time of production and there is no precipitation. ×: Coloring advances or precipitation occurs during production.)

<Example 2>
Mixtures 8 to 10 were prepared in the same manner as in Test Example 1 except that triethanolamine was used as the catalyst for pH adjustment during the esterification reaction among the formulations of Mixtures 5, 6, and 7 having high stability in Test Example 1. Obtained. Table 2 shows the amount of PO added, the MS before the OSA reaction, and the stability of the aqueous solution.

<Example 3>
In a reactor equipped with a cooling reflux tube, 2 parts of sodium hydroxide was added to 100 parts of water to dissolve, 100 parts of β-CD was dispersed, 20 parts of PO was added as an etherifying agent, and 40° C. for 24 hours. An etherification reaction was carried out (MS=4.4). Then, OSA was added in the amount shown in Table 3, and the pH was adjusted to 7.3 with a 25% aqueous solution of sodium hydroxide while stirring and mixing at 40° C., and the reaction was carried out for 3 hours. After the reaction, the final concentration was set to 50% to obtain HPCD-OSA mixtures 11 to 14. Table 3 shows the amount of OSA added, the foamability and the stability of the aqueous solution.

<Example 4>
To 100 parts of water, 2 parts of sodium hydroxide was added and dissolved, 100 parts of β-CD was dispersed, and butylene oxide as an etherifying agent was added in an amount shown in Table 4 to bring the pH to 11.5. After adjusting, the etherification reaction was carried out at 40° C. for 24 hours, then 60 parts of OSA was added, and while stirring and mixing at 40° C., the pH was adjusted to 7.3 with a 25% aqueous solution of sodium hydroxide, and then 3 hours Reacted. After the reaction, the final concentration was set to 50% to obtain hydroxybutyl cyclodextrin octenyl succinic acid ester mixture (hereinafter, referred to as HBCD-OSA mixture) 15 to 20. Table 4 shows the amount of butylene oxide added, the MS before the OSA reaction, the foamability of the aqueous solution, and the stability.

From the results of Examples 1 to 4, those having excellent foaming property and stability are those having improved solubility of cyclodextrins, for example, in the case of β-CD, MS of hydroxyalkyl group is 4 or more. It was confirmed that the addition amount of octenylsuccinic acid was 40 to 60 parts with respect to 100 parts of β-CD, and the reaction was performed with alkali.

<Example 5>
In Examples 1 to 4, the mixture which was excellent in foamability and stability was subjected to an albumin undenaturation test by the method described below. As a comparative example, the same test was performed using sodium lauryl sulfate (SLS), which is an anionic surfactant commonly used in cosmetics. The results are shown in Table 5. The test method is based on the author name: K.K. MIYAZAWA, M.; OGAWA and T.A. MITSU, Bibliographic name: "The physico-chemical properties and protein denaturation potential of surfactant mixes. It is a test method that serves as an index.

<Test method and measurement conditions>
Various sample solutions (solid content concentration 10%): ovalbumin (dissolved in phosphate buffer (pH 7.0) so that the concentration becomes 0.025%)=1:9, and left at 30° C. for 20 minutes A sample diluted with deionized water 10 times was used as a sample, and the albumin undenaturation rate (%) was determined by the following formula using HPLC. A blank was prepared by adding deionized water instead of the sample solution. The results are shown in Table 5.

[HPLC measurement conditions]
Column used: Asahipak GS-320HQ (Showa Denko KK size 7.6mm ID-300mmL)
Column temperature: 50°C
Mobile phase: Phosphate buffer (Na ₂ HPO ₄ 0.05 mol/L, Na ₂ SO ₄ 0.15 mol/L to pH 7 with phosphoric acid)
Flow rate: 0.4 mL/min Detector: TOSOH UV-8020 (Tosoh Corporation wavelength: 215 nm)

[Calculation formula of albumin native rate]
Albumin native rate (%)=(H ₁ /H ₀ )×100
H ₀ : Peak height of blank albumin H ₁ : Peak height of albumin treated with surfactant

From the above results, it was confirmed that the hydroxyalkyl cyclodextrin alkenyl succinic acid ester mixture having excellent foaming property and stability has a very high unmodified ratio of ovalbumin and a very low skin irritation.

<Example 6>
In Examples 1 to 4, the mixture having excellent foamability and stability was subjected to a deodorizing test by the headspace method by the method described below. As a comparative example, the same test was conducted using unreacted β-CD. The test was conducted under the conditions shown in Table 6 using isovaleric acid (IVA, odor of soles) and acetaldehyde (odor of tobacco) as odor indicators. As a blank, 10 g of deionized water was used instead of the mixture aqueous solution, and as a comparative example, unreacted β-CD 1 g/10 mL suspension (partially dissolved) was used, and the same test was performed. It was The results are shown in Table 7.

From the above results, the hydroxyalkyl cyclodextrin alkenyl succinic acid ester mixture, which is excellent in foamability and stability, can include various odor-causing substances and reduce volatilization to the head space. Moreover, it was confirmed that the amount of the substance causing the odor included in β-CD was significantly larger than that of β-CD.

<Example 7>
In Examples 1 to 4, a mixture having excellent foamability and stability was subjected to a deodorant test by sensory evaluation (7 men and women) by the following method. As a comparative example, the same test was conducted using unreacted β-CD. The test was conducted under the conditions shown in Table 8 using nonenal (aging odor) as the odor indicator substance. As a blank, 10 g of deionized water was used instead of the mixture aqueous solution, and as a comparative example, unreacted β-CD 1 g/10 mL suspension (partially dissolved) was used, and the same test was performed. It was The results are shown in Table 9.

From the above results, the hydroxyalkyl cyclodextrin alkenyl succinic acid ester mixture, which is excellent in foamability and stability, can include nonenal and reduce volatilization of nonenal into the headspace. In addition, it was confirmed that the amount of nonenal included in β-CD was significantly higher than that of β-CD.

<Example 8>
The HPCD-OSA mixture 5 obtained in Test Example 1 was used to prepare a shampoo having a formulation composition A shown in Table 10. For comparison, a composition B containing no mixture and a composition C containing β-CD instead of the mixture were also prepared. Using this shampoo, smokers were asked to use it, and they were evaluated at the time of use and after use by the following evaluations. The results are shown in Table 10.

<Evaluation during use>
◯: Gives a smooth finger passage, and the remaining feeling disappears smoothly.
×: There is resistance in the fingers, and it takes time until the remaining feeling disappears.
<Evaluation after use>
Good: No unpleasant odor remains during washing and after use, and gives a suitable feeling.
X: An unpleasant odor remains on the washed part during and after washing, and is also generated from bubbles.

From the above results, the shampoo using the HPCD-OSA mixture 5 gives a suitable feel during and after use, but the shampoo containing no mixture was not evaluated well during and after use. .. In addition, when β-CD, which generally has a deodorizing effect, was added, the deodorizing effect was obtained, but the touch could not be improved.

<Example 9>
The HPCD-OSA mixture 8 obtained in Test Example 2 was used to prepare a rinse having a formulation composition D shown in Table 11. For comparison, a composition E containing no mixture and a composition F containing β-CD instead of the mixture were also prepared. Using this rinse, a smoker was asked to use it, and the same evaluations as in Example 8 were performed during and after use. The results are shown in Table 10.

From the above results, the rinse using the HPCD-OSA mixture 5 gives a suitable feel during and after use, but the rinse without the mixture was not evaluated well during use and after use. .. In addition, when β-CD, which generally has a deodorizing effect, was added, the deodorizing effect was obtained, but the touch could not be improved.

<Example 10>
The HPCD-OSA mixture 5 obtained in Test Example 1 was used to prepare a body shampoo having a formulation composition G shown in Table 12. For comparison, a composition H containing no mixture and a composition I containing β-CD instead of the mixture were also prepared. Middle-aged and elderly men were asked to use this body shampoo, and the same evaluations as in Example 8 were made during and after use. The results are shown in Table 12.

From the above results, the body shampoo using the HPCD-OSA mixture 5 gives a suitable feel during and after use, but the body shampoo without the mixture is evaluated well both before and after use. There wasn't. In addition, when β-CD, which generally has a deodorizing effect, was added, the deodorizing effect was obtained, but the touch could not be improved.

<Example 11>
Using the HPCD-OSA mixture 7 obtained in Test Example 1, a face-wash foam having a blending composition J shown in Table 13 was prepared. For comparison, a composition K containing no mixture and a composition L containing β-CD instead of the mixture were also prepared. Using this facial cleansing foam, middle-aged and elderly men were asked to use it, and the same evaluations as in Example 8 were performed during and after use. The results are shown in Table 12.

From the above results, the facial cleansing foam using the HPCD-OSA mixture 7 gives a suitable feel during and after use, but the facial cleansing foam containing no mixture is evaluated well during and after use. There wasn't. In addition, when β-CD, which generally has a deodorizing effect, was added, the deodorizing effect was obtained, but the touch could not be improved.

Claims (2)

Under alkaline conditions, cyclodextrin is reacted with 1,2-alkylene oxide or 1-halogeno-2-hydroxyalkane, and then octenyl succinic anhydride is reacted in an amount of 40 to 60 parts by mass with respect to 100 parts by mass of cyclodextrin. A method for producing a mixture of hydroxyalkyl cyclodextrins octenyl succinate obtained by the method. 1,2-alkylene oxide or 1-halogeno-2-hydroxyalkane is one or more selected from ethylene chlorohydrin, propylene oxide and butylene oxide, and is 20 to 30 with respect to 100 parts by mass of cyclodextrins. The method for producing a mixture of hydroxyalkyl cyclodextrins octenyl succinate according to claim 1, wherein the reaction is carried out in parts by mass.