JPS63139106A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a hair cosmetic, containing an organopolyciloxane containing primary amino groups modified with a saccharide residue, capable of particularly improving glossing and gloss imparting effects with improved feeling of use and having effects on appearance of dark hair color. CONSTITUTION:A cosmetic, containing an organopolysiloxane (saccharide- modified silicone) containing primary amino groups modified with at least one saccharide residue. The saccharide-modified silicone is obtained by reacting an organopolysiloxane containing the primary amino groups with aldonic acid or a lactone compound in which uronic acid is intramolecularly dehydrated and cyclized at the amino groups, e.g. the compound expressed by the formula, and having effects on dark appearance of hair color. Thereby the hair color with depth can be shown by blending the above-mentioned saccharide-modified silicone. The amount of the saccharide-modified silicone is preferably 0.1-5wt% for the rinsing type and 0.05-3wt% for the nonrinsing type.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to organopolysiloxanes (hereinafter referred to as "sugar-modified silicones") containing a primary amino group modified with at least one sugar residue in one molecule. It relates to cosmetics containing (referred to as).

[Conventional technology]

Conventionally, oily zomethylborisiloxane (commonly known as silicone oil) has been applied to a wide variety of cosmetics because of its properties such as water repellency, lubricity, and gloss-imparting properties.

However, silicone oil has no affinity with water and is difficult to be emulsified in water, so there are limitations to its usage. In order to improve these drawbacks and provide new properties to silicone oil, we have developed so-called modified silicone cosmetics into which long-chain alkyl groups, flexible oxyalkylene groups, amino groups, carboxyl groups, or nixyl groups have been introduced. are being used.

[Problem that the invention seeks to solve]

Among these modified silicones? Lioxyalkylene-modified silicone is interesting because it has a nonionic surfactant structure in which the zomethyl siloxane portion is a hydrophobic group and the oxyalkylene portion is a hydrophilic group. However, since the hydrophilicity of the -lioxyalkylene moiety is relatively low,
? In order to make the lyoxyalkylene-modified silicone water-soluble and to balance the hydrophilic and hydrophobic properties, it is necessary to It is necessary to use a material with a high proportion of lyoxyalkylene moieties. But in such cases, what are the properties of silicone? There is a possibility that it will be canceled out by the properties of lyoxyalkylene. Further? What about lyoxyalkylene-modified silicone? It has a cloud point originating from the lyoxyalkylene moiety, which poses a problem in that the temperature at which it can be used is limited.

Therefore, there is a need for a modified silicone that has the properties of silicone oil and also contains a good amount of nonionic hydrophilic groups.

[Means for solving problems]

Under these circumstances, the present inventors have conducted extensive research and found that sugar-modified silicones in which at least one amino group of an organopolysiloxane having at least one amino group in one molecule is modified with a sugar residue. Has excellent properties,
The present invention was completed based on the discovery that extremely excellent cosmetics can be obtained by incorporating this into cosmetics.

That is, the present invention provides a cosmetic containing an organopolysiloxane containing a primary amino group modified with at least one sugar residue in one molecule.

31 The sugar-modified silicone used in the present invention is a new compound. It is produced by a method in which a cyclized lactone compound is reacted at the amino group (see Japanese Patent Application No. 60-207326).

Here, the organopolysiloxane containing at least one primary amino group in one molecule (hereinafter referred to as amino-modified silicone) may be linear or branched. The primary amino group contained may be introduced at either the terminal or internal site of the molecular chain. If a primary amino group is not present at the end, the end may be capped with a triorganosiloxane or with something else.

Such amino-modified silicones include those of the formula (I) type having an aminoalkyl group at both ends, those of the formula (6) type having an aminoalkyl group in the side chain, and those having two nitrogen atoms in the side chain. Examples include those of the formula (III) type having an aminoalkyl group with an atom.

(In the formula, R represents CH3 or OCH3, and n is 1 to 50
0 and m is a number from 0 to 500) Examples of lactone compounds (hereinafter referred to as sugar lactones) in which aldonic acids or uronic acids are each dehydrated and cyclized within the molecule include D-glucose, D-galactose, D-glucose, D-galactose, and -Allose, D-aldrose, D-mannose, D-/loose, D-idose,
Lactones of aldonic acids derived from reducing monosaccharides such as D-talose; lactones of aldonic acids derived from reducing trisaccharides such as maltose, cellobiose, 2-ctose, xylobiose, isomaltose, dicalose, cosobiose; maltotriose Lactones of aldonic acids derived from reducing trisaccharides such as , noQnose, and inmaltotriose; Lactones of aldonic acids derived from reducing oligosaccharides of tetrasaccharide or higher; D-glucuronic acid, L-iduronic acid, mannuron Examples include lactones of uronic acids such as acids. These can be used alone or as a mixture.

The reaction between the amino-modified silicone and the sugar lactone can be carried out by mixing or suspending both preferably in a solvent and heating the mixture under reflux with stirring. As the solvent, a polar solvent is preferable, and among them, lower alcohols such as methanol, ethanol, nf rono Q-nol, and inzorono-Q nol are preferably used. Note that the presence of water in the reaction system is undesirable because it decomposes the sugar lactone and produces the corresponding acid, and it is desirable to remove water from the reaction system and use a dry solvent.

The reaction time varies depending on the solvent used, but when a lower alcohol is used as the solvent, about 1 hour is possible, but 3 to 6 hours is preferable. The reaction temperature is preferably the reflux temperature of the reaction solvent used.

Examples of the refined silicone produced in this manner include the following.

■Those obtained from the amino-modified silicone of formula (I) and sugar lactone (R1 represents H or a sugar residue) ■Those obtained from the amino-modified silicone of formula (6) and sugar lactone (v) (R , R1, m and n are the same as above) (VI) obtained from amino-modified silicone of formula (m) and sugar lactone (wherein R, R1, m and n are the same as above) In the present invention, These sugar content silicones have an average molecular weight of 700 to 50,000, especially 1.0 for those of formula (■).
00-5,000, (B) type 700-50,0
00, especially 700 to 5,000, and those of formula (VI) are 7
00 to 50,000, particularly preferably 2,000 to 6,000.

The cosmetic composition of the present invention is prepared in exactly the same manner as conventional cosmetic compositions except that a sugar-containing silicone is added. Any cosmetic may be used, but especially when blended into hair cosmetics, it provides a pleasant feeling when used, improves luster imparting effects, and has a color-enhancing effect that makes hair appear darker.

The amount of sugar-containing silicone added to cosmetics is as follows: shampoo,
In the case of rinse-type products such as rinses, conditioners, hair dyes, etc., 0.01 to 10% by weight of the total composition (hereinafter referred to as
(simply indicated as excellent), especially 0.1 to 5%, and 0 for non-rinsing type products such as setting agents, blow-drying agents, and temporary hair dyes.
．． 01-8%, particularly 0.05-3% is preferred.

[Effect]

11. The effect of deepening hair color by the cosmetic silicone of the present invention is as follows. That is, sugar content silicone 1%
A water/ethanol (go/20) solution containing the following was applied to Chinese black hair and dried, and the L value before and after the treatment was measured using a colorimeter. The result is the change in lightness of hair before and after treatment [△
L-Lo (before treatment) Lt (after treatment)] shown in Table 1.

The larger the negative value of ΔL (the larger the positive value of −ΔL), the higher the color deepening effect. As is clear from Table 1, sugar-containing silicone has a high color-deepening effect, so if it is blended with it, hair color can be made to appear deeper even when treated with a hair dye containing the same amount of dye. can.

〔Example〕

Next, explanation will be given with reference to synthesis examples and examples.

Synthesis Example 1 Zomethyl substituted with 3-aminozolopyl at both ends? Resiloxane (Chisso Corporation [FM-3311゜Mw=1,000
)2Of, a mixture of 82 glucono-δ-lactone and 100 rnl methanol was refluxed for 6 hours. Methanol was distilled off under reduced pressure, and the residue was washed with water and then dried under reduced pressure to obtain 26f of siloxane (IV-6) having zomethyl substituted with 3-gluconamidozorogyl at both ends.

Compound IV-6 is a white, brittle solid that swells in the presence of water. The IR spectrum of compound IV-6 is 3400c
Absorption derived from the H-0 stretching vibration of the hydroxyl group of the sugar residue at m'''l, absorption derived from the C=O stretching vibration of the niamide at 16501M-', and 5i at 1110-1000ctn-1
The absorption derived from -0 stretching vibration is shown as a characteristic absorption. Furthermore, neutralization titration with hydrochloric acid using methanol as a solvent showed that there was no unreacted amino group in compound (1)-1.

Synthesis Example 2 6-amino-4-azahexyl modified zomethyl? Risiloxane (Shin-Etsu Chemical Exhibition KF393. Amino equivalent 360) 50
r, glucono-δ-lactone 131, methanol 200
fn1. The mixture was refluxed for 6 hours. Methanol was distilled off under reduced pressure, and the residue was dissolved in water. Next, the aqueous solution of the reaction mixture was put into a cellophane tube for dialysis, and gluconic acid derived from unreacted glucono-δ-lactone was removed by dialysis. Then, 6-gluconamido-4-azahexyl modified organo-destructive siloxane (V
602 pieces of I-1) were obtained.

Compound Vl-1 is a highly hygroscopic white powder and water-soluble. The IR spectrum of compound Vl-1 is 3400 an-
'Absorption derived from H-0 stretching vibration of hydroxyl group of sugar residue,
Characteristic absorptions were shown at 16503'''1 due to the C=0 stretching vibration of the Niamide, and from 1110 to 1001000a due to the 5i-0 stretching vibration. Neutralization with hydrochloric acid using methanol as a solvent. The amino value of compound VI-1 determined by titration was 52KQH peak. Compound VI-1 was determined by reacting with salicylaldehyde in methanol and then neutralizing titration with hydrochloric acid.
The amino value of 1 (derived only from secondary amino acids) is 61 K
OHxy/l. Assuming that only the primary amino group in KF 393 is reacted with glucono-δ-lactone, the expected amino value of the product is 62 KOH x g/
It is t. From these results, it can be said that only the primary amino group in KF393 was reacted.

Synthesis Example 3 3-aminozolopyl modified zomethyl? Resiloxane (Shin-Etsu Chemical Exhibition KF-865. Amino equivalent 4.400) 50 t
, maltobionolactone 5.0? , ethanol 200-
The mixture was refluxed for 5 hours. Ethanol was distilled off under reduced pressure, and the residue was washed with water and then dried under reduced pressure to obtain 3-
Maltopionamide zorovir modified dimethyl? 52 of resiloxane (V-1) was obtained.

The IR spectrum of compound v-1 is that of compound IV of synthesis example 1.
-6 and the IR spectra of compound Vl-1 of Synthesis Example 2, sugar residues, amide bonds, and zomethyl? It showed characteristic absorption derived from resiloxane units. Furthermore, neutralization titration with hydrochloric acid using methanol as a solvent showed that there was no unreacted amino group in compound v-1.

Example 1 A permanent hair dye solution having the following composition was prepared.

p-) Luenzoamino 1.0 (
%) m-cyaminoanisole sulfate 0.
05 Resolun 0.
5m-aminophenol 0,15
p-aminophenol 0.1 pholyoxyethylene (9) nonylphenyl ether 2
0.0 oleic acid
7.0 lauryl alcohol 8
．． 0 ethylene glycol motuptyl ether 9.
0PG 9
．． 0 Ammonia water (20 cm) 10
．． 0 edetic acid/4 Na
4.040% Sodium Sulfite 1.
Pentasaccharide-modified silicone (synthesis example 1) 0.
1 Water Balance A mixture of the above liquid No. 1 and an equal amount of 6% H2O2 water was applied to gray hair, left for 30 minutes, and then rinsed. The gray hair was dyed a deep chestnut color.

Example 2 A semi-permanent hair dye having the following composition was prepared.

HCRed 3 0.5(%
) Benzyl alcohol 3.
0PG 10
．． 0? Sodium lyoxyethylene lauryl sulfate (25
%) 3.0 Oleic acid zoethanolamide
2.0 fragrance
0.1 hydroxyethyl cellulose
0.3 modified silicone (synthesis example 1)
0.2 water
Balance The above semi-permanent hair dye was applied to black to dark brown hair, left for 20 minutes, and then rinsed, resulting in the hair being dyed a deep dark red.

Further, the above solution can be used as it is or as an aerosol.

Example 3 A temporary hair dye having the following composition was prepared.

Coca Foamer AM75 (30%) 8
．． 0(%) carbon black
1.0 ethanol
85.0 fragrance
0.3 modified silicone (synthesis example 2)
0.3 water
Balance Apply the above temporary hair dye to gray hair,
When dried, it turned a glossy black color. Also, can I use the above solution as it is? It may be sprayed as a spray or as an aerosol.

21-1 Example 4 A hair styling agent having the following composition was prepared.

Coca Foamer AM75 (30%) 5.
0 (→ethanol
10.0 Pre-lioxyethylene (9) nonylphenyl ether 0.5 Cetostearyltrimethylammonium chloride (23%) 0.5 Hydroxyethyl cellulose 0.3 Modified silicone (Synthesis example 2
) 0.15 water
When the above hair styling agent was applied to the hair and dried, the hair became smooth and shiny. Further, the above solution may be used as it is, or may be sprayed as a pump spray, or may be in the form of an aerosol.

Example 5 A shampoo having the following composition was prepared.

Ethylene glycol cystearate 0.5
(g) Oleic acid zoethanolamide
5.0 Citric acid 0.15 Disodium edetate 0.1 Methyl-Q Lapen 0.15 Sodium benzoate 0.15 Fragrance 0.3 Modified silicone (Synthesis example 3) 0.25 Purified water Balance Use the above shampoo As a result, the hair became shiny, shiny, and moisturized.

Example 6 A rinse having the following composition was prepared.

〆Lioxyethylene (SO) lanolin 1.7
Benzalkonium chloride 4.8 Disodium edetate 0.1 Flavor 0.35
Modified silicone (synthesis example 3) 0.
2. Purified Water Balance When I applied the above rinse after washing my hair and rinsed it, my hair felt glossy, shiny, and silky.

Example 7 After heating the skin lotion oil phase to 60°C and uniformly dissolving all ingredients, 3
Cool to 6°C and keep constant, then add to this oil phase at 36°C with stirring.
An alcohol phase adjusted to the above was added to emulsify. Thereafter, a 25°C aqueous phase was added to give a predetermined composition.

Claims (1)

[Claims] 1. A cosmetic comprising an organopolysiloxane containing in each molecule a primary amino group modified with at least one sugar residue.