JPH11130822A - Hydrophilic polymer and humectant containing the same - Google Patents

Abstract

(57) Abstract: A hydrophilic polymer comprising a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) and having a weight average molecular weight of 500 to 500,000. A coalescence and a humectant containing the same. Embedded image [R ¹ and R ⁴ represent H or a methyl group, and X and Z represent-
NH- or -O- are shown, R ² and R ³ represents an alkyl group of a hydroxyl group which may be substituted by C1-10, Y is a divalent saturated hydroxyl groups may be substituted by C1-10 P represents a number of 2 to 5, and A represents a C2 to 4 alkylene group. [Effect] When applied to skin and hair, the present polymer has excellent moisturizing ability, its effect is not affected by sweat or water, lasts for a long time, and has a good feel. It is useful as a humectant for ingredients, cleaning compositions and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic polymer having excellent moisturizing ability, the effect of which is maintained for a long period of time even by perspiration or water, and even after washing, and which has a good feeling in use. Humectant.

[0002]

2. Description of the Related Art Conventionally, various humectants have been added to many cosmetics and cleaning compositions to impart a moist feeling to hair and skin. As such humectants, glycerin, propylene glycol, urea, alkylene oxide adducts of saccharides and the like are used.

[0003]

However, none of these humectants is necessarily satisfactory in terms of moisturizing property, feel, etc., and easily diffuses with sweat or water.
There was also a problem that the effect was not sustained. Furthermore, in cosmetics used after washing, such as rinsing and body rinsing, and in detergents containing a large amount of surfactants, most of them are often washed away, so that the original effects cannot be sufficiently exhibited.

[0004] Therefore, there has been a demand for a moisturizing agent which has excellent moisturizing properties and feel, and has a moisturizing effect for a long period of time even with sweat or water or even after washing.

[0005]

Under these circumstances, the present inventors have conducted intensive studies and as a result, have found that a polymer having a specific structural unit can be blended into various cosmetics and detergent compositions and used on the skin. In this case, the present inventors have found that while exhibiting excellent moisturizing properties, the effect is maintained for a long time and the feel is good, and the present invention has been completed.

That is, the present invention provides a hydrophilic polymer comprising a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), and having a weight average molecular weight of 500 to 500,000. It is intended to provide a humectant containing the same.

[0007]

Embedded image

[Wherein, R ¹ and R ⁴ each represent a hydrogen atom or a methyl group, X and Z each represent -NH- or -O-, and R ² and R ³ each represent a hydroxyl group. A represents an alkyl group having 1 to 10 carbon atoms, Y represents a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a hydroxyl group, p represents a number of 2 to 5, Represents an alkylene group having 2 to 4 carbon atoms. ]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), as the alkyl group having 1 to 10 carbon atoms which may be substituted by the hydroxyl group represented by R ² and R ³ , a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl,
Examples thereof include an octyl group, a nonyl group, a decyl group and a hydroxyethyl group, and a methyl group, an ethyl group and a hydroxyethyl group are particularly preferable. Examples of the divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted by the hydroxyl group represented by Y include a methylene group, an alkylene group and an alkylidene group, and include, for example, a methylene group, an ethylene group, and a trimethylene group. Group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, hydroxyethylene group, 2-hydroxyethylidene group, and the like. Groups are preferred. p
Represents a number of 2 to 5, particularly preferably 3. In the general formula (2), the alkylene group having 2 to 4 carbon atoms represented by A includes an ethylene group, a trimethylene group, a propylene group,
Examples thereof include a tetramethylene group, and an ethylene group is particularly preferable.

The weight composition ratio of the structural unit (1) to the structural unit (2) contained in the hydrophilic polymer of the present invention is not particularly limited, but may be from 10:90 to 90:10, in particular, 2: 1.
Those having a ratio of 0:80 to 80:20 have a high moisturizing ability and a good feel and are preferred. The hydrophilic polymer of the present invention includes any of a block copolymer, a random copolymer, an alternating copolymer and the like.

The hydrophilic polymer of the present invention needs to have a weight average molecular weight of 500 to 500,000.
It is preferably from 00 to 200,000 in terms of moisturizing ability and feel.

The hydrophilic polymer of the present invention can be produced, for example, according to the following reaction formula.

[0013]

Embedded image

[Wherein R ¹ , R ² , R ³ , R ⁴ , X,
Y, Z, A and p have the same meaning as described above, and m and n each represent an arbitrary positive number having a weight average molecular weight of 500 to 500,000. ]

That is, the monomers represented by the general formulas (1) 'and (2)' are copolymerized using a radical polymerization initiator in the presence of a polymerization solvent, whereby the monomers represented by the general formula (3) are obtained. The polymer of the present invention having the following structure can be obtained.

The monomer (1) 'used in this reaction is
For example, it can be produced according to the method described in JP-A-6-257348 and the like, and the monomer (2) 'can be produced, for example, in JP-A-4-305860 and JP-A-59-190.
It can be manufactured according to the method described in Japanese Patent Publication No. 280, etc. As the polymerization solvent used for the copolymerization, polar solvents such as water, methanol, ethanol, and dimethylformamide are preferable, and water is particularly preferable. As the radical polymerization initiator, an azo radical initiator such as V-50
Commercial products such as (manufactured by Wako Pure Chemical Industries) can be used.
The polymerization reaction is preferably performed at 30 to 100 ° C, particularly preferably at 40 to 80 ° C.

When the hydrophilic polymer of the present invention thus obtained is applied to skin or hair, it has excellent moisturizing ability and its effect lasts for a long time without being affected by sweat, water, etc. And is useful as a humectant for various cosmetics and cleaning compositions.

[0018]

EXAMPLES The present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Example 1 A separable flask equipped with a cooling tube was purged with nitrogen.
10.72 g of N- (3-acrylamidopropyl) -N-carboxymethyl-N, N-dimethylammonium hydroxide salt, 5 g of N- (2-hydroxyethyl) acrylamide, V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) 1327
g and 140 g of water were added, the temperature was raised to 50 ° C., and the reaction was performed for 9 hours. After completion of the polymerization, the polymerization solution was reprecipitated in 20 times the volume of acetone, and the precipitate was collected by filtration. The precipitate collected by filtration was dissolved in water and freeze-dried to obtain 13.3 g of a copolymer. As a result of NMR analysis, it was confirmed that the polymer had the following structure.

[0020]

Embedded image

NMR (200 MHz, D ₂ O, pp
m): 1.1-1.67 (4H, m , -C H 2 -CH- × 2) 1.67-2.0 (4H, m, -CH 2 -C H - × 2, -NH-CH 2 -C H 2 -CH ₂ -N (CH ₃ )
_{2 -) 2.9-3.28 (10H, m} , -NH-CH 2 -CH 2 -C H 2 -N (C H 3) 2 -, - C H 2 -CH 2 -O
H) 3.41-3.6 (4H, m, -NH-C H ₂ -CH ₂ -CH ₂ -N (CH ₃ ) ₂ -,-CH ₂ -C H ₂ -O
H) 3.74 (2H, s, -N (CH 3) 2 -C H 2 -COO -) Molecular weight (GPC, 0.2 M phosphate buffer, PEG terms): Mw = 7
10,000, Mn = 50,000 Composition ratio (from NMR): Structural unit (1) / Structural unit (2) = 62.1 wt% / 37.9 wt%

Example 2 After a separable flask equipped with a cooling tube was purged with nitrogen,
N- (3-acrylamidopropyl) -N-carboxymethyl-N, N-dimethylammonium hydroxide salt 3.45 g, N- (2-hydroxyethyl) acrylamide 11.55 g, V-50 (manufactured by Wako Pure Chemical Industries) 0.1
237 g and water 140 g were added, and the temperature was raised to 50 ° C.
A time reaction was performed. After completion of the polymerization, the polymerization solution was reprecipitated in 20 times the volume of acetone, and the precipitate was collected by filtration. After dissolving the precipitate collected by filtration in water and subjecting to freeze-drying, the copolymer 12.
8 g were obtained. As a result of NMR analysis, it was confirmed that the polymer had the following structure.

[0023]

Embedded image

NMR (200 MHz, D ₂ O, pp
m): 1.1-1.67 (4H, m , -C H 2 -CH- × 2) 1.67-2.0 (4H, m, -CH 2 -C H - × 2, -NH-CH 2 -C H 2 -CH ₂ -N (CH ₃ )
_{2 -) 2.9-3.28 (10H, m} , -NH-CH 2 -CH 2 -C H 2 -N (C H 3) 2 -, - C H 2 -CH 2 -O
H) 3.41-3.6 (4H, m, -NH-C H ₂ -CH ₂ -CH ₂ -N (CH ₃ ) ₂ -,-CH ₂ -C H ₂ -O
H) 3.74 (2H, s, -N (CH 3) 2 -C H 2 -COO -) Molecular weight (GPC, 0.2 M phosphate buffer, PEG terms): Mw = 5
10,000, Mn = 35,000 Composition ratio (from NMR): Structural unit (1) / Structural unit (2) = 20.7 wt% / 79.3 wt%

Example 3 After a separable flask equipped with a cooling tube was purged with nitrogen,
N- (3-acrylamidopropyl) -N-carboxymethyl-N, N-dimethylammonium hydroxide salt 13.5 g, N- (2-hydroxyethyl) acrylamide 1.52 g, V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.07
4 g and 140 g of water were added, the temperature was raised to 50 ° C., and the reaction was performed for 9 hours. After completion of the polymerization, the polymerization solution was reprecipitated in 20 times the volume of acetone, and the precipitate was collected by filtration. The precipitate collected by filtration was dissolved in water and freeze-dried, after which 16.2 g of the copolymer was obtained.
I got As a result of NMR analysis, it was confirmed that the polymer had the following structure.

[0026]

Embedded image

NMR (200 MHz, D ₂ O, pp
m): 1.1-1.67 (4H, m , -C H 2 -CH- × 2) 1.67-2.0 (4H, m, -CH 2 -C H - × 2, -NH-CH 2 -C H 2 -CH ₂ -N (CH ₃ )
_{2 -) 2.9-3.28 (10H, m} , -NH-CH 2 -CH 2 -C H 2 -N (C H 3) 2 -, - C H 2 -CH 2 -O
H) 3.41-3.6 (4H, m, -NH-C H ₂ -CH ₂ -CH ₂ -N (CH ₃ ) ₂ -,-CH ₂ -C H ₂ -O
H) 3.74 (2H, s, -N (CH 3) 2 -C H 2 -COO -) Molecular weight (GPC, 0.2 M phosphate buffer, PEG terms): Mw = 9
10,000, Mn = 80,000 Composition ratio (from NMR): Structural unit (1) / Structural unit (2) = 85.5 wt% / 14.5 wt%

Example 4 After a separable flask equipped with a cooling tube was purged with nitrogen,
10.76 g of N- (3-acryloylpropyl) -N-carboxymethyl-N, N-dimethylammonium hydroxide salt, 5 g of N- (2-hydroxyethyl) acrylamide, V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) 1327g
And 140 g of water were added, the temperature was raised to 50 ° C., and the reaction was performed for 9 hours. After completion of the polymerization, the polymerization solution was reprecipitated in 20 times the volume of acetone, and the precipitate was collected by filtration. The precipitate collected by filtration was dissolved in water and freeze-dried to obtain 13.5 g of a copolymer. As a result of NMR analysis, it was confirmed that the polymer had the following structure.

[0029]

Embedded image

NMR (200 MHz, D ₂ O, pp
m): 1.1-1.67 (4H, m , -C H 2 -CH- × 2) 1.67-2.0 (4H, m, -CH 2 -C H - × 2, -0-CH 2 -C H 2 -CH _{2 -N (CH 3) 2 -} ) 2.9-3.28 (10H, m, -O-CH 2 -CH 2 -C H 2 -N (C H 3) 2 -, - C H 2 -CH 2 -O
H) 3.41-3.6 (4H, m, -OC H 2 -CH 2 -CH 2 -N (CH 3) 2 -, - CH 2 -C H 2 -OH) 3.74 (2H, s, -N (CH 3 ) ₂ -C H ₂ -COO ^-) molecular weight (GPC, 0.2 M phosphate buffer, PEG terms): Mw = 7.5
10,000, Mn = 50,000 Composition ratio (from NMR): Structural unit (1) / Structural unit (2) = 87 wt% / 13 wt%

Example 5 After a separable flask equipped with a cooling tube was purged with nitrogen,
N- (3-methacrylamidopropyl) -N-carboxymethyl-N, N-dimethylammonium hydroxide salt 11.36 g, N- (2-hydroxyethyl) acrylamide 5 g, V-50 (manufactured by Wako Pure Chemical Industries) 0 .132
7 g and 140 g of water were added, the temperature was raised to 50 ° C., and the reaction was performed for 9 hours. After completion of the polymerization, the polymerization solution was reprecipitated in 20 times the volume of acetone, and the precipitate was collected by filtration. The precipitate collected by filtration was dissolved in water and freeze-dried, and then 14.5 g of a copolymer was obtained.
I got As a result of NMR analysis, it was confirmed that the polymer had the following structure.

[0032]

Embedded image

NMR (200 MHz, D ₂ O, pp
m): 1.1-1.67 (4H, m , -C H 2 -C (CH 3) - × 2) 1.67-2.0 (8H, m, -CH 2 -C (C H 3) - × 2, -NH- _{CH 2 -C H 2 -CH 2 -N} (CH
_{3) 2 -) 2.9-3.28 (10H} , m, -NH-CH 2 -CH 2 -C H 2 -N (C H 3) 2 -, - C H 2 -CH 2 -O
H) 3.41-3.6 (4H, m, -NH-C H ₂ -CH ₂ -CH ₂ -N (CH ₃ ) ₂ -,-CH ₂ -C H ₂ -O
H) 3.74 (2H, s, -N (CH 3) 2 -C H 2 -COO -) Molecular weight (GPC, 0.2 M phosphate buffer, PEG terms): Mw = 8
10,000, Mn = 70,000 Composition ratio (from NMR): Structural unit (1) / Structural unit (2) = 83.5 wt% / 16.5 wt%

Example 6 After a separable flask equipped with a cooling tube was purged with nitrogen,
N- (3-acrylamidopropyl) -N-carboxymethyl-N, N-dimethylammonium hydroxide salt 10 g, N- (5-hydroxypentyl) acrylamide 6 g, V-50 (manufactured by Wako Pure Chemical Industries) 0.089 g and 150 g of water was added, the temperature was raised to 50 ° C., and the reaction was performed for 9 hours. After the completion of the polymerization, the polymerization solution was reprecipitated in 20 times the volume of acetone, and the precipitate was collected by filtration. The precipitate collected by filtration was dissolved in water and freeze-dried to obtain 13.4 g of a copolymer.
As a result of NMR analysis, it was confirmed that the polymer had the following structure.

[0035]

Embedded image

NMR (200 MHz, D ₂ O, pp
m): 1.1-1.67 (10H, m , -C H 2 -CH- × 2, -CH 2 - (C H 2) 3 -CH 2 -OH) 1.67-2.0 (4H, m, -CH 2 -C H- × 2, -NH-CH ₂ -C H ₂ -CH ₂ -N (CH ₃ )
_{2 -) 2.9-3.28 (10H, m} , -NH-CH 2 -CH 2 -C H 2 -N (C H 3) 2 -, - C H 2 - (CH 2)
₃ -CH ₂ -OH) 3.41-3.6 (4H, m, -NH-C H ₂ -CH ₂ -CH ₂ -N (CH ₃ ) ₂ -,-CH _2- (CH ₂ ) _{3
-C H 2 -OH) 3.74 (2H} , s, -N (CH 3) 2 -C H 2 -COO -) Molecular weight (GPC, 0.2 M phosphate buffer, PEG terms): Mw = 5
10,000, Mn = 30,000 composition ratio (from NMR): structural unit (1) / structural unit (2) =
65.2wt% / 34.8wt%

Example 7 After a separable flask equipped with a cooling tube was purged with nitrogen,
N- (5-acrylamidopentyl) -N-carboxymethyl-N, N-dimethylammonium hydroxide salt 13.5 g, N- (2-hydroxyethyl) acrylamide 5.63 g, V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.10
6 g and 120 g of water were added, the temperature was raised to 50 ° C., and the reaction was performed for 9 hours. After the completion of the polymerization, the polymerization solution was reprecipitated in 20 times the volume of acetone, and the precipitate was collected by filtration. The precipitate obtained by filtration was dissolved in water and freeze-dried, and then 1.34 g of a copolymer was obtained.
I got As a result of NMR analysis, it was confirmed that the polymer had the following structure.

[0038]

Embedded image

NMR (200 MHz, D ₂ O, pp
m): 1.1-1.67 (10H, m , -C H 2 -CH- × 2, -NH-CH 2 - (C H 2) 3 -CH 2 -N (CH
₃ ) _2- ) 1.67-2.0 (4H, m, -CH ₂ -C H- × 2, -NH-CH ₂ -C H ₂ -CH ₂ -N (CH ₃ )
_2- ) 2.9-3.28 (10H, m, -NH-CH _2- (CH ₂ ) ₃ -C H ₂ -N (C H ₃ ) ₂ -,-C H ₂ -CH
₂ -OH) 3.41-3.6 (4H, m, -NH-C H _2- (CH ₂ ) ₃ -CH ₂ -N (CH ₃ ) ₂ -,-CH ₂ -C H ₂
-OH) 3.74 (2H, s, -N (CH 3) 2 -C H 2 -COO -) Molecular weight (GPC, 0.2 M phosphate buffer, PEG terms): Mw = 7
10,000, Mn = 50,000 Composition ratio (from NMR): Structural unit (1) / Structural unit (2) =
55wt% / 45wt%

Example 8 After a separable flask equipped with a cooling tube was purged with nitrogen,
N- (3-acrylamidopropyl) -N-carboxymethyl-N-methyl-N-hydroxyethylammonium hydroxide salt 10 g, N- (2-hydroxyethyl) acrylamide 4.14 g, V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.008 g and 127 g of water were added, the temperature was raised to 50 ° C, and the reaction was performed for 9 hours. After the polymerization is completed, the polymerization solution is
The precipitate was reprecipitated in 0 volumes of acetone, and the precipitate was collected by filtration. The precipitate collected by filtration was dissolved in water and freeze-dried to obtain 10 g of a copolymer. As a result of NMR analysis, it was confirmed that the polymer had the following structure.

[0041]

Embedded image

NMR (200 MHz, D ₂ O, pp
m): 1.1-1.67 (4H, m , -C H 2 -CH- × 2) 1.67-2.0 (4H, m, -CH 2 -C H - × 2, -NH-CH 2 -C H 2 -CH ₂ -N (CH ₃ )
_{2 -) 2.9-3.28 (12H, m} , -NH-CH 2 -CH 2 -C H 2 -N (C H 3) 2 -, - C H 2 -CH 2 -O
H × 2) 3.41-3.6 (6H, m, -NH-C H ₂ -CH ₂ -CH ₂ -N (CH ₃ ) ₂ -,-CH ₂ -C H ₂ -OH
× 2) 3.74 (2H, s , -N (CH 3) 2 -C H 2 -COO -) Molecular weight (GPC, 0.2 M phosphate buffer, PEG terms): Mw = 4
10,000, Mn = 30,000 composition ratio (from NMR): structural unit (1) / structural unit (2) =
59wt% / 41wt%

Test Example 1 Each component shown in Table 1 was evaluated for its moisture retention and feel. Table 1 shows the results.

<Humidity> A 0.5% aqueous solution of each sample is prepared, and 10 μl of a sample solution per 1 cm ² is applied to a bent portion of a human forearm conditioned at 20 ° C./44% RH, and left for 10 minutes. Before and after this processing, SKICON-
The conductance of the skin was measured using a 200 (manufactured by IBS), and the ratio “conductance after the treatment ÷ conductance before the treatment” was determined as the moisturizing ability. Perform the above operations for 10
The result of the repetition is shown as an average value. Rinse the treatment area with running water, wipe off the water with a towel, and
Leave it for a minute and measure the skin conductance in the same way. "Conductance after rinsing ÷ Conductance before rinsing"
Was determined as the moisturizing ability after rinsing.

<Feel> A 5% aqueous solution of potassium myristate containing 0.2% of each sample is prepared. Take 2 ml of the solution in the palm, whip well, rinse with running water and wipe off the water with a towel. The feeling of the palm after about 5 minutes was evaluated according to the following criteria. · Moist feeling ○: Moist △: Slightly moist ×: Not moist · Sticky ○: Not sticky △: Not very sticky ×: Sticky

[0046]

[Table 1]

As is evident from the results shown in Table 1, the product of the present invention exhibited excellent moisturizing ability, which was retained even after rinsing, and which gave a good feel.

[0048]

The hydrophilic polymer of the present invention, when applied to the skin or hair, has an excellent moisturizing ability and its effect lasts for a long time even with sweat or water, and even after washing. The feel at the time and after use is also good,
It is useful as a humectant for various cosmetics and cleaning compositions.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3/37 C11D 3/37

Claims (3)

[Claims] 1. A hydrophilic polymer comprising a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), and having a weight average molecular weight of 500 to 500,000. Embedded image [Wherein, R ¹ and R ⁴ each represent a hydrogen atom or a methyl group, X and Z each represent -NH- or -O-, and R ² and R ³ each represent a carbon atom which may be substituted by a hydroxyl group. Y represents an alkyl group having 1 to 10 carbon atoms, Y represents a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a hydroxyl group, p represents a number of 2 to 5, and A represents a carbon number. And represents 2 to 4 alkylene groups. ] 2. The hydrophilic polymer according to claim 1, wherein the weight composition ratio of the structural unit (1) to the structural unit (2) is from 10:90 to 90:10. 3. A humectant containing the hydrophilic polymer according to claim 1.