JP4051016B2 - Moisturizer composition - Google Patents

Description

  The present invention relates to a humectant composition containing a copolymer having a urea residue and a sugar residue. More specifically, the present invention relates to a humectant composition that can be suitably used for cosmetics, medicines, and the like.

  Urea and saccharides are known as compounds deeply involved in water retention in human skin. Urea is strongly bound to water molecules by hydrogen bonds, and prevents water from scattering. Since saccharides also have many hydroxyl groups, they are combined with water molecules to prevent water from scattering. Sensitive skin and atopic dermatitis skin are dry skin with little moisture, and moisturizing compounds such as urea and saccharides are indispensable ingredients for care cosmetics.

However, since urea is irritating to the skin, it cannot be formulated in a large amount. In addition, since saccharides have a sticky feeling when used, there is a great restriction on blending. Therefore, there is a need for a moisturizer that contains urea and non-sticky saccharides that have excellent moisturizing properties and are not irritating.
JP-A-5-301812 (Claim 1) JP-A-8-268860 (Claim 1) JP 2000-86453 A (Claim 1)

  An object of the present invention is to provide a moisturizing composition that is excellent in moisturizing properties, has little irritation to the skin, and does not have a sticky feeling.

  Furthermore, the other object of this invention is to provide the cosmetics or medicine containing the said moisturizing composition.

That is, the gist of the present invention is as follows.
[1] Formula (I):

Urea ethyl methacrylate (A) represented by the formula (II):

A copolymer obtained by polymerizing a monomer composition containing the glucosylurea ethyl methacrylate (B) represented by the formula (B) with a weight ratio of (1/99 to 25/75) [(A) / (B)] And a cosmetic or medicine containing the moisturizing composition according to [1] above.

  The humectant composition of the present invention has a urea residue and a glucosamine residue in the side chain, and has an excellent effect that it has excellent moisturizing properties, little irritation to the skin, and no sticky feeling. Furthermore, the humectant composition of the present invention can be suitably used for pharmaceuticals such as cosmetics, pharmaceuticals, and quasi drugs, utilizing the characteristics.

  The humectant composition of the present invention has the formula (I):

Urea ethyl methacrylate (A) [hereinafter referred to as monomer (A)] and formula (II):

It contains a copolymer obtained by polymerizing a monomer composition containing glucosyl urea ethyl methacrylate (B) [hereinafter referred to as monomer (B)]. Such a copolymer exhibits excellent moisturizing properties without accompanying urea-specific irritation and saccharide-specific stickiness despite having urea and glucosamine residues in the side chain. It is.

  The weight ratio [monomer (A) / monomer (B)] of the monomer (A) to the monomer (B) in the monomer composition is 1/99 to 25/75 from the viewpoint of usability and the difficulty in synthesis. , Preferably 5/95 to 25/75.

  In the present invention, the monomer composition includes, in addition to the monomer (A) and the monomer (B), the formula (III):

Monomer (C) represented by the following (hereinafter referred to as monomer (C)) and formula (IV):

It is preferable that at least one monomer selected from the group consisting of a betaine monomer (D) represented by the following [hereinafter referred to as a monomer (D)] is used.

In the formula (III), R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ each independently represents an alkylene group having 2 to 4 carbon atoms. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a phenyl group. X represents an oxygen atom or NH. m and n each independently represent 0 or an integer of 1 to 50 (provided that m and n are not 0 at the same time).

  Specific examples of the monomer (C) include methyl carbitol (meth) acrylate, methyl carbitol (meth) acrylamide, ethyl carbitol (meth) acrylate, ethyl carbitol (meth) acrylamide, hydroxydiethylene glycol (meth) acrylate, hydroxy Diethylene glycol (meth) acrylamide, methoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylamide, hydroxy polyethylene glycol (meth) acrylate, hydroxy polyethylene glycol (meth) acrylamide, methoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) Acrylamide, ethoxypolyethylene glycol (meth) acrylate Ethoxypolyethyleneglycol (meth) acrylamide, phenoxypolyethyleneglycol (meth) acrylate, phenoxypolyethyleneglycol (meth) acrylamide, methoxymethyl (meth) acrylate, methoxymethyl (meth) acrylamide, methoxyethyl (meth) acrylate, methoxyethyl ( Examples include meth) acrylamide, ethoxymethyl (meth) acrylate, ethoxymethyl (meth) acrylamide, ethoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylamide, and the like. Among these, formula (IIIa):

(In the formula, n ′ represents 5 to 25, and R ¹ is the same as above)
The methoxypolyethylene glycol (meth) acrylate represented by these is preferable.

In the formula (IV), R ¹ and X are the same as described above. R ⁵ represents an alkylene group having 1 to 8 carbon atoms, preferably an ethyl group. R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. R ⁸ represents an alkylene group having 1 to 4 carbon atoms, preferably a methylene group.

  Specific examples of the monomer (D) include N- (meth) acryloyloxymethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloyloxyethyl-N, N-dimethylammonium- α-N-methylcarboxybetaine, N- (meth) acryloyloxypropyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloyloxymethyl-N, N-diethylammonium-α- N-methylcarboxybetaine, N- (meth) acryloyloxyethyl-N, N-diethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloyloxypropyl-N, N-diethylammonium-α-N- And methyl carboxybetaine.

  The total content of one or more monomers selected from the group consisting of the monomer (C) and the monomer (D) in the monomer composition is 100 parts by weight based on the total amount of the monomer (A) and the monomer (B). From the viewpoints of usability, feel when attached to the skin, and moisture retention, 50 to 400 parts by weight is preferable, and 75 to 350 parts by weight is more preferable.

  The weight ratio [monomer (C) / monomer (D)] of the monomer (C) and the monomer (D) in the monomer composition is 1/99 from the viewpoint of usability, feel when attached to the skin, and moisture retention. -99/1 are preferable and 20 / 80-80 / 20 are more preferable.

  Polymerization of the monomer composition containing the monomer (A) and the monomer (B) or the monomer (C) and / or the monomer (D) in addition to the monomer (A) and the monomer (B) uses water or an organic solvent. Can be carried out by solution polymerization or the like. For example, after the monomer composition is sufficiently dissolved in purified water or an organic solvent, the monomer can be polymerized by adding a polymerization initiator and stirring in an inert gas atmosphere such as nitrogen gas.

  Examples of organic solvents include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; alkyl ethers such as diethyl ether and tetrahydrofuran; and normal solution polymerization such as water. What is used can be used without particular limitation.

  When the polymerization is carried out in water or an organic solvent, the concentration of the monomer composition is preferably about 5 to 80% by weight.

  As polymerization initiators, conventional azo polymerization initiators such as azoisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, peroxide polymerization initiators, etc. Can be used without any particular limitation. The amount of the polymerization initiator is preferably about 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer composition.

  For the polymerization of the monomer composition, a chain transfer agent may be used as necessary. As the chain transfer agent, a compound having a mercaptan group such as lauryl mercaptan, dodecyl mercaptan or thioglycerol, an inorganic salt such as sodium hypophosphite or sodium bisulfite can be used without particular limitation. The amount of the chain transfer agent is preferably about 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer composition.

  The polymerization temperature varies depending on the type of polymerization initiator to be used, and thus cannot be determined unconditionally. However, it is usually preferable to use the 10-hour half-life temperature of the polymerization initiator. The polymerization time is desirably 2 hours or more, preferably about 2 to 24 hours, in order to eliminate the possibility of incomplete copolymerization and unreacted monomers remaining. The presence or absence of the unreacted monomer can be confirmed by a general analysis method such as the PSDB method (diodor persulfate pyridine method).

  The moisturizing composition of the present invention containing the copolymer thus obtained assists the skin barrier function by forming a film, and retains moisture under the influence of glucosamine residues and urea residues. Has properties. The film is less uncomfortable with the skin and has rheological properties suitable as a protective film. Furthermore, the moisturizing composition of the present invention has reduced irritation and stickiness without impairing the moisturizing properties of urea and saccharides, and has excellent properties such as smoothness, glossiness, moisture absorption, and biocompatibility. Have

  Since the content of the copolymer in the humectant composition of the present invention varies depending on the use application, etc., it cannot be determined unconditionally. For example, when the copolymer is produced by the solution polymerization, the type of solvent used Depending on the case, the polymerized solution can be used as a moisturizing composition as it is.

  The humectant composition of the present invention can be appropriately blended with a known humectant and can be used in a wide range. Therefore, the present invention further provides a cosmetic and a medicine containing the humectant composition of the present invention.

  Examples of cosmetics include scalp and hair cosmetics, body care cosmetics, and the like.

  As the cosmetic for scalp and hair, forms such as hair tonic, pomade, hair spray, hair mist, mousse, gel, hair wax, shampoo, rinse, treatment, hair cream and the like are used.

  Body care cosmetics include various lotions such as astringent lotions, various lotions such as after shave lotions, various creams such as emulsions, massage creams and nutritional creams, eye packs and paste-type rinse packs. Various forms such as pack agents are used.

  Examples of the medicine include a skin external preparation such as a sheet and cream, a hair color such as a cream and wax, a pharmaceutical such as a permanent agent, and a quasi-drug.

  In addition to the humectant composition of the present invention, arbitrary ingredients can be used in cosmetics and medicines depending on the purpose of use. For example, emulsifiers, fragrances, preservatives, pigments, and, if necessary, nutrients, humectants, UV inhibitors, hair restorers, and the like can be appropriately blended according to conventional methods.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

Production Example 1
After cooling 56 g (1.0 mol) of 30% aqueous ammonia to 10 ° C. in a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device, 155 g of methacryloxyethyl isocyanate ( Showa Denko KK, Karenz MOI) was mixed. The reaction solution became uniform and transparent as the reaction progressed, and finally white crystals were precipitated.
The precipitated white crystals are filtered, washed several times with acetone, and then dried under reduced pressure to obtain 170 g (yield: 90%) of urea ethyl methacrylate represented by the above formula (I) in the form of a white powder. Obtained.

  It was confirmed by the following physical properties that the obtained white crystals were urea ethyl methacrylate represented by the formula (I).

¹ H-NMR: δ = 1.949 ppm (3H, s, CH ₃ ),
3.466 to 3.522 ppm (2H, m, O—CH ₂ —),
4.211 ~4.261 ppm (2H, m, -C H 2 -NH),
4.593 ppm (1H, broad, -N H -CO-NH 2),
5.586-5.605 ppm (1H, m, CH),
6.125 ppm (1H, s, CH)

Production Example 2
100 g (0.4638 mol) of glucosamine hydrochloride and 267 g of purified water were mixed in a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer, and cooled to 10 ° C. Roxyethyl isocyanate (produced by Showa Denko, Karenz MOI) was mixed, and while stirring the heterogeneous solvent, 38 g (0.4638 mol) of 50 wt% sodium hydroxide was maintained at a reaction temperature of 10 ° C. over 30 minutes. It was dripped. The reaction solution became uniform and transparent as the reaction proceeded, and finally white crystals were precipitated.
The precipitated white crystals were filtered, washed several times with acetone, and then dried under reduced pressure to obtain 90 g (yield 62%) of glucosylurea ethyl methacrylate represented by the above formula (II) in the form of a white powder. Obtained.

  It was confirmed by the following physical properties that the obtained white crystals were glucosyl urea ethyl methacrylate represented by the formula (II).

Melting point: 300 ° C or higher
¹ H-NMR: δ = 1.765 ppm (3H, s, CH ₃ ),
3.291-3.330 ppm (4H, m, glucose),
3.498 ~3.517 ppm (2H, m, CH 2),
3.600-3.704 ppm (3H, m, glucose),
4.060 ~4.094 ppm (2H, m, CH 2),
5.561 ppm (1H, s, CH),
5.977 ppm (1H, s, CH)
MS: Molecular weight 334
^{IR: 1100cm -1, 1140cm -1,} 1395cm -1, 1580cm -1, 1635cm -1, 1725cm -1, 2900cm -1, 2950cm -1, 3360cm -1
UV: 195nm
Elemental analysis (monohydrate, 1NaCl):
Theoretical values: C, 38.01; H, 5.89; N, 6.82; Cl, 8.63;
Na, 5.60; O, 35.05
Found: C, 37.85; H, 5.13; N, 6.82

Examples 1-7
The raw material monomers shown in Table 1 are added and mixed in a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device so that the concentration of the raw material monomers becomes 10% by weight. Purified water was added to the solution to completely dissolve the raw material monomer.
Next, 0.1 part by weight of methyl azobisisobutyrate (manufactured by Wako Pure Chemicals, V-601) as a polymerization initiator was added to the obtained solution with respect to 100 parts by weight of the raw material monomers, and the mixture was stirred at 80 ° C. for 8 hours. Then, the polymerization was completed, and a 10% by weight copolymer solution was obtained as a humectant composition.

Comparative Example 1
A moisturizer composition was obtained by dissolving 5 g of urea in 100 g of purified water.

Comparative Example 2
A moisturizer composition was obtained by dissolving 5 g of hyaluronic acid in 100 g of purified water.

Test Examples The moisturizer compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were applied to the forearms of five subjects, and after 30 minutes, sensory evaluation was performed for irritation, stickiness, and moisturizing properties. The average value was obtained. The results are shown in Table 2.

[Irritation]
○: Not irritating.
Δ: Slightly irritating.
X: There is irritation.

[A feeling of stickiness]
○: There is no stickiness.
Δ: Slightly sticky.
X: There is a sticky feeling.

[Moisture retention]
○: Skin becomes moist than before application.
Δ: Skin becomes slightly moist than before application.
X: Same as before application.

  From the above results, it can be seen that the moisturizing compositions of Examples 1 to 7 have no irritation and stickiness and high moisturizing properties as compared with Comparative Examples 1 and 2.

  The humectant composition of the present invention can be suitably used for cosmetics, medicines and the like.

Claims (3)

Formula (I):

Urea ethyl methacrylate (A) represented by the formula (II):

A copolymer obtained by polymerizing a monomer composition containing the glucosylurea ethyl methacrylate (B) represented by the formula (B) with a weight ratio of (1/99 to 25/75) [(A) / (B)] A humectant composition. In addition to the monomer composition, the formula (III):

Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently an alkylene group having 2 to 4 carbon atoms, R ⁴ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a phenyl group, X is an oxygen atom or NH, m and n are each independently 0 or an integer of 1 to 50 (provided that m and n are not 0 at the same time)
Monomer (C) and formula (IV):

(Wherein R ⁵ is an alkylene group having 1 to 8 carbon atoms, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms, R ⁸ is an alkylene group having 1 to 4 carbon atoms, R ¹ and X are the same as above)
One or more monomers selected from the group consisting of betaine monomers (D) represented by the formula (B) are contained in an amount of 50 to 400 parts by weight with respect to 100 parts by weight as a total of (A) and (B). Item 2. A humectant composition according to Item 1.   A cosmetic or pharmaceutical comprising the humectant composition according to claim 1 or 2.