DE3511135A1 - HUMIDIFIER - Google Patents

Description

Humectants

The invention relates to a new humectant / particularly an outstanding humectant Moisture retention capacity with a special water-soluble silicon compound and a water-soluble one Polymer.

The skin is an interface between the living body and the external environment and acts as a protection of the living body against, for example, moisture, sun rays, microorganisms, chemicals and mechanical or physical stimuli. In addition, it maintains the homeostasis of living bodies through appropriate ones Cessation of water evaporation from the living body. The outermost layer of skin is found a corneal layer that usually holds a suitable amount of moisture. But when the corneal layer does not retain a suitable amount of moisture due to external or internal circumstances, the skin becomes dry and rough. This in turn leads to the fact that the corneal layer is theirs can no longer fulfill the function described, since the flexibility and elasticity of the skin deteriorates. To be able to counteract this phenomenon, it is necessary to add moisture to the corneal layer or to "anchor" in this or excessive evaporation of moisture from the corneal

layer to prevent. Consequently, humectants are commonly used in skin treatment and cosmetics used.

Because of their good skin affinity and their ability to convey a pleasant feeling when applied, propylene glycol, glycerine, sodium pyrrolidone carboxylate, Sodium lactate and sorbitol are used in cosmetics in large quantities. Disadvantageous to this customary Moisturizing agents are, however, that the skin can feel sticky after their application and that the moisture contained in the skin - in an undesirable manner - in those containing such moisturizers Cosmetics migrate. In certain cases, this leads to the application of such Cosmetics in conditions of relatively low humidity cause dehydration of the skin.

Recently, compounds with a moisturizing effect, which are also found in the skin, for example mucopolysaccharides such as chondroitin sulfate, Hyaluronic acid, mucoitin sulfate, charonin sulfate, Collagen and polypeptides. With the help of such compounds, skin aging can be up to one prevent to a certain extent, but their moisture-preserving effect still leaves much to be desired.

The object of the invention was to avoid it of the disadvantages of conventional humidifying agents outlined to indicate a humidifying agent that at its application does not make the skin feel sticky and has excellent moisture retention has on the skin.

The subject of the invention is thus a humidifying agent

tel off

(A) a silicon compound having at least one silanol group in its molecule and

(B) a water-soluble polymer.

Silicon compounds which can be used as component (A) in a humectant according to the invention are suitable those with at least one silanol group in their

₁ Q molecule. Examples of such silicon compounds are monosilanol compounds with one silicon atom in their molecule and polysilanol compounds with two or more silicon atoms in their molecule, preferably silanol compounds with 1 to 3 silicon atom (s). Into the-

j5 are particularly suitable as component (A) of one according to the invention Humectant silanol compounds of the formula:

R _n Si (OH) ₄ _ _n (I)

wherein R represents an alkyl group with 1 to 6 carbon atoms, an aralkyl group with 6 to 11 carbon atoms, an alkenyl group with 2 to 7 carbon atoms or an alkoxy group with 1 to 6 carbon atoms, where in the case that η = 2 or 3, the different R ¹ S can be the same or different, and η = 0 or an integer from 1 to 3. Some of the hydrogen atoms of the hydroxyl groups of the silanol compounds (I) can also be replaced by basic substances, for example alkali metals, alkaline earth metals or amines be replaced.

Typical silanol compounds of the general formula (I) are silanol, trimethylsilanol, dimethylsilanediol, Methylethylsilanediol, methylsilanetriol, triethylsilanol,

Diethylsilanediol, Ethylsilanetriol, Di-n-propylsilanediol, Diisopropylsilanediol, di-n-butylsilanediol, diisobutylsilanediol, Di-tert-butylsilanediol, diallylsilanediol / Triphenylsilanol, diphenylsilanediol, phenylsilanetriol, Methylcyclohexylsilanediol and dicyclohexylsilanediol. Examples of polysilanol compounds are Tetramethyldisiloxane-1,3-diol, tetramethyldisilmethylene-1,3-diol, Tetramethyldisilethylene-1,4-diol and bis (methylvinyl) -disiloxanediol.

The silanol compounds mentioned are usually unstable and easily polymerize, but they will when used in combination with the other component (B), i.e. the water-soluble polymer, stabilized. The stabilization mechanism of the silanol compounds has not yet been fully clarified, presumably however, the silanol compounds are formed by the formation of hydrogen bonds between SiOH in the Stabilized silanol compounds and -OH groups and / or -NH "groups in the water-soluble polymer.

As component (B) in humectants according to the invention usable water-soluble polymers are those with at least a hydroxyl group and / or at least one amino group. Examples of such water-soluble polymers are water-soluble biopolymers, such as mucopolysaccharides, and water-soluble proteins, cellulose derivatives, Starch derivatives and polyvinyl alcohols. These water-soluble polymers can be used alone or in any mixtures can be used.

"Mucopolysaccharides" are to be understood as meaning mucopolysaccharides in the general sense. Examples of such Mucopolysaccharides are neutral mucopolysaccharides,

acidic mucopolysaccharides such as hyaluronic acid, chondroitin, (chondroitin sulfate) and heparin, mucoproteins, glycoprotein and glucolipids.

Examples of water-soluble proteins are lipopeptides obtained by condensation of the amino groups of protein hydrolyzates and the carboxyl groups of fatty acids, soluble collagen, soluble elastin and soluble keratin.
10

Examples of cellulose derivatives are carboxymethyl cellulose (CMC), methyl cellulose (MC), and hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose (HPC).

Examples of protein derivatives are those with a higher water solubility than common proteins, e.g. partially hydrolyzed proteins, as well as the acetic acid derivatives, phosphoric acid derivatives and hydroxyalkyl derivatives of proteins.

Examples of polyvinyl alcohols are preferably those with a not very high degree of saponification (for example about 97 mol% or less), although their water solubility depends on their degree of polymerization and degree of saponification.

Of the water-soluble polymers mentioned, the water-soluble biopolymers, e.g. mucopolysaccharides and water-soluble proteins are particularly preferred, since these polymers are favorable as such develop pharmaceutical effects on the skin and have a moisture retention capacity.

The mixing ratio of silanol compound (s), i.e. component (A) / water-soluble polymer (s), i.e. Component (B) is in humidifying agents according to the invention

average is not critical, but the preferred weight ratio of component (A) / component (B) is 1/10 up to 10/1.

The humectants of the present invention are obtained by stabilizing the silanol compound (s), i. E. of component (A) through the water-soluble polymer (s), i.e. component (B). This stabilization can be achieved by incorporating the silanol compounds into aqueous solutions of the water-soluble ones Polymers. However, since the silanol compounds are unstable and easily polymerize, one serves preferably the process described below for the production of humectants according to the invention:

First, a relatively stable aqueous solution of a silanoate compound is prepared and then this mixed with an aqueous solution of the respective water-soluble polymer. Finally, the in the resulting solution containing silanoate compound, for example with a cation exchange resin from Η-type converted into the desired silanol compound, one containing the stabilized silanol compound inventive humectant obtained.

An aqueous solution of the silanoate compound is obtained, for example, according to the method described in "Journal of The Chemical Society ", 105, p. 679. In this process, a halogen-containing, hydrocarbon-substituted Silane derivative used as the starting derivative. The starting silane derivative is hydrolyzed and the hydrolyzate is shown in pure form. The pure hydrolyzate is then dissolved in an aqueous alkali metal hydroxide solution entered under

· "· ^: '"'"""35TIi 3

Chen conditions that there is at least one equivalent weight of a base, ie of the alkali metal hydroxide, based on 1 gram atom of silicon ^{in the} mixture obtained. On the other hand, the desired aqueous solution of a silanoate compound is also obtained by introducing a halogen-containing, hydrocarbon-substituted silane derivative into an aqueous solution of an alkali metal hydroxide in which the base, ie the alkali metal hydroxide, is in a total amount of the neutralization equivalent weight based on the amount of the halogen contained in the silanoate derivative , and at least one equivalent weight based on 1 gram atom of silicon is present.

As a starting material in the preparation of the aqueous solution of the silanoate compounds, halogen-containing, optionally hydrocarbon-substituted silane derivatives are, for example, silicon tetrachloride, Methyltrichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, Dimethyldichlorosilane, chloromethyltrichlorosilane, chlorophenyltrichlorosilane, methylcyclohexyldichlorosilane and benzyltrichlorosilane. With the help of the latter silanes one obtains aqueous solutions of mono-, di- or Trisilanoate compounds.

The concentration of components (A) and (B) in their aqueous solution is not critical, it is expediently 0.001-10% by weight, preferably 0.01-5% by weight.

Moisturizing agents according to the invention can be used in skin.

conditioning lotions and nutritional lotions, in aqueous cosmetic lotions, such as astringent lotions, Shaving lotions, body lotions and liquid packs, in creams, e.g. nourishing creams, eye creams, body creams,

Hand creams / massage creams, cooling creams and emollient Creams, in liquid creams, e.g. liquid nutritional creams, liquid body creams, liquid throat creams and liquid hand creams, in face packs and in other skin cosmetics. Furthermore, incorporate the humectants according to the invention into hair cosmetics, e.g. shampoos and conditioners.

If the humectants according to the invention are also used in the preparations mentioned, initially the other necessary ingredients entered in the humidifying agents or the humidifying agents in a suitable amount of aqueous solutions, aqueous dispersions or solid bases with the others necessary components are added. Although in these cosmetic formulations the amount of the inventive Moisturizing agents is not critical, they should be based on the cosmetic preparations their total weight, in an amount of 0.01-10% by weight, preferably 0.1-5% by weight (total amount of the Components (A) and (B)) are incorporated.

The following examples are intended to illustrate the invention in more detail. Unless otherwise stated, all of the data mean “percentages” - “percentages by weight”.

example 1

Methyltrichlorosilane is hydrolyzed in a beaker with distilled water. After the precipitate formed has been separated off, an equimolar amount of an aqueous sodium hydroxide solution is added to it. The reaction product is then brought into solution with stirring, an aqueous silanoate solution [CH ₃ Si (OH) ₃ ONa] having a silanoate concentration of

A4 " ^: ~ -""* · *" ·· "3Bi ti

10% in terms of silanol is obtained.

In addition, 100 ml of a 1% strength aqueous solution of purified commercial grade are placed in another beaker Hyaluronic acid, i.e. a mucopolysaccharide. The latter solution is mixed with 10 ml of the previously prepared 10% aqueous silanoate solution, whereupon the pH of the solution obtained is increased to 6.5 with the aid of a cation exchange resin of the Η type is set. After removing the cation exchanger, the solution obtained is diluted to about 200 ml, whereby a humectant is obtained. The solids concentration of the resulting humectant is (determined by vacuum drying) about 1%.

Example 2

Insoluble collagen obtained from calf skin is brought into solution with the help of pepsin in water, whereby a 4% aqueous solution of the purified, water-soluble Collagens.

80 ml of the solution obtained are mixed with 10 ml of the 10% strength aqueous silanoate solution prepared according to Example 1 added, whereupon the pH of the resulting solution with the help of a cation exchanger of the Η-type to 6.5 is set. The solution is then made up to 100 ml with water, using a humectant receives. Its solids concentration is (determined by vacuum drying) 5%.

example

By cutting out a commercially available pork rind, two square pieces of skin measuring 2 cm 2 cm are made

won.

In addition, various aqueous wetting agents are prepared according to Table I. 5

A given amount of the Applied humectants listed in Table I, whereupon the two pieces of skin from the pork skin in a desiccator at a relative humidity of 65% or 30% at room temperature Can be left for 24 hours.

Now the water content of the surface of the pork skin is determined by measuring the impedance. The results can be found in Table II. The impedance is determined with the aid of a commercially available impedance measuring device. The water content results from the impedance value with the help of a calibration curve. The specified is Average of both measured values.

TABLE I.

Sample No. humectant

A sodium pyrrolidone (5% aqueous solution) carboxylate

(5% aqueous solution)

_a0 C sorbitol (5% aqueous solution)

(1% aqueous solution) (solids content: 1%)

B. Glycerin C. Sorbitol D. Hyaluronic acid E. Humectants
according to example 1

Al * ^: - ^: "3511135 TABLE II Sample no. Water content (%) of the
Pork rind Skin surface of the 65% relative humidity
activity 30% relative humidity
activity A. 66 15th B. 29 7th C. 20th 4th D. 42 29 E. 68 66

From Table II it can be seen that the humectant stabilized with hyaluronic acid according to the invention is a Hyaluronic acid alone and other common humectants have superior excellent moisture retention properties shows.

Example 4

By cutting out pork skin, two square pieces of skin, each 2 cm χ 2 cm in size, are made

won.

The two pieces of skin from the pork skin are then for 5 minutes at room temperature in one according to the example 2 prepared aqueous humectant solution with a solids concentration of 5%, a 5% aqueous Collagen solution or immersed in water. Then the two pieces of skin from the pork skin become one

left desiccator kept at 50% relative humidity for 6 hours at room temperature. Finally, the water content of the surfaces of the pieces of skin from the pork skin is determined according to the example 3 determined by impedance measurement.

In the case of the humectant according to the invention according to Example 2, there is a 75% water content at which 5% aqueous collagen solution has a 55% water content and, in the case of water, a 5% water content.

example

According to Example 2, a 5% strength aqueous solution of a mixture of dimethylsilanediol and chondroitin sulfate acid is used B (weight ratio 1/4) prepared.

Using this humectant, a cosmetic lotion of the following composition is then made manufactured:

component

Dimethylsilanediol / Chondroitin Sulfuric Acid B

²⁵ propylene glycol ethanol

Methyl p-hydroxybenzoate disodium hydrogen phosphate

Perfume
^ O distilled water

If the cosmetic lotion obtained is applied to the skin of 20 female test persons, there is an improvement recorded in the feeling of moisture and smoothness. The degree of significance is 1%.

Salary ι 5 1 6th O ₁ 0, O ₁ (in %) ,1 , 06 , 2 rest

Example 6

According to Example 1, a humectant in the form of a 1% aqueous solution of a mixture is made Ethylsilanetriol and hyaluronic acid (weight ratio 1/1) prepared.

using the moisturizing agent obtained, an emollient cream of the following composition is prepared:
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Component content (in%)

Ethylsilanetriol / hyaluronic acid 1

liquid paraffin 6

Sgualan 3

Cetyl palmitate 2

Cetyl alcohol 2

Stearic acid 2

Antioxidant 3

distilled water remainder

If the emollient cream obtained is applied to the skin of 20 female test persons, there is an improvement achievable with a feeling of moisture and smoothness. The degree of significance is 1%.

B is ρ ie 1

According to Example 1, a humectant in the form of a 1% aqueous solution of a mixture is made Phenylsilanetriol and hyaluronic acid (weight ratio 1/1) prepared.

Using the moisturizing agent obtained, a hair shampoo of the following composition is prepared:

-Vf-

St (,

Component content (in%)

Phenylsilanetriol / hyaluronic acid sodium C -.- a-olefin sulfonate Triethanolamine lauryl sulfate

Perfume 0.1

distilled water remainder

The hair shampoo obtained shows an excellent moisture retention capacity for the hair.

example

According to Example 2, a humectant is used

in the form of a 2% aqueous solution of a mixture 15

prepared from trimethylsilanol / collagen (weight ratio 1 / 1.5).

Using the obtained humectant

becomes a hair conditioner of the following composition 20

manufactured:

component Salary (in%) Trimethylsilanol / collagen 2 commercial cationic top
area active agent 2 Cetyl alcohol 3 Stearyl ethoxylate
(Ethylene oxide addition product of
5 moles of ethylene oxide) 1 Perfume 0.1 distilled water rest

The hair conditioner obtained has an excellent ability to retain moisture on the hair.

Claims (7)

PATENT CLAIMS 1. Humidifier, characterized by (A) a silicon compound having at least one silanol group in its molecule and (B) a water-soluble polymer. 2. Moisturizing agent according to claim 1, characterized in that the silicon compound in its molecule Contains 1 to 3 silicon atom (s). 3. Moisturizing agent according to claim 1, characterized in that the polymer is at least one Contains hydroxyl and / or at least one amino group. 4. wetting agent according to claim 1, characterized in that the water-soluble polymer consists of consists of a water-soluble biopolymer. 5. humidifying agent according to claim 1, characterized in that that the silicon compound of the formula: RftSi (OH) ₄ _ _n (I) corresponds to where R represents an alkyl group with 1 to 6 carbon atom (s), an aralkyl group with 6 to 11 Carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkoxy group having 1 to 6 Carbon atom (s), with the proviso that in the case that η = 2 or 3, the various R ¹ S may be the same or different, and η = 0, 1, 2 or 3, where some of the hydrogen atoms of the hydroxyl groups Silanol compounds (I) can be replaced by a basic substance. 6. wetting agent according to claim 3, characterized in that the polymer consists of a mucopolysaccharide, a water-soluble protein, a cellulose derivative, a starch derivative and / or a polyvinyl alcohol. 7. wetting agent according to claim 1, characterized in that the weight ratio of component (A) / Component (B) is 1/10 to 10/1.