JPS6042763B2 - Cosmetics with good affinity - Google Patents

Description

Detailed Description of the Invention The present invention contains a novel thionated hydroxyalkyl starch that has good affinity for hair and skin, good film flexibility and moisture retention, and is highly safe for the skin. Regarding cosmetics.

In general, hair cosmetics and skin cosmetics must be harmless to the human body, so each component used therein is also required to be highly safe.

The use of natural products and their derivatives is becoming more common as they satisfy this condition of being safe for the human body and have good affinity for hair and skin, such as hydrolyzed proteins, lanolin, lipids, vitamins, etc. Polysaccharides such as cellulose and starch and their derivatives are used for this purpose. Among these, water-soluble proteins, polysaccharides, and their derivatives have been used as protective colloids, thickeners,
They are used as film-forming agents, but as the performance requirements for cosmetics have become more sophisticated in recent years, it is no longer possible to obtain satisfactory cosmetics using these conventionally used raw materials.

As an alternative to these conventional components, the use of water-soluble polymer compounds obtained by cationically modifying cellulose derivatives and starch has recently been attracting attention.

For example, U.S. Pat. No. 3,186,911 describes a tertiary aminoalkyl ether of starch containing 25% to 75% by weight of amylose and 75% to 75% by weight of amylopectin.
Japanese Patent Publication No. 47-20635 describes the use of water-soluble cationic nitrogen-containing polymers in Jumpoo and hair cosmetics. In this case, the water-soluble cationic nitrogen-containing polymer includes cellulose derivatives into which quaternary nitrogen has been introduced. However, all of these cationic modified starches containing tertiary amino groups and quaternary nitrogen have insufficient adsorption properties to hair, and are inferior in texture, such as the smoothness of the hair after use. I still wasn't satisfied with it. The inventors
As a result of intensive research to overcome these drawbacks of conventional cationized starch, we discovered that starch is a mixture of amylose and amylopectin, and has a high content of amylopectin, which causes the film to have a drawback of poor flexibility. On the other hand, cationized hydroxyalkyl starch containing a predetermined amount of quaternary nitrogen by adding a predetermined mole of alkylene oxide thereto and then etherifying it with an etherification agent having a quaternary ammonium group. Now, we have discovered that these difficulties can be completely eliminated and that by using this, a cosmetic product with excellent adsorption to hair and improved film flexibility can be obtained.Based on this knowledge, we have created the present invention. It came to this.

That is, the present invention provides a hydroxyalkyl starch obtained by adding 0.1 to 2 moles of alkylene oxide per anhydroglucose unit to starch, in which some of the hydroxyl groups have the general formula (R1 in the formula, R2,
R3 is an alkyl group having 1 to 3 carbon atoms, and Xθ is a monovalent anion.

) and a cationized hydroxyalkyl starch having a nitrogen content of 0.5 to 5% by weight. It is something.

The cationized hydroxyalkyl starch used in the present invention is obtained by adding 0.1 to 2 moles of alkylene oxide per anhydroglucose unit to starch, and is obtained by adding the general formula (in the formula Hal is a halogen atom, and it can be produced by reacting a compound represented by (R1, R2, R3 and Xθ have the same meanings as above).

As the alkylene oxide to be added to the starch, 1,2-alkylene oxide having 2 to 14 carbon atoms, ie, ethylene oxide, 1,2-propylene oxide, and 1*2-butylene oxide are used.

These alkylene oxides are used in such a proportion that the average number of moles added per anhydrous glycose unit of starch is in the range of 0.1 to 2, preferably 0.3 to 2.0. If the number of added moles is less than 0.1, the flexibility of the film that covers the skin and hair will be poor, resulting in poor feel and combability.If the number of added moles exceeds 2.0, the water absorption will be poor. This is undesirable because it increases in size and gives a sticky feeling after use.

Next, as the base starch for the cationized hydroxyalkyl starch in the present invention, any ordinary starch such as potato starch, Japanese starch, corn starch, etc. can be used. Normally, starch consists of amylose and amylopectin, and the amylose content is 30% by weight or less, but in recent years, due to breed improvement, starches with increased amylose content have appeared. In the present invention, such modified starch and amylose separated by a fractionation method or the like can also be used. Next, the reaction of the compound of the general formula (■) or (■)'' with the hydroxyalkyl starch can be carried out according to a known etherification method.

For example, in the presence of an alkaline catalyst, an aqueous suspension of hydroxyalkyl starch containing the general formula (■) or (■)''
This can be carried out by adding a compound of the above, causing a heating reaction, and neutralizing after the reaction is completed. In this way, quaternary ammonium groups are introduced into the hydroxyalkyl starch.

Examples of the compounds of the general formula (■) or (■)'' include glycidyl trialkylammonium salts and 3-halo 2-
Hydroxypropyltrialkylammonium salts, such as glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltripropylammonium chloride, glycidylethyldimethylammonium chloride, glycidyldiethylmethylammonium chloride and their corresponding bromides, iodides, and 3-chloro2 -Hydroxypropyltrimethylammonium chloride, 3-chloro2-hydroxypropyltriethylammonium chloride, 3-chloro2-hydroxypropyltripropylammonium chloride, 3-chloro2-hydroxypropylethyldimethylammonium chloride and their corresponding bromides and iodides can give.

The cationized hydroxyalkyl starch used in the cosmetic composition of the present invention needs to have a nitrogen content in the range of 0.5 to 5% by weight.

If the content is less than 0.5% by weight, the affinity for hair and skin will be low even if it is blended into cosmetics, and if it exceeds 5% by weight, the cosmetic will feel sticky when used. I don't like it because it looks like this. A particularly preferable range of nitrogen content is 1.0 to 3. Heel volume %. After the reaction is complete, the cationic hydroxyalkyl starch thus obtained is neutralized and then separated from the reaction solution by a conventional method. This is purified by reprecipitation or the like, if necessary. The cosmetic composition of the present invention can be obtained by blending a required amount of this cationized hydroxyalkyl starch into a hair cosmetic composition, a skin cosmetic composition, etc. having a known formulation.

Cosmetics are not limited to those mentioned above, but particularly preferred are cosmetics that can be washed off with water when used, such as cleansing creams, jumpers, and conditioners. The blending amount varies depending on the use and the like, but it is usually preferably in the range of 0.1 to 5% by weight. The cosmetics of the present invention may contain surfactants, oils such as hydrocarbons and fatty acid esters, hydrolyzed proteins, lanolin, lipids, vitamins, fragrances, pigments,
Conventionally used ingredients such as bactericides and hydrotropes can be blended. The cationized hydroxyalkyl starch used in the cosmetics of the present invention has the following characteristics. (a) Hydroxyalkylation of starch,
Furthermore, since it has been cationized by introducing a quaternary ammonium group, it has good affinity for hair and skin. (b) A complex salt is formed with an anionic surfactant and an amphoteric surfactant, and since this complex salt is dissolved in an aqueous surfactant solution, it can be used in combination with an anionic surfactant or an amphoteric surfactant.

(c) Excellent protective colloid effect.

(d) Good foam stability.

(e) Excellent film forming properties.

Therefore, cosmetics using this product have the following excellent effects.

(b) It has good hydrophilicity to hair and skin and has a large amount of adsorption.

(b) Even if an anionic or amphoteric surfactant is used in combination,
The performance of the cationized hydroxyalkyl starch is not impaired.

(c) Excellent emulsion stability and dispersion stability.

(d) Rich foaming can be sustained. (e) Provides a flexible film.

(F) (Because it has good adsorption and film-forming properties), it has excellent moisturizing properties, moisturizes the hair and skin, gives the hair firm flexibility, curl retention, and improves the shine of the hair. Improve.

Moreover, these effects are long-lasting. (G) It gives smoothness to the hair and skin, so it feels smooth after use, and the hair combs easily, creating a squeaky feeling (feeling that the hair gets tangled and stuck due to high friction). decreases.

Next, the present invention will be explained in more detail based on Examples and Reference Examples. Reference Example 1 60 f of potato starch is added to a glass pressure-resistant reactor containing 300 g of a 1% aqueous sodium hydroxide solution while stirring.

Ethylene oxide 33y was then diluted with nitrogen to 1.5
After introducing at a pressure of 9 nods, the reaction was carried out at 50°C.
The starch dissolves by heating. As the reaction progressed, a decrease in the pressure within the system was observed. After no decrease in pressure was observed, the reaction was further carried out at 50°C for 1 hour, the pressure in the reaction system was released, and 41.4y of glycidyltrimethylammonium chloride was added as an aqueous solution and the reaction was continued at 50°C for 3 hours.
Allow time to react. After the reaction is completed, 30 g of 10% aqueous hydrochloric acid solution is added and neutralization is carried out at room temperature for 1 hour. After neutralization, the reaction solution was poured into a large amount of methanol, and the reaction product was precipitated and separated. The obtained precipitate was washed three times with 500f of methanol each time, and then dried under reduced pressure to obtain reaction product 108f. The number of moles of ethylene oxide added to the cationically modified hydroxyethyl starch thus obtained is 1.3 moles per anhydroglucose unit, and the nitrogen content is 2. Capacity%
It was hot.

Reference Example 2 Cationized hydroxyalkyl starches having different contents of alkylene oxide and quaternary nitrogen groups were synthesized according to the method of Reference Example 1, and the flexibility of these films was measured.

The results are shown in Tables 1 and 2. The thickness of the film at this time was 0.025Tn! n, and the measurement conditions were 25
℃ and 50% RH. Incidentally, the sample code (E) was synthesized in Reference Example 1. Example 1 Using the cationized hydroxyalkyl starch obtained in Reference Example 2, Jumpu having the composition (4) shown in Table 3 was prepared.

Composition (B) is a composition prepared for comparison and does not contain cationized hydroxyalkyl starch.
From the results in Table 4, it can be seen that if the number of moles of alkylene oxide added is 0.1 mole or more per anhydroglucose unit, the catalysis is improved both during and after use.

(From a comparison of (a), (guchi), (c), (e), and (卜)). Moreover, if the nitrogen content is 0.5% by weight or more,
It can be seen that although the performance of Jumpu is improved, when the nitrogen content exceeds 5% by weight, it becomes more sticky after use, which becomes a negative factor in overall preference ((
From a comparison of e), (ru), ke), (yo) and (yu)).
Example 2 Cationized hydroxyalkyl starch (a), (ku), (c), (e), (g), (l), ke) from the samples of Reference Example 2 as cationized hydroxyalkyl starch I chose nine types: , (yo), and (evening).

These 9 types of Jumpu combined with composition (B) 1
Each type of Jumpu was used by one woman, and their performance in terms of lathering, sliminess, and softness of the skin after use was compared. The results are shown in Table 4. The values shown in Table 4 are the values obtained by subtracting the number of people who found composition (B) to be superior from the number of people who found composition (4) to be superior. A transparent type shampoo having the following composition was prepared using sample code (E).

This Jumpoo was superior to the Jumpoo using the same cationized hydroxyalkyl starch in Example 1 in terms of lathering during use, smoothness of the hair after use, ease of combing, and softness.

In addition, in the above composition, instead of the magnesium salt of lauryl ether sulfate, the same triethanolamine salt, sodium salt of lauryl sulfate, magnesium salt, triethanolamine salt, olefin sulfonate, etc. are used to prepare a similar jumpu. I was able to do that. It is also possible to use non-ionic active agents in this jumper. Example 3 Jumpu having the following composition was prepared using sample code (E) as a cationized hydroxyalkyl starch.

This Jumpoo showed the same performance as the Jumpoo of Example 2.

Example 4 Using sample code (e) as a cationized hydroxyalkyl starch, a burl-shaped jumpo having the following composition was prepared.

Eye catching talent k small
Slo P This Jumpu had superior hair smoothness and softness during and after use compared to products that did not contain cationized hydroxyalkyl starch.

Example 5 A transparent hair rinse having the following composition was prepared using sample code (E) as a cationized hydroxyalkyl starch.

This hair rinse had better texture during and after use than a hair rinse that did not contain cationized hydroxyalkyl starch.

Example 6 A cream-type hair rinse having the following composition was prepared using sample code (E) as a cationized hydroxyalkyl starch.

This hair rinse had better texture during and after use than a hair rinse that did not contain cationized hydroxyalkyl starch.

Example 7 A cleansing cream having the following composition was prepared using sample code (E) as a cationized hydroxyalkyl starch.

Next, this cream and a cream containing no cationized hydroxyalkyl starch were used by 15 women each, and their performance in terms of spreadability, oily feel, moisturizing feel, smoothness, etc. was evaluated.

The results are shown in Table 5. However, I in the table indicates that the cream of this example is superior, ■ indicates that the cream that does not contain cationized hydroxyalkyl starch is superior, and ■ indicates that there is no difference between the two. meaning, each number is a number of people. As is clear from this table, the cream of the present invention spreads better than the cream that does not contain cationized hydroxyalkyl starch, and has an excellent oily feel during use.

Example 8 A neutral cream having the following composition was prepared using sample code (E) as a cationized hydroxyalkyl starch.

This cream had superior smoothness and moisturizing feeling compared to a cream that did not contain cationized hydroxyalkyl starch, and the effect lasted for a long time.

Comparative Example In order to compare the effects of the cationically modified starch used in the present invention, a polymerization degree of about 15001 was prepared according to the method of Example 7 described in Japanese Patent Publication No. 45-20318.
Average number of moles of ethylene oxide added: 1.65. Nitrogen content 1. A cationically modified hydroxycellulose with a weight of % was produced.

Next, Jumpoo (4) of the present invention obtained in Example 1 and Jumpoo (4) containing 1 part by weight of the above cation-modified hydroxyethyl cellulose instead of 1 part by weight of the cationized hydroxyalkyl starch in Jumpoo (4) were added.
B) were prepared and used by 15 women to evaluate their performance.

The results are shown in Table 6. However, in Table 6, 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 hydroxylalkyl starch of the present invention is excellent in terms of non-stickiness after use and ease of combing.

Claims (1)

[Claims] 1.0.1 per anhydroglucose unit for starch
In hydroxyalkyl starch formed by adding ~2 moles of alkylene oxide, some of the hydroxyl groups therein have the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R_1, R_2, R_3 in the formula are carbon numbers 1 to 3 alkyl groups, and X■ is a monovalent anion), and has a nitrogen content of 0.
A cosmetic with good affinity, characterized by containing 2 to 5% by weight of cationized hydroxyalkyl starch. 2 Alkylene oxide is ethylene oxide, 1,2-
The cosmetic according to claim 1, which is propylene oxide or 1,2-butylene oxide.