JP7422541B2 - skin cleansing composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to skin cleansing compositions.

Conventionally, fatty acid soaps have been used as the main ingredient in cream detergents because of their excellent foaming, foam quality, and detergency. However, fatty acid soaps sometimes cause a squeaky feeling during rinsing, and because of their high detergency, the moisture content of the skin after washing decreases, resulting in a dry feeling. For this reason, skin cleansers that have excellent lathering and foam quality as well as excellent skin feel after cleansing are being investigated.
For example, Patent Document 1 discloses that potassium salt of a saturated fatty acid having 12 to 18 carbon atoms, a polymer whose constituent monomers are 2-methacryloyloxyethylphosphorylcholine and 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, glycerin, and water. It is described that the creamy detergent contained therein can produce a sufficient amount of creamy lather in a short lathering time, has an excellent feel during rinsing and after drying, and maintains a moisturizing feeling. Furthermore, Patent Document 2 describes a polymer whose constituent monomers are saturated fatty acids having 12 to 18 carbon atoms, allium hydroxide, alkyldimethylaminoacetic acid betaine, 2-methacryloyloxyethylphosphorylcholine, and butyl methacrylate, and dimethyldiallylammonium chloride. It is described that a creamy detergent containing a polymer, glycerin, and water as monomers has excellent foaming properties, foam creaminess, and skin feel during rinsing and after drying.

JP 2017-160133 Publication JP2015-24974A

The above-mentioned conventional detergent compositions were not sufficiently satisfactory in terms of foam quality, and the skin feel after washing, especially the moist feeling, was also not sufficient.

The present inventor has discovered that by using a specific phospholipid polymer in combination with a cationic polymer, polyethylene glycol, and a fatty acid salt, it is possible to obtain a foam with a thick feeling and good foam quality, and which is excellent for the skin after washing. The present invention was completed based on the discovery that a skin cleansing composition that provides a moisturizing feeling can be obtained.

The present invention comprises the following components (A), (B), (C) and (D):
(A) Phospholipid polymer containing 2-methacryloyloxyethylphosphorylcholine as a constituent monomer,
(B) cationic polymer,
(C) polyethylene glycol with an average molecular weight of 2,000 or more,
(D) A cream skin cleansing composition containing a fatty acid salt.

The skin cleansing composition of the present invention provides foam with a good foam quality that has a thick feeling, and this foam has a function of adsorbing dirt, and also provides an excellent moisturizing feeling on the skin after washing. It is something that can be done.
In the present invention, the thick feeling of foam indicates that the foam has contradictory rheological properties, such as being elastic and easy to expand.

In Test Example 1, the storage modulus (G') and loss modulus (G") measured for the foam of the skin cleansing compositions of Reference Examples 1 to 4 and Example 1 were determined from G"/G'. FIG. 2 is a diagram showing a loss tangent (tan δ).

Component (A) used in the present invention is a phospholipid polymer containing 2-methacryloyloxyethylphosphorylcholine as a constituent monomer.
The phospholipid polymer of component (A) contains 2-methacryloyloxyethylphosphorylcholine as a constituent monomer, and may be a copolymer with other monomers.
As other monomers, alkyl methacrylates are preferred, alkyl methacrylates in which the alkyl group has 4 to 20 carbon atoms are more preferred, and butyl methacrylate, stearyl methacrylate, etc. are more preferred.

More specifically, as component (A), polymethacryloyloxyethylphosphorylcholine, 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer, 2-methacryloyloxyethylphosphorylcholine/stearyl methacrylate copolymer, etc. are preferable.
For example, 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer is a polymer obtained by copolymerizing 2-methacryloyloxyethylphosphorylcholine and butyl methacrylate, and 2-methacryloyloxyethylphosphorylcholine in the polymer The molar ratio of butyl methacrylate is preferably 1:0.2 to 1:3. Further, the weight average molecular weight is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,000,000. Weight average molecular weight is measured by gel permeation chromatography.
In addition, Lipidure-HM (2-polymethacryloyloxyethylphosphorine choline), Lipidure-PMB (2-polymethacryloyloxyethylphosphorine/butyl methacrylate copolymer liquid), Lipidure-S (2-polymethacryloyloxyethylphosphorine) Commercially available products such as Lincholine/stearyl methacrylate copolymer (manufactured by NOF Corporation) can be used.

Component (A) can be used alone or in combination of two or more, and the content is 0.01% in the total composition from the viewpoint of thickening of the foam, ease of spreading, and moisturizing of the skin after washing. It is preferably at least 0.05% by mass, even more preferably at least 0.08% by mass, and from the viewpoint of thickening and moisturizing the skin after washing, it is 0.5% by mass. It is preferably at most 0.3% by mass, more preferably at most 0.2% by mass. Further, from the same viewpoint as above, the content of component (A) is preferably 0.01 to 0.5% by mass, more preferably 0.05 to 0.3% by mass, and 0.08 to 0.0% by mass in the total composition. .2% by mass is more preferred.

The cationic polymer of component (B) used in the present invention includes polymers containing amino groups, imidazolyl groups, pyridyl groups, salts thereof, quaternized salts, etc., and is not one used in ordinary skin cleansers. Either one is fine. In particular, from the viewpoint of moisturizing the skin after washing, thickening of the foam, and rapid foaming properties, the cationic charge density is preferably 2 meq/g or more, more preferably 3 to 7 meq/g.
Here, the cationic charge density refers to the number of equivalents (meq/g) of cationic charges in the monomer units constituting the polymer.

Such cationic polymers include, for example, homopolymers of dimethyldiallylammonium chloride; copolymers of dimethyldiallylammonium chloride with other monomers such as (meth)acrylic acid, (meth)acrylic acid ester, and (meth)acrylamide; Examples include polychlorinated methacryloyloxyethyltrimethylammonium chloride.

More specifically, a homopolymer of dimethyldiallylammonium chloride (Marquat 100; manufactured by NALCO, charge density 6.2 meq/g), a copolymer of dimethyldiallylammonium chloride and acrylic acid (Marquat 295; manufactured by NALCO, charge density 6.2 meq/g), Density 5.9meq/g), copolymer of dimethyldiallylammonium chloride and acrylic acid (Marquat 280; manufactured by NALCO, charge density 5.0meq/g), copolymer of dimethyldiallylammonium chloride and acrylamide (Marquat 550, Marquat 550PR; manufactured by NALCO, charge density 3.2 meq/g), polymethacryloyloxyethyltrimethylammonium chloride (manufactured by Kao Corporation, charge density 4.8 meq/g), copolymer of methylvinylimidazolium chloride and vinylpyrrolidone (Rubycut excellence; manufactured by BASF Corporation: charge density 6.1 meq/g, Rubycut FC550; manufactured by BASF Corporation: charge density 4.4 meq/g), and the like.

The cationic polymer of component (B) is a homopolymer of dimethyldiallylammonium chloride, a homopolymer of dimethyldiallylammonium chloride and acrylic acid, from the viewpoint of moisturizing the skin after washing, thickening of the foam, rapid foaming properties, and foam volume. Copolymers, dimethyldiallylammonium chloride and acrylamide copolymers are preferred.

Component (B) can be used alone or in combination of two or more, and the content is 0.01% by mass or more in the total composition from the viewpoint of foam elasticity and moisturizing feeling of the skin after washing. It is preferably 0.04% by mass or more, more preferably 0.06% by mass or more, and preferably 0.7% by mass or less from the viewpoint of ease of foam expansion and thick feeling, and 0.5% by mass. % or less, more preferably 0.4% by mass or less. Further, from the same viewpoint as above, the content of component (B) is preferably 0.01 to 0.7% by mass, more preferably 0.04 to 0.5% by mass, and 0.06 to 0.0% by mass in the total composition. .4% by mass is more preferred.

In the present invention, the mass ratio (A)/(B) of component (A) to component (B) is 0.1 or more from the viewpoint of ease of spreading the foam, thickening feeling, and moisturizing feeling of the skin after washing. It is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 1 or more, and from the viewpoint of foam elasticity and skin moisturizing feeling after washing, 5.5 or less. is preferable, 3 or less is more preferable, 2.5 or less is even more preferable, and 2 or less is even more preferable. Furthermore, from the above viewpoint, the mass ratio (A)/(B) of component (A) to component (B) is preferably 0.1 to 5.5, more preferably 0.2 to 3, and 0.4 -2.5 is more preferred, and 1-2 is even more preferred.

The polyethylene glycol used as component (C) in the present invention may be any polyethylene glycol used in ordinary skin cleansers, and from the viewpoint of foam elasticity and moisturizing feeling on the skin after washing, the polyethylene glycol has an average molecular weight of 2,000. The average molecular weight is preferably 4,000 or more, more preferably 6,000 or more, and from the viewpoint of ease of foam expansion and stability, the average molecular weight is preferably 200,000 or less, and 150,000 or less. is preferable, and 100,000 or less is more preferable. In addition, from the above viewpoint, the polyethylene glycol of component (C) preferably has an average molecular weight of 2,000 to 200,000, more preferably an average molecular weight of 4,000 to 150,000, and an average molecular weight of 6,000 to 100,000. is even more preferable.

Component (C) can be used alone or in combination of two or more, and the content is 0.1% by mass in the total composition from the viewpoint of foam elasticity, thickening feeling, and moisturizing feeling of the skin after washing. It is preferably at least 0.5% by mass, more preferably at least 0.7% by mass, and from the viewpoint of ease of foam expansion, thickening and foaming, it is preferably at most 8% by mass. The content is more preferably 5% by mass or less, and even more preferably 3% by mass or less. Further, from the same viewpoint as above, the content of component (C) is preferably 0.1 to 8% by mass in the total composition, more preferably 0.5 to 5% by mass, and furthermore 0.7 to 3% by mass. preferable.

Further, the mass ratio of component (C) in the total polyhydric alcohol containing component (C) (component (C)/total polyhydric alcohol) is preferably 0.005 or more, and more preferably 0.01 or more. It is preferably 0.015 or more, more preferably 0.17 or less, more preferably 0.15 or less, and even more preferably 0.14 or less.

In the present invention, the mass ratio (A)/(C) of component (A) to component (C) is preferably 0.02 or more, from the viewpoint of ease of foam expansion, thickening, and foaming. 0.05 or more is more preferable, 0.08 or more is even more preferable, 0.1 or more is even more preferable, and 0.3 or less is preferable from the point of view of foam elasticity and skin moisturizing feeling after washing. It is more preferably .25 or less, even more preferably 0.2 or less, and even more preferably 0.18 or less. Further, from the same viewpoint as above, the mass ratio (A)/(C) of component (A) to component (C) is preferably 0.02 to 0.3, more preferably 0.05 to 0.25, and 0. .08 to 0.2 is more preferable, and 0.1 to 0.18 is even more preferable.

The fatty acid salt of component (D) used in the present invention is represented by the general formula (1)

(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 9 to 21 carbon atoms, and X represents an alkali metal, ammonium, ammonium derived from an alkanolamine, or a basic amino acid.)
The one represented by is preferable.
More specifically, examples thereof include salts of lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, arachidic acid, behenic acid, and the like. Among these, from the viewpoint of improving detergency and foaming, it is preferable to contain at least one salt selected from lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid; It is more preferable that at least one kind selected from acids is included.
Examples of these salts include alkali metals such as sodium and potassium; ammonium; ammonium derived from alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and basic amino acids such as arginine and lysine. Among these, it is preferable to contain at least one kind selected from sodium, potassium, ammonium, and arginine, from the viewpoint of achieving both good compatibility with water and detergency, and at least one kind selected from potassium and arginine. More preferably, it contains at least potassium.

The fatty acid salt of component (D) can be present in the composition by, for example, mixing an unneutralized fatty acid with a neutralizing agent to form a fatty acid salt.
The neutralizing agent is a compound exhibiting basicity, and examples thereof include sodium hydroxide, potassium hydroxide, triethanolamine, and basic amino acids. Among these, from the viewpoint of improving detergency and compatibility with water, it is preferable to contain at least one selected from potassium hydroxide and sodium hydroxide, and it is preferable to contain at least potassium hydroxide. More preferred.

Component (D) can be used alone or in combination of two or more, and the content should be 10% by mass or more as fatty acids in the total composition from the viewpoint of foaming and moisturizing the skin after washing. It is preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. Further, the content of component (D) is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and even more preferably 25 to 35% by mass in the total composition as a fatty acid.

The skin cleansing composition of the present invention can contain a polyhydric alcohol (component (E)) other than component (C). Component (E) may contain one or more selected from (E1) dihydric alcohols and (D2) trihydric alcohols.
(E1) As the dihydric alcohol, specifically, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,2-pentylene glycol, 1,3-pentylene glycol, 1,4-pentylene glycol , 1,5-pentylene glycol, hexylene glycol, and other alkylene glycols; diethylene glycol, dipropylene glycol, and polyethylene glycol having an average molecular weight of less than 2,000. Among these, ethylene glycol, diethylene glycol, polyethylene glycol with an average molecular weight of less than 2000, propylene glycol, dipropylene glycol, and 1,3-butylene are considered from the viewpoint of foam thickness, skin moisturization after washing, and foam sustainability. It is preferable to include one or more types selected from glycols.
(E2) Examples of the trihydric alcohol include glycerin and trimethylolpropane.

Component (E) can be used alone or in combination, and the content is determined from the viewpoint of improving the thickening of the foam, the moisturizing feeling of the skin after washing, and the sustainability of the foam. It is preferably 20% by mass or more, more preferably 25% by mass or more, and preferably 50% by mass or less, and more preferably 45% by mass or less. Further, the content of component (E) is preferably 20 to 50% by mass, more preferably 25 to 45% by mass in the total composition.

In the present invention, water constitutes the remainder of each component, and the content is preferably 5 to 30% by mass, and 10 to 25% by mass of the total composition, from the viewpoint of ease of discharging when filled into a tube. % is more preferable, and 15 to 23% by mass is even more preferable.

The skin cleansing composition of the present invention includes, in addition to the above-mentioned components, ingredients used in ordinary skin cleansing compositions, such as surfactants and ingredients other than component (D), to the extent that the effects of the present invention are not impaired. High molecular compounds other than (A) to (C), oily ingredients, pH adjusters, bactericidal agents, anti-inflammatory agents, preservatives, chelating agents, salts, pearling agents, scrubbing agents, fragrances, cooling agents, pigments, It can contain ultraviolet absorbers, antioxidants, plant extracts, etc. Note that each of these agents is not limited to its use as an individual agent, but may be used for other purposes depending on the purpose, such as as a cooling agent as a fragrance, or as a cooling agent in combination with other purposes, such as as a cooling agent. It can also be used as a fragrance.

The skin cleansing composition of the present invention preferably has a pH of 7 to 14, more preferably 8 to 12, from the viewpoints of foaming, ease of crystal precipitation, and storage stability.
In the present invention, the pH is measured by directly measuring the bulk of the skin cleansing composition at 20° C. using a pH meter (F-22, manufactured by HORIBA).
Further, as the pH adjusting agent for adjusting the pH, inorganic acids, organic acids, inorganic alkaline agents, organic alkaline agents, basic amino acids, and the like can be used without limitation. Among these, from the viewpoint of foaming and stability, inorganic alkaline agents such as potassium hydroxide and sodium hydroxide, organic alkaline agents such as triethanolamine, and basic amino acids such as lysine and arginine are preferred, and inorganic alkaline agents are more preferred. preferable.

The skin cleansing composition of the present invention can be manufactured according to conventional methods. Further, the skin cleansing composition of the present invention is cream-like and in a cream-like crystallized state, and is in a non-uniform state in which fine crystals of the surfactant are dispersed in a saturated aqueous solution of the surfactant. It is.
In the present invention, the term "cream-like" does not refer to an emulsifier type, but rather a cream-like form that is not liquid, that is, a state in which there is no fluidity at room temperature, or if there is, it is small. Specifically, it is preferable that the viscosity is 100 Pa·s or more when measured under the following conditions. Moreover, it is more preferable that it is 800 Pa·s or less from the viewpoint of water solubility.
Measuring equipment: Digital viscometer TVB-10R type (manufactured by Toki Sangyo Co., Ltd.)
Measuring jig: T-D
Rotation speed: 5rpm
Measurement time: 60s
Measurement temperature: 20℃
Moreover, the creamy skin cleansing composition is preferably filled into a container such as a tube.

The skin cleansing composition of the present invention can be applied as a skin cleansing agent that is lathered and cleansed, such as a hand wash, a face wash, a cleansing agent, a body soap, a scalp cleanser, and the like.
Further, the skin cleansing composition of the present invention can be applied to the skin, more specifically, the scalp, face, body, limbs, etc., preferably to the skin excluding the scalp, and then washed off with water. It can be used by.

Reference Examples 1 to 4, Examples 1 to 20, and Comparative Examples 1 to 5
Skin cleansing compositions having the compositions shown in Tables 1 to 3 were produced.
The viscosity of the obtained skin cleansing composition was measured, and the elasticity of the foam, the ease of spreading the foam, the thick feeling of the foam, and the moist feeling of the skin after washing were evaluated. The results are also shown in Tables 1 to 3. Note that the contents in the table are active amounts.

(Production method)
Component (C), water, and polyhydric alcohol were mixed, heated to 80°C, and then fatty acids were added. Furthermore, after saponifying at 90°C or higher, the mixture was cooled to 50°C, components (A) and (B) were added, and the mixture was cooled to 35°C to obtain a skin cleansing composition.

(Evaluation method)
(1) Viscosity measurement:
Viscosity was measured using a digital viscometer model TVB-10R (manufactured by Toki Sangyo Co., Ltd.) under the following measurement conditions.
Measuring jig: T-D
Rotation speed: 5rpm
Measurement time: 60s
Measurement temperature: 20℃

(2) Foam elasticity:
Each of the prepared skin cleansing compositions was lathered by hand for 30 seconds using a 10-fold dilution of water, and the elasticity of the foam was evaluated when the palms were pressed together with both hands sandwiching the foam. . In addition, the evaluation was made using Reference Example 1 as a control, using the following 5 levels and 9 levels between them.
5: Compared to Reference Example 1, elasticity is sufficient.
4: Compared to Reference Example 1, there is elasticity.
3: Same as Reference Example 1.
2: Compared to Reference Example 1, there is no elasticity.
1: Compared to Reference Example 1, there is no elasticity at all.

(3) Ease of foam expansion:
Each prepared skin cleansing composition was lathered by hand for 30 seconds using 10 times diluted water, and the ease with which the foam was spread was evaluated by holding the foam between both hands and then stretching it between the palms of the hands. did. In addition, the evaluation was made using Reference Example 1 as a control, using the following 5 levels and 9 levels between them.
5: Compared to Reference Example 1, it is sufficiently easy to stretch and expand.
4: Easier to stretch and expand compared to Reference Example 1.
3: Same as Reference Example 1.
2: Compared to Reference Example 1, it is difficult to stretch and expand.
1: Compared to Reference Example 1, it is extremely difficult to stretch and expand.

(4) Thickness of foam:
Lather each of the prepared skin cleansing compositions by hand for 30 seconds using 10 times diluted water, and when you remove the foam from both hands, the foam becomes stringy. The state of connection was evaluated as a feeling of thickness. In addition, the evaluation was made using Reference Example 1 as a control, and was evaluated using the following five stages and nine stages between them.
5: Compared to Reference Example 1, the texture is sufficiently thick.
4: Compared to Reference Example 1, it feels thicker.
3: Same as Reference Example 1.
2: Compared to Reference Example 1, there is no thick feeling.
1: Compared to Reference Example 1, there is no thick feeling at all.

(5) Moisture feeling on the skin after washing:
In the same manner as in (4) above, the prepared skin cleansing composition was lathered by hand for 30 seconds using 10 times diluted water, and after washing the face, rinsing thoroughly until the foam disappeared, and drying with a towel. The skin's moisture feeling was evaluated using the following five levels and nine levels between them.
5: Compared to Reference Example 1, there is a sufficient moist feeling.
4: Compared to Reference Example 1, there is a feeling of moisture.
3: Same as Reference Example 1.
2: Compared to Reference Example 1, there is no moist feeling.
1: Compared to Reference Example 1, there is no moist feeling at all.

*1 LIPIDURE-PMB, manufactured by NOF Corporation *2 LIPIDURE-S, manufactured by NOF Corporation *3 MERQUAT 550PR POLYMER, Lubrizol Advanced Materials, Inc. Manufactured by *4 MERQUAT 3330PR POLYMER, Lubrizol Advanced Materials, Inc. made

Test example 1
Regarding the skin cleansing compositions of Table 1 (Reference Examples 1 to 4) and Example 1, the rheology of the foam prepared in the same manner as in (3) above was determined by storage modulus (G') using Anton Paar Physica MCR301. The dependence of loss modulus (G'') on shear stress was measured. The measurement jig was a parallel plate PP-50, and the measurement temperature was 20°C.
Among the obtained values, the value of G' at a shear stress of 0.01 Pa is taken as the elasticity of the foam, and the loss tangent (tan δ) obtained from G''/G' is shown in FIG. 1.Component (A) of the present invention In Example 1, compared to Reference Example 1 (standard composition) which does not contain (C), the inflection point of the loss tangent (tan δ) is greatly reduced, so the force required to move the bubbles is reduced. In other words, it is clear that the foam is easy to expand and expand.

Claims (5)

The following ingredients (A), (B), (C) and (D):
(A) 0.01 to 0.5% by mass of a phospholipid polymer containing 2-methacryloyloxyethylphosphorylcholine as a constituent monomer,
(B) Homopolymer of dimethyldiallylammonium chloride, copolymer of dimethyldiallylammonium chloride and (meth)acrylic acid, copolymer of dimethyldiallylammonium chloride and (meth)acrylic acid ester, dimethyldiallylammonium chloride and (meth)acrylic acid ester copolymer 0.01 to 0.7% by mass of at least one cationic polymer selected from acrylamide copolymers and polychlorinated methacryloyloxyethyltrimethylammonium chloride ;
(C) 0.1 to 8% by mass of polyethylene glycol having an average molecular weight of 2,000 or more,
(D) At least one fatty acid salt selected from salts of lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid 10 to 50% by mass as fatty acid
A creamy skin cleansing composition containing the following, wherein the mass ratio (A)/(C) of component (A) to component (C) is 0.02 to 0.3 . The skin cleansing composition according to claim 1, wherein component (A) is a 2-methacryloyloxyethylphosphorylcholine/alkyl methacrylate copolymer. The skin cleansing composition according to claim 1 or 2, wherein component (C) is polyethylene glycol having an average molecular weight of 4,000 or more. The skin cleansing composition according to any one of claims 1 to 3, wherein component (C) is polyethylene glycol having an average molecular weight of 6,000 or more. The skin cleansing composition according to any one of claims 1 to 4, wherein the mass ratio (A)/(B) of component (A) to component (B) is 0.1 to 5.5.