JP6254638B2 - Liquid skin cleansers and liquid skin cleansing products - Google Patents

Description

  The present invention relates to a liquid skin cleanser and a liquid skin cleanser product.

  In recent years, skin cleansing agents that give a smooth and moist feeling to the skin after washing and those that are fine and dense in terms of the comfort when the foam comes into contact with the skin are preferred. Various studies have been made to meet such demands. In order to improve the smoothness and moist feeling of the back skin, it is widely known to use a cationized polymer. In addition, it is known to use a nonionic polymer such as polyethylene glycol to make the foam dense.

  For example, Patent Document 1 describes that a cleansing composition that imparts a conditioning action can be obtained by using a cationic polymer combined with a specific anionic surfactant. Patent Document 2 describes that a non-neutralized fatty acid soap, a cationic polymer, a polyethylene glycol having a specific molecular weight, etc. can be used to obtain a paste-like cleaning agent with fine foam and good elongation. ing. Furthermore, Patent Document 3 describes that a composition excellent in skin protection can be obtained by using a cationic polymer having a specific degree of cation substitution and molecular weight.

Japanese Patent No. 4965452 Japanese Patent No. 5555003 Japanese Patent No. 5436778

  In order to improve the smoothness of the back skin, it is known that when the cationic polymer contains, for example, cationized polygalactomannan, the content viscosity of the composition increases. If the content viscosity is too high, there is a problem that the liquid cleaning material cannot be discharged from the discharge port of the container with a dispenser. Moreover, the cleaning composition containing unneutralized fatty acid soap tends to increase in winter due to excess fatty acid. On the other hand, if too much polyethylene glycol is added to make the foam dense, the smoothness of the back skin tends to be impaired, and there is a problem that stringing occurs from the discharge port of the container. In the liquid skin cleanser, the formulation described in the above-mentioned patent document is not sufficient to achieve both the density of foam and the smoothness of the back skin and the discharge property from the container with a dispenser at a low temperature. The liquid here has fluidity at normal temperature, and the measured value with a B-type viscometer is 50000 mPa · s or less.

  The present invention has been made in view of the above circumstances, and provides a liquid skin cleansing product and a liquid skin cleansing product having smoothness of the back skin and dense foam, and good dischargeability from the dispenser even at low temperatures. It is intended to do.

The liquid skin cleanser of the present invention is a liquid skin cleanser containing a fatty acid soap, a cationized polygalactomannan, and polyethylene glycol,
The neutralization rate of the fatty acid soap is 90 mol% or more and 99 mol% or less,
The content ratio of the cationized polygalactomannan to the total amount of the liquid skin cleanser is 0.05% by mass or more,
The weight average molecular weight Mw of polyethylene glycol is 2 million or more.

  The content ratio of polyethylene glycol to the total amount of the liquid skin cleanser is preferably 0.01% by mass or more and 0.1% by mass or less.

  Furthermore, you may contain cationized polymers other than cationized polygalactomannan.

  The N content of the cationized polygalactomannan is preferably 0.2% or more and 3.0% or less.

  The liquid skin cleanser of the present invention may further contain a dihydric alcohol.

  The mass ratio of the dihydric alcohol to the mass ratio of the dihydric alcohol to the cationized polygalactomannan / the mass of the cationized polygalactomannan is preferably 20 or more.

  The liquid skin cleansing product of the present invention is obtained by filling a container with the liquid skin cleansing material of the present invention.

  The liquid skin cleanser of the present invention is a liquid skin cleanser containing fatty acid soap, cationized polygalactomannan, and polyethylene glycol, and the neutralization rate of the fatty acid soap is 90 mol% or more and 99 mol% or less, Since the content ratio of the modified polygalactomannan to the total amount of the liquid skin cleanser is 0.05% by mass or more, and the weight average molecular weight Mw of the polyethylene glycol is 2 million or more, it has smoothness of the back skin and foam density. And can be discharged from a dispenser.

Hereinafter, the liquid skin cleansing material of the present invention will be described in detail.
The liquid skin cleanser of the present invention is a liquid skin cleanser containing fatty acid soap, cationized polygalactomannan, and polyethylene glycol, and the neutralization rate of the fatty acid soap is 90 mol% or more and 99 mol% or less, The content ratio of the modified polygalactomannan to the total amount of the liquid skin cleanser is 0.05% by mass or more, and the weight average molecular weight Mw of polyethylene glycol is 2 million or more.
Hereinafter, each component will be described in detail.

(Fatty acid soap)
The fatty acid soap used in the present invention is a fatty acid salt obtained by neutralizing a fatty acid and an alkali. Examples of the fatty acid constituting the fatty acid salt include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, lignoceric acid, and coconut oil fatty acid.

  Moreover, potassium hydroxide can be mentioned as an alkali.

The neutralization rate of the fatty acid soap is 90 mol% or more and 99 mol% or less, and preferably 93 mol% or more and 96 mol% or less. By setting the neutralization rate to 90 mol% or more, for example, even if the viscosity increases at a low temperature of 5 ° C., it can be discharged from the dispenser. Moreover, it can have the smoothness of a back skin by setting it as 99% mol or less.
Here, the neutralization rate of the fatty acid soap is a value obtained by dividing the amount of neutralized fatty acid (mol) by the total amount of fatty acid (mol).

  The content ratio of the fatty acid soap to the total amount of the liquid skin cleanser is preferably 5% by mass or more and 30% by mass or less, more preferably 10% by mass or more and 25% by mass or less, and more preferably 15% by mass or more, from the viewpoint of ensuring detergency and foaming. 25 mass% or less is more preferable.

(Cationized polygalactomannan)
Cationized polygalactomannan is a cationized water-soluble polymer having a main chain of mannose and a side chain of galactose. A galactose to mannose ratio of 1: 2 is referred to as cationized guar gum, 1: 3 as cationized tara gum, and 1: 4 as cationized locust bean gum. Any ratio may be used in the present invention.
The cationized polygalactomannan is obtained by reacting galactomannan with a cationizing agent. As the cationizing agent, a tertiary amino compound or a quaternary ammonium compound containing a group capable of reacting with a reactive hydrogen ion present in galactomannan can be used. Examples include 2-dialkylaminoethyl chloride and quaternary ammonium compounds such as 3-chloro-2-hydroxypropyltrimethylammonium chloride and 2,3-epoxy-propyltrimethylammonium chloride. Preferred examples include glycidyl trialkyl ammonium salts and 3-halo-2-hydroxypropyl trialkyl ammonium salts such as glycidyl trimethyl ammonium chloride, glycidyl triethyl ammonium chloride, glycidyl tripropyl ammonium chloride, glycidyl ethyl dimethyl ammonium. Chloride, glycidyl diethylmethylammonium chloride and their corresponding bromides and iodides; 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltriethylammonium chloride, 3-chloro 2-hydroxypropyltripropylammonium chloride, 3-chloro-2-hydroxypropylethyldimethylammonium chloride, and Corresponding bromides and iodides; and quaternary ammonium compounds such as halides of imidazoline ring containing compounds.
Only one kind of cationized polygalactomannan may be used, or two or more kinds may be used in combination.

  As a commercial item, DSP Gokyo Food & Chemical Co., Ltd. Laborum gum CG-M6L (N content 1.0-1.5%), Laborum gum CG-M (N content 1.7-2.3%) , Labor gum CG-M8M (N content: 2.2 to 2.8%), Kachinal CG-100S (N content: 1.0 to 1, 7%) manufactured by Toho Chemical Co., Ltd.

The N content of the cationized polygalactomannan is preferably 0.2% or more and 3.0% or less, and more preferably 0.5% or more and 2.5% or less.
Here, the N content is a value determined by the ratio (% by weight) of nitrogen atoms contained in the component.

  The molecular weight of the cationized polygalactomannan used in the liquid skin cleansing agent of the present invention is preferably 10,000 to 10,000,000, preferably from 10,000 to 10,000,000 from the viewpoint of ejection from a container with a pump or dispenser and the like, and from the viewpoint of preventing stringing. It is more preferably 3 million or less and more preferably 100,000 or more and 2 million or less.

  The content ratio of the cationized polygalactomannan to the total amount of the liquid skin cleanser is 0.05% by mass or more. The upper limit is preferably 1.0% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less from the viewpoint of dischargeability from a container with a pump or a dispenser and the like and prevention of stringing.

(Polyethylene glycol)
The polyethylene glycol used in the present invention has a weight average molecular weight Mw of 2 million or more. The upper limit is preferably 8 million or less. Furthermore, more than 3 million and 7 million or less are preferable.
The content ratio of polyethylene glycol to the total amount of the liquid skin cleanser is preferably 0.01% by mass or more and 0.20% by mass or less, more preferably 0.01% by mass or more and 0.10% by mass or less, and 0.02% by mass. % To 0.05% by mass is more preferable. By setting it as 0.01 mass% or more, a bubble can be made dense. Moreover, by setting it as 0.20 mass% or less, it can prevent that foaming worsens and the volume of foam reduces.
Here, the weight average molecular weight Mw of polyethylene glycol is a value determined by column analysis.

  Commercially available products include Alcox E-300 (weight average molecular weight of about 7 million), Alcox E-240 (weight average molecular weight of about 5 million), and Alcox E-160 (weight average molecular weight of about 400 million) manufactured by Meisei Chemical Industry Co., Ltd. ), Alcox E-100 (weight average molecular weight of about 3 million), Alcox E-75 (weight average molecular weight of about 2 million), Polyox WSR 301 (weight average molecular weight of about 4 million) manufactured by Dow Chemical Japan Ltd. ), Polyox WSR N60K CG (weight average molecular weight of about 2 million), Polyox N80 (weight average molecular weight of 220,000), PEO-27P (weight average molecular weight of about 7.2 million) manufactured by Sumitomo Seika Co., Ltd., PEO-18P (weight) Average molecular weight of about 4.8 million), PEO-15P (weight average molecular weight of about 4 million), PEO-8P (weight average molecular weight of about 2 00000), and the like.

(Cationized polymers other than cationized polygalactomannan)
Examples of the cationized polymer include cationized cellulose, cationized starch, diallyldialkyl quaternary ammonium salt / acrylamide copolymer, diallyldialkyl quaternary ammonium salt / acrylamide / acrylic acid copolymer, and the like. Among them, cationized cellulose and diallyldialkyl quaternary ammonium salt / acrylamide copolymer are preferable, and diallyldialkyl quaternary ammonium salt / acrylamide copolymer is more preferable.
As diallyldialkyl quaternary ammonium salt / acrylamide copolymer, for example, Marquat 550 (weight average molecular weight: 160,000, cationic charge density: 4.22 meq / g), Marquat 2200 (weight average molecular weight: 90,000, cationic charge density: 4.22 meq / g), Marquat S (weight average molecular weight: 260,000, cationic charge density: 4.22 meq / g) [Nippon Lubrizol Co., Ltd., copolymer of acrylamide and diallyldimethylammonium salt], Poise C- 60H (weight average molecular weight: 600,000, cationic charge density: 1.07 to 1.78 meq / g), Katachiro M-80 (weight average molecular weight: 800,000, cationic charge density: 0.93 to 1.21 meq / g) , Poise C-150L (weight average molecular weight: 1,500,000, cationic charge density: 0.71-1.07 meq / g) [more Kao Corporation, cationic cellulose (chloride O- [2- hydroxy-3- (trimethylammonio) propyl] hydroxyethyl cellulose).

(Dihydric alcohol)
The liquid skin cleanser of the present invention may further contain a dihydric alcohol. Examples of the dihydric alcohol include propylene glycol, dipropylene glycol, butylene glycol, and isoprene glycol. The dihydric alcohol has a role of a humectant.

  The content ratio of the dihydric alcohol to the total amount of the liquid skin cleanser is preferably 1 or more and 15 or less, and more preferably 4 or more and 10 or less.

  The mass of the dihydric alcohol, which is the mass ratio of the dihydric alcohol to the cationized polygalactomannan / the mass of the cationized polygalactomannan, is preferably 16 or more, and preferably 20 or more from the viewpoint of improving dischargeability from the dispenser. Is more preferable. The upper limit is preferably 30 or less from the viewpoint of improving foaming. A more preferable range is 22 or more and 28 or less.

(Other ingredients)
The liquid skin cleanser of the present invention may contain other components as long as the effects of the present invention are not impaired. Examples of other components include anionic surfactants, nonionic surfactants, amphoteric surfactants, thickeners, polyhydric alcohols, chelating agents, humectants, aqueous carriers, pH adjusters, and fragrances. It is done.

  Anionic surfactants include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, Diethanolamine laureth sulfate, sodium lauryl monoglyceride sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate Lauroyl Sodium acid, cocoyl potassium sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, cocoyl sulfate, monoethanolamine lauryl sulfate, monoethanolamine, and combinations thereof.

  Also, reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide (eg, fatty acids are derived from coconut oil or palm kernel oil), and sodium or potassium salts of fatty acid amides of methyl tauride (eg, Fatty acids may be derived from coconut oil or palm kernel oil).

  Nonionic surfactants are generally defined as compounds that include a hydrophobic component and a nonionic hydrophilic component. Examples of hydrophobic components include alkyls, alkyl aromatics, dialkyl siloxanes, polyoxyalkylenes, and alkyls substituted with fluoro. Examples of hydrophilic components are polyoxyalkylenes, phosphine oxides, sulfoxides, amine oxides and amides. Other examples of nonionic surfactants include alkyl polysaccharides, such as alkyl polysaccharides.

  Examples of amphoteric surfactants include amine oxides, sulfobetaines, and carbobetaines.

Examples of the thickener include NaCl, NH ₄ Cl, KCl, Na ₂ SO ₄ , aliphatic alcohol, fatty acid ester, fatty acid amide, aliphatic alcohol polyethylene glycol ether, sorbitol polyethylene glycol ether, cocamide monoethanolamide (cocamide). MEA), cocamide diethanolamide, cocamide propyl betaine, clay, silica, cellulosic polymers, and xanthan.

  Examples of the polyhydric alcohol include glycerin, sorbitol, xylitol, and maltitol.

  Examples of chelating agents include ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, L-glutamic acid-N, N-diacetic acid, One or more selected from N-2-hydroxyethyliminodiacetic acid, citric acid, succinic acid and salts thereof are preferred.

Examples of the aqueous carrier include purified water and lower alcohols having 2 to 6 carbon atoms. Preferably it is purified water. The aqueous carrier is preferably contained in an amount of 30% by mass to 70% by mass with respect to the total amount of the liquid skin cleanser.

  The liquid skin cleanser of the present invention can be filled into, for example, a one-touch stopper or a container with a liquid dispenser to obtain a liquid skin cleansing product.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Moreover, the compounding quantity in a following example etc. shows the mass% unless there is particular notice.

[Examples 1 to 17, Comparative Examples 1 to 8]
Liquid skin cleansing materials having the compositions described in Tables 1 to 4 below were produced by a conventional method, and the dischargeability from the liquid dispenser, the smoothness of the back skin, and the density of foam were evaluated.

<Dischargeability from liquid dispenser at low temperature (5 ° C)>
The dischargeability from the liquid dispenser at a low temperature (5 ° C.) of the liquid skin cleanser was evaluated based on the following evaluation criteria.
A sample placed in a container with a liquid dispenser was stored in a thermostatic bath at 5 ° C. for 24 hours, and the operability of the dispenser immediately after removal was evaluated as follows. As the dispenser, P-308 manufactured by Yoshino Kogyo Co., Ltd., which is generally used as a liquid cleaning material, was used.

(Evaluation criteria)
A: A sample can be easily discharged.
B: The dispenser feels weight, or the dispenser returns slowly after discharge (less than 10 seconds), but can be discharged.
C: Unable to discharge or dispenser after discharging does not return for more than 10 seconds.

<Smooth of back skin, dense foam>
After having each professional panel use each sample in the usual usage method, a questionnaire on the following items was conducted, and an average score was given based on the results.
Smoothness of the back skin: The skin after washing is smooth.
Bubble density: Bubbles are elastic.
1: I don't think so at all 2: I don't think so 4: I think so 5: I think so

(Evaluation criteria)
Based on the average score, the evaluation was as follows.
AA: Average score ≧ 4.5
A: 4.5> Average score> 3.5
B: 2.5 ≦ average score ≦ 3.5
C: Average score <2.5

  The evaluation results are shown in Tables 1 to 4 together with the composition of the materials.

The details of the materials in Tables 1 to 4 are as follows.
(Polygalactomannan)
-Guahydroxypropyltrimonium chloride (low N content): Labor gum CG-M6L (manufactured by DSP Gokyo Food & Chemical Co., Ltd.)
-Guahydroxypropyltrimonium chloride (N content): Labor gum CG-M (DSP Gokyo Food & Chemical Co., Ltd.)
-Guahydroxypropyltrimonium chloride (high N content): Labor gum CG-M8M (DSP Gokyo Food & Chemical Co., Ltd.)
・ Cougar gum (nonion): Meyprogat 90-S (manufactured by Sanki Co., Ltd.)

(Polyethylene glycol)
-Weight average molecular weight (about 7 million): Alcox E-300 (manufactured by Meisei Chemical Co., Ltd.)
-Weight average molecular weight (about 5 million): Alcox E-240 (Madesei Chemical Co., Ltd.)
-Weight average molecular weight (about 4 million): Alcox E-160 (manufactured by Meisei Chemical Co., Ltd.)
-Weight average molecular weight (about 3 million): Alcox E-100 (manufactured by Meisei Chemical Co., Ltd.)
-Weight average molecular weight (approximately 2 million): Alcox E-75 (manufactured by Meisei Chemical Co., Ltd.)
-Weight average molecular weight (about 220,000): Polyox WSR N80 (manufactured by Dow Chemical Japan Co., Ltd.)

As can be seen from Table 1, Examples 1 to 3, in which the N content of the cationized polygalactomannan is 1.0 to 2.8%, have good pump discharge at low temperature, smoothness of the back skin, and foam The denseness was also good. In particular, Examples 2 and 3 having an N content of 1.0 to 2.3% obtained good results in all evaluations.
On the other hand, Comparative Example 1 using nonionic guar gum and Comparative Example 2 not using cationized polygalactomannan were inferior to the smoothness of the back skin. Moreover, the comparative example 3 which does not contain any cationized polygalactomannan and polyethylene glycol was inferior to the Example in the smoothness of the back skin and the density of foam.

  As can be seen from Table 2, Comparative Example 4 using polyethylene glycol having a molecular weight of 220,000, and Comparative Example 5 using no polyethylene glycol were used in Examples 4 to 7 using those having a molecular weight of 2 million or more. Compared with the density of bubbles, it was inferior.

  As can be seen from Table 3, Comparative Example 6 in which the content ratio of the cationized polygalactomannan to the total amount of the liquid skin cleanser was less than 0.05% by mass was inferior to the examples in terms of the smoothness of the back skin.

  As can be seen from Table 4, Comparative Example 7, in which the neutralization rate of the fatty acid soap was as low as 87 mol%, was inferior in dischargeability from the dispenser. On the other hand, Comparative Example 8, which is too high at a neutralization rate of 102 mol%, was inferior to the smoothness of the back skin and the density of bubbles.

(Prescription example)
Below, the formulation example of the liquid skin cleaning material of this invention is given. The present invention is not limited by this formulation example. In addition, all compounding quantities are represented by the mass% with respect to the product whole quantity.

Formulation example 1: The neutralization rate of fatty acid soap is 93 mol%.
Palm oil fatty acid 5.0
Lauric acid 6.0
Myristic acid 5.0
Palmitic acid 5.0
Propylene glycol 7.0
Ethylene glycol distearate 1.5
Gua-hydroxypropyltrimonium chloride 0.2
(Labor gum CG-M6L, DSP Gokyo Food & Chemical Co., Ltd.)
Polyethylene glycol 0.03
(Alcox E-240, manufactured by Meisei Chemical Co., Ltd.)
Laureth sulfate Na (30% aqueous solution) 7.5
Cocamidopropyl betaine (30% aqueous solution) 5.0
Cocamide MEA 0.1
Yuzu Extract 0.001
Polyquaternium-7 1.0
(Mercoat 550, made by Nihon Lubrizol)
Polyquaternium-39 1.0
(Marcote 3330, made by Nihon Lubrizol)
Potassium hydroxide appropriate amount Chelating agent appropriate amount Fragrance appropriate amount Purified water residue Dischargeability from the liquid dispenser of Formulation Example 1, smoothness of the back skin, and foam density were all evaluated as A.

Formulation example 2: The neutralization rate of fatty acid soap is 95 mol%.
Palm oil fatty acid 5.0
Lauric acid 7.0
Myristic acid 6.0
Palmitic acid 5.0
Propylene glycol 8.0
Ethylene glycol distearate 2.0
Gua-hydroxypropyltrimonium chloride 0.3
(Kachinar CG-100S, manufactured by Toho Chemical Co., Ltd.)
Polyethylene glycol 0.05
(Polyox WSR 301, manufactured by Dow Chemical Japan Co., Ltd.)
Laureth sulfate Na (30% aqueous solution) 6.5
Cocamidopropyl betaine (30% aqueous solution) 6.5
Cocamide MEA 0.2
Polyquaternium-7 1.5
(Mercoat 550, made by Nihon Lubrizol)
Polyquaternium-51 0.01
Sodium hyaluronate 0.001
Hydroxypropyl methylcellulose 0.05
Potassium hydroxide Appropriate amount Chelating agent Appropriate amount Fragrance Appropriate amount Purified water Residue The dischargeability from the liquid dispenser of Formulation Example 2, the smoothness of the back skin, and the density of the foam were all evaluated as A.

Claims (4)

A liquid skin cleanser containing fatty acid soap, cationized polygalactomannan, polyethylene glycol, and dihydric alcohol ,
The neutralization rate of the fatty acid soap is 90 mol% or more and 99 mol% or less,
The content ratio of the cationized polygalactomannan to the total amount of the liquid skin cleanser is 0.05% by mass or more,
The polyethylene glycol has a weight average molecular weight Mw of 2 million or more,
A liquid skin cleanser having a mass of dihydric alcohol / mass of cationized polygalactomannan which is a mass ratio of the dihydric alcohol to the cationized polygalactomannan of 20 or more . Furthermore, the liquid skin cleanser according to claim 1, further comprising a cationized polymer other than the cationized polygalactomannan. The liquid skin cleanser according to claim 1 or 2, wherein the N content of the cationized polygalactomannan is 0.2% or more and 3.0% or less. A liquid skin cleansing product comprising a container filled with the liquid skin cleanser according to any one of claims 1 to 3 .