JPS6042761B2 - cosmetic base material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel cosmetic base material comprising a cationically modified starch, and more specifically, a quaternary nitrogen base material that provides a good feeling of use and finish, and provides a dermatologically stable cosmetic product. The present invention relates to a cosmetic base material comprising a high content of cationically modified starch.

In recent years, there has been a tendency for natural products or their derivatives to be widely used as cosmetic base materials due to their harmlessness to the human body, affinity for hair and skin, and their excellent properties. ,′・１、゜嘗、ノzar−
It is blended into skin care products such as care products, creams, and emulsions to improve the range of use, such as smoothness, softness, sliminess, and ease of combing. Hydrolyzed proteins, lanolin, vitamins, and their derivatives have been proposed as cosmetic base materials for the purpose of improving hair styling, moisturizing, and gloss after use.

However, when cosmetics are actually prepared using these natural products and their derivatives as base materials, the expected results can be obtained in terms of the application range, but especially in the case of hair care products, the finish after use is not as expected. The reality is that it is not as effective as it should have been. The reason for this is thought to be that conventional base materials do not have a sufficiently strong adsorption power to hair or skin, so when the base materials are washed away with water after use, they are removed together with other components. Therefore, if a substance that has good affinity with hair and skin and is not easily removed by washing with water is used as the base material, a more excellent finish can be obtained. The present inventors focused on this point, and when processed into shampoos and conditioners, they remain on the skin and hair even after rinsing, giving a good finish. As a result of intensive research to develop cosmetic base materials that can maintain a good finish over a long period of time, certain cationically modified starches have been found to have a strong affinity for hair and skin. The present inventors have discovered that the present invention has properties and is suitable as a base material for cosmetics, and based on this knowledge, the present invention has been completed.

Cationo-modified starch has traditionally been used mainly as a paper strength enhancer, retention improver, freeness improver, or flocculant for paper manufacturing, but conventional cation-modified starch can also be used as a base for cosmetics such as jumpers, rinses, and creams. Even when used as a material, there is almost no improvement in the feeling of use or finish.

In contrast, cationically modified starch with a higher quaternary nitrogen content than conventional starch, which is obtained by reacting starch with a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt, is used as a cosmetic base material. It has been found that when used as a material, the feel of use and finish can be improved. Therefore, the present invention consists of a cationically modified starch with a quaternary nitrogen content of 1 to 5% by weight obtained by reacting starch with a glycidyl trialkylammonium salt or a 3-halogeno 2-hydroxypropyl trialkylammonium salt. It provides a base material for cosmetics.

The starch that is the raw material for the cationically modified starch of the present invention may be derived from Japanese starch, potato starch, wheat starch, corn starch, rice starch, tapioca starch, etc., and commercially available products can be used as they are. .

In addition, starch is used as a raw material, and inorganic or organic acids are used.
Soluble starch that has undergone hydrolysis (acid-treated starch) can also be used. Examples of the glycidyltrialkylammonium salts to be reacted with this starch include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyldimethylethylammonium chloride, glycidylmethyldiethylammonium chloride, glycidyltripropylammonium chloride, glycidylmethylethylpropylammonium chloride, and Corresponding promids, iodides, etc. can be mentioned.

In addition, examples of 3-halogeno 2-hydroxypropyltrialkylammonium salts include 3-chloro2-hydroxypropyltrimethylammonium chloride, 3-
Chloro 2-hydroxypropyl triethylammonium chloride, 3-chloro 2-hydroxypropyldimethylethylammonium chloride, 3-chloro 2-hydroxypropylmethyldiethylammonium chloride, 3-chloro 2-hydroxypropyltripropylammonium chloride, 3-chloro 2- Mention may be made of hydroxypropylmethylethylpropylammonium chloride and the corresponding bromides, iodides, and the like. The reaction of starch with a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt is carried out by adding a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt to a suspension of starch in the presence of an alkaline catalyst such as sodium hydroxide. - Halogeno 2-Hydroxypropyl trialkylammonium salt solution is added and the heating reaction is followed by neutralizing the reaction mixture with an acid such as hydrochloric acid.

When a hydrophilic solvent such as methanol is added to the reaction mixture thus obtained, cationically modified starch precipitates as a white solid, which is collected and dried. In this case, the quaternary nitrogen content of the cationically modified starch is 1 to 5.
It is necessary to carry out the reaction under conditions such that the weight % range is achieved. Cationically modified starch containing quaternary nitrogen in this range has sufficient affinity for hair and skin, but
If the content of quaternary nitrogen is less than 1% by weight, the affinity will be insufficient, and no effect will be observed even when used in jumpers, rinses, creams, etc. If the quaternary nitrogen content exceeds 5% by weight, not only will a sticky feeling occur during use, worsening the feeling of use, but the finish after use will not improve as much as expected, making it economically undesirable. is also disadvantageous.
The cation-modified starch obtained as described above does not contain quaternary nitrogen within a suitable range, so it has excellent affinity with the carboxyl groups of proteins that make up hair and skin, and has good affinity for hair and skin. Adsorption is greatly improved.

Therefore, when used for rinsing, it is effective in coexistence with all cationic surfactants such as monoalkyltrimethylammonium salts and dialkyldimethylammonium salts, and especially improves curl retention after use. The cationic modified starch of the present invention is a polymer with sufficient quaternary nitrogen groups, so it can improve the combability, gloss, etc. This complex is soluble in an aqueous solution containing the anionic active agent, so it can coexist stably without impairing the appearance of the product.Moreover, Jumpu using the cationically modified starch of the present invention is easy to use. In some cases, it improves the stickiness of the foam, reduces the squeaky feel of the hair, and improves the smoothness of the hair, and after use, it significantly improves the ease of combing, curl retention, moisturizing feeling, and shine. It is effective. This is thought to be because the complex of the cationically modified starch obtained by the present invention and the anionic activator used is well adsorbed to the hair, similar to the case of the cationically modified starch alone. When used in Jumpu These effects vary depending on the type of anionic activator used.The most effective effects are when used in combination with alkyl ethoxy sulfates, magnesium and calcium salts of alkyl sulfates, or amphoteric activators; The effect decreases in the order of triethanolamine salt and sodium salt of alkyl sulfate and alkyl sulfate.Furthermore, when the cationically modified starch according to the present invention is dissolved in water, a smooth aqueous solution with better transparency can be obtained compared to starch. When added to skin care products such as creams, it can give a good feel and finish without damaging the appearance of the product.Furthermore, it remains adsorbed to the skin for a long time, making it smooth and durable. A strong effect can be exhibited for a long time.The amount of the cationically modified starch according to the present invention added to hair care products such as Jumpoo and conditioner is preferably 0.1 to 5% by weight, and 0.1 to 5% by weight. If it is less than 0.05% by weight, the effect will not be sufficiently exhibited, and if it is more than 5% by weight, it will feel sticky when used, resulting in a poor feeling of use.The amount to be added to skin care products such as creams is preferably 0.5 to 10% by weight. The cationically modified starch of the present invention can be incorporated into various cosmetics in the same manner as conventional hydrolyzed proteins, lanolin, vitamins, or derivatives thereof.

Next, the present invention will be explained in more detail with reference to Examples. Example 1 30f of potato starch was dispersed in 150y of a 5% by weight isopropanol aqueous solution, 9.9q of a 15% by weight aqueous sodium hydroxide solution (0.2 times the molar amount of starch) was added, and the mixture was heated at 45°C for 1 hour. Heat treated.

Next, an aqueous solution of glycidyltrimethylammonium chloride (hereinafter referred to as GTA) is added so that the active ingredient is 14.0y (0.5 times the molar amount of starch), heated, and reacted at 50°C for 3 hours. After the reaction was completed, 4.2 y of concentrated hydrochloric acid (1.1 times the molar amount of sodium hydroxide charged) was diluted with 150 q of a 5% isopropanol aqueous solution and used for neutralization.
After neutralization at room temperature for 1 hour, the reaction solution was poured into 300 y of methanol to precipitate the reaction product, which was filtered. After washing the obtained precipitate three times with 300 g of methanol, the reaction product was dried under reduced pressure. The nitrogen content of the cationically modified starch thus obtained was 2.6% by weight, and the content of ionic chlorine was 6.6% by weight.

The degree of substitution (DS) of the cationic group was calculated from this nitrogen content using the following formula and was found to be 0.425. Example 2 In order to examine the effect of blending the cationically modified starch of the present invention, the cationically modified starch obtained in Example 1 was used and the cationically modified starch was blended with an anionic surfactant of lauryl ether sulfate magnesium salt. (
Two transparent types of Jumpu were prepared: 4) and one containing no cationic modified starch in the anionic surfactant of lauryl ether sulfate sodium salt (B), and were used on 20 women to evaluate their performance. I went to

Table 1 shows the components of Jumpu and their blending amounts, and Table 2 shows their performance evaluation for Jumpu.

However, in Table 2, I indicates that the product containing cationically modified starch is superior, ■ indicates that there is no difference between those containing and not containing cationically modified starch, and ■ indicates that the product containing no cationically modified starch is superior. This means that each number represents a number of people. As is clear from Table 2, there is no particularly noticeable difference in the performance during use, but when the base material of the present invention is used, there is a considerable improvement in performance when finished.

Example 3 Performance evaluation was carried out in the same manner as in Example 2 using two types of transparent Jumpu, one containing the cation-modified starch prepared in Example 2 (4) and one without it for comparison (C). I went to

Table 3 shows the components of Jumpu and their blending amounts, and Table 4 shows their performance evaluation.

However, 11■, ■, and numbers in Table 4 have the same meanings as in Table 2. As is clear from Table 4, there is no particularly noticeable difference between the two during use, but in terms of performance during finishing, a considerable improvement in performance is observed when the base material of the present invention is used.

Example 4 Using the cationically modified starch obtained in Example 1, a product (2) was prepared in which the cationically modified starch was blended with an amphoteric surfactant of 2-lauryl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, The performance was evaluated in the same manner as in Example 2 using two types of transparent Jumpu (B), which was prepared in Example 2 and containing no cationic modified starch in the anionic surfactant of sodium lauryl sulfate. I went to

Table 5 shows the components of Jumpu and their blending amounts, and Table 6 shows their performance evaluation.

However, 11■, ■ and numbers in Table 6 have the same meanings as in Table 2. As is clear from Table 6, lauryl ether sulfate was used as the anionic surfactant in Example 2. As with the case of using magnesium salt, a considerable improvement in finishing performance is observed.

Example 5 A transparent type Jumpu (E) was prepared using the cationically modified starch obtained in Example 1 and lauryl ether sulfate triethanolamine salt was blended as an anionic surfactant. Performance evaluation was performed in the same manner as in Example 2 using the transparent type shampoo (B) prepared in Example 2.

Table 7 shows the components of Jumpu and their blending amounts, and Table 8 shows their performance evaluation.

However, 11■, ■, and numbers in Table 8 have the same meanings as in Table 2. As is clear from Table 8, in Example 2 or Example 4, lauryl ether sulfate magnesium salt was used as the anionic surfactant, or 2-lauryl-N-carboxymethyl-N was used as the amphoteric surfactant.
Although it is slightly inferior to the case where -hydroxyethylimidazolinium betaine is used, a certain effect is recognized in terms of performance during finishing.

Example 6 A transparent type Jumpu (F) was prepared using the cationically modified starch obtained in Example 1 and lauryl ether sulfate sodium salt was blended as an anionic surfactant, and also prepared in Example 2 for comparison. The performance was evaluated in the same manner as in Example 2 using transparent type Jumpu (B).

Table 9 shows the components of Jumpu and their blending amounts, and the first cough shows its performance evaluation. However, 11■, ■, and numbers in the first cough have the same meanings as in Table 2. As is clear from the first cough, a slight performance improvement was observed due to the combination of cationically modified starch.

Example 7 Two types of crowbar-shaped jumpu were prepared, one containing the cationically modified starch obtained in Example 1 (A'') and one without (B''), and used on 30 women. The performance was evaluated in the same manner as in Example 2.

Table 11 shows Jumpu composition components and their blending amounts, and Method 1 shows their performance evaluation.

However, 11■, ■, and numbers in the first sentence have the same meaning as in Table 2. As is clear from the first method, when the base material of the present invention is used, the performance during finishing is significantly improved.

Example 8 Soluble starch 30y in 7% ethanol aqueous solution 1
50', 4.9y of a 15% aqueous sodium hydroxide solution (0.1 times the molar amount of soluble starch) was added, and then 20.8y of the active ingredient (0.1 times the molar amount of soluble starch) was added.
6. Add GTA aqueous solution so that the amount is 74 times the molar amount, and heat at 60°C. Allow time to react.

After the reaction was completed, 150 g of a 70% by weight aqueous ethanol solution was added to the reaction system, and the system was cooled until the internal temperature reached about 25°C.
The mixture was neutralized with 1N hydrochloric acid so that the pH was in the range of 5.5 to 6.5 using a PH meter, and stirring was continued for an additional hour for washing. After neutralization and washing, the reaction solution was separated to obtain a reaction product. The obtained product was added to a 7% ethanol aqueous solution (150% by weight).
After washing with y, it was dried under reduced pressure. The nitrogen content of the cationically modified soluble starch thus obtained is 2.
．． The content of ionic chlorine was 6.5% by weight.

From this nitrogen content, the degree of substitution at the cation position (D.S.)
The result was 0.403. In order to investigate the effect of blending the cationically modified soluble starch of the present invention, a transparent type Jumpu (G) was prepared using the cationically modified soluble starch obtained above and containing lauryl ether sulfate magnesium salt as an anionic surfactant. In addition, performance evaluation was performed in the same manner as in Example 2 using the transparent type shampoo (B) prepared in Example 2 for comparison.

Table 14 shows the components of Jumpu and their blending amounts, and Table 14 shows their performance evaluation.

However, 11■, ■ and numbers in Table 14 have the same meanings as in Table 2. As is clear from Table 14, when the base material of the present invention is used, a considerable improvement in performance is recognized.

Example 9 A mixture containing the cationically modified starch obtained in Example 1 (A″) and a mixture without the cationic modified starch (B″) for comparison.
) Two types of transparent liquid type hair rinses were prepared,
This was used by 30 women and the performance was evaluated in the same manner as in Example 2.

Table 15 shows the composition of the hair rinse and its blending amount.
The bale is its performance evaluation.

However, 11■, ■ and numbers have the same meanings as in Table 2. As is clear from the first bale, when the substrate of the present invention is used, the performance is significantly improved both during use and during finishing.

Example 10 Two types of cream-type hair rinses were prepared, one containing the cationically modified starch obtained in Example 1 (A'''') and one without (B''''), which were administered to 30 people. The performance was evaluated in the same manner as in Example 2.

Table 17 shows the composition of the hair rinse and its blending amount, and Table 17 shows its performance evaluation.

However, 11■, ■ and their numbers in Table 18 have the same meanings as in Table 2. As is clear from the first bale, the performance is improved by using the base material of the present invention both during use and during finishing.

Example 11 A mixture of 1 part by weight of liquid paraffin (7@), 10 parts by weight of petrolatum, 0.5 parts by weight of glycerin monostearate, 2 parts by weight of isopropyl palmitate and 3 parts by weight of glycerin was treated with the same force as in Example 1. A neutral cream was prepared by blending 2 parts by weight of modified starch, adding appropriate amounts of fragrance and preservative, and adjusting the total amount to 10 parts by weight with purified water.

Comparative Example In order to compare the effects of the cationically modified starch used in the present invention, a polymer with a degree of polymerization of about 1500,
Average number of moles of ethylene oxide added Jl. Cation-modified hydroxyethyl cellulose having a nitrogen content of 1.6% was produced.

Next, Jumpoo (4) of the present invention obtained in Example 2 and ``Jumpoo'' (B ) and
Each was used by 20 women and their performance was evaluated.

The results are shown in the second cough. However, in the second cough, I is the number of people who thought Jumpu (4) was better, ■ is the number of people who thought Jumpu (B) was better, and ■ is the number of people who thought there was no difference between the two. It is a number. As is clear from this table, Jumpoo containing the cationized starch of the present invention is superior to Jumpoo containing cation-modified hydroxyethyl cellulose in terms of ease of combing and gloss during finishing.

The neutral cream thus obtained was used by 20 women to evaluate its performance, and the results are shown in First Cough.

11■, ■ and their numbers in this table have the same meanings as in Table 2. As is clear from the table below, the neutral cream containing cationically modified starch has a marked improvement in smoothness and moisturizing feeling compared to the cream containing no cationic modified starch, and the effect is long-lasting. sustained over time.

Claims (1)

[Scope of Claims] 1 Consists of a cationically modified starch with a quaternary nitrogen content of 1 to 5% by weight obtained by reacting starch with a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt. Cosmetic base material. 2. The cosmetic base material according to claim 1, wherein the glycidyl trialkylammonium salt is a glycidyl trialkylammonium halide. 3. The cosmetic base material according to claim 1, wherein the 3-halogeno-2-hydroxypropyltrialkylammonium salt is a 3-halogeno-2-hydroxypropyltrialkylammonium halide.