JP7779649B2 - Cleaning composition - Google Patents

Description

The present invention relates to a cleaning composition.

The swelling clay mineral has the property of thickening the composition and also adsorbing sebum, so when it is blended into a cleanser, it can thoroughly remove dirt even from pores.
For example, Patent Document 1 describes that a paste-like cleanser composition containing a mixture of fatty acid potassium salts, an alkyliminodicarboxylic acid-type amphoteric surfactant, an acylmethyltaurine-type anionic surfactant, a water-swellable clay mineral, and a dihydric or trihydric alcohol has excellent spreadability, rapid foaming, foam volume, and foam quality during use, and leaves the skin feeling refreshed after rinsing, while being less likely to cause a tight feeling.

JP 2014-193981 A

However, while conventional cleanser compositions contain clay minerals and have the ability to adsorb sebum, none of them offer the change in feel or granular texture that clay minerals provide. As a result, none of them offer the sebum-adsorbing effect of clay minerals in terms of feel when used.
Therefore, we investigated ways to realize the sebum-absorbing effect of clay minerals through use, and found that one way to do this is to apply and massage the cleanser composition into the skin, so that it does not foam immediately after application, but can be sufficiently massaged onto the skin while it is not dissolved in water, and then foams after an appropriate number of massages.
However, conventional cleanser compositions foam immediately after application to the skin and massage, making it difficult to achieve a satisfactory massage effect. Furthermore, they have problems with ease of spreading when applied to the skin with water and then spread on the skin, and with dischargeability from the container when stored at low temperatures.

The inventors discovered that by using a combination of clay minerals, cationic polymers of specific molecular weights, and fatty acids and their salts, it is possible to obtain a cleanser composition that spreads easily when applied to the skin and spread on the skin after application, does not immediately lather when applied to the skin and is massaged into the skin, and is in a cream or gel state, and in which the satisfactory granular texture of the clay minerals is fully felt, and which exhibits excellent dischargeability from the container after storage, thereby completing the present invention.

The present invention comprises the following components (A), (B) and (C):
(A) clay minerals,
(B) a cationic polymer having a weight-average molecular weight of 30,000 to 1,000,000;
(C) General formula (1):
R ¹ -COOX (1)
(wherein ^R1 represents an alkyl group or alkenyl group having 9 to 23 carbon atoms, and X represents a hydrogen atom, an alkali metal, ammonium, ammonium derived from an alkanolamine, or a basic amino acid)
The present invention relates to a detergent composition containing a fatty acid represented by the formula (I) and a salt thereof.

The cleanser composition of the present invention spreads easily when applied to the skin with water and spread on the skin. When massaged, the cleanser composition does not immediately foam, but can be used in a cream or gel state, providing a pleasant, textured feel on the skin due to the clay minerals, while still providing a satisfying massage sensation. It also has excellent dischargeability from the container after storage.

Examples of clay minerals of component (A) used in the present invention include smectite clay minerals such as bentonite (including natural and synthetic bentonite), montmorillonite (including natural and synthetic montmorillonite), beidellite, nontronite, laponite, sauconite, hectorite (including natural and synthetic hectorite), and stevensite such as Moroccan lava clay; kaolinite such as rhyolite powder; vermiculite; swellable synthetic fluorine mica (Na-type and Li-type synthetic mica); swellable mica; and marine mud (marine sediments) such as Tanakura clay.
Among these, from the viewpoints of improving the spreadability when the cleanser composition is applied to the skin and spread, not immediately lathering when massaged onto the skin, providing a satisfactory massage feeling with a creamy or gel-like cleanser composition, providing a good rough texture due to the clay minerals, and improving the ease of discharge from the container after storage, it is preferable to include at least one or two or more selected from stevensite, kaolinite, and sea mud (sea sediments), more preferably at least one or two or more selected from Moroccan lava clay, rhyolite powder, and Tanakura clay, even more preferably at least one or two or more selected from Moroccan lava clay and Tanakura clay, and even more preferably Moroccan lava clay.
As the Tanakura clay, a granulated product with agar is preferred.

The clay mineral of component (A) is preferably a water-swellable clay mineral, from the viewpoints of improving the spreadability of the cleanser composition when applied with water to the skin, not immediately lathering when massaged onto the skin, providing a satisfactory massage feeling with a creamy or gel-like cleanser composition, providing a good rough texture due to the clay mineral, and improving the ease of discharge from the container after storage. The clay mineral has a swelling ratio in water of preferably 1 to 50 cm ³ /2g, more preferably 2 to 20 cm ³ /2g, and even more preferably 3 to 10 cm ³ /2g.
In this invention, the swelling ratio is measured according to the Bentonite Test Method in the Japanese Pharmacopoeia. Specifically, 2.0 g of sample adjusted to 8.0% moisture is added in approximately 10 portions to a 100 mL stoppered measuring cylinder containing 100 mL of distilled water. The next addition is made after the previous addition has settled to the bottom of the measuring cylinder. After 24 hours, the apparent volume of the swollen sample mass at the bottom of the measuring cylinder is read from the measuring cylinder scale and recorded as the swelling ratio SP ( ^cm3 /2 g).

Furthermore, the clay mineral of component (A) preferably has a number-average particle size of 30 to 2,000 μm, more preferably 50 to 1,200 μm, and even more preferably 80 to 500 μm, from the viewpoints of improving the spreadability of the cleanser composition when applied to the skin with water, not immediately foaming when massaged onto the skin, providing a satisfactory massage feeling with a creamy or gel-like cleanser composition, providing a satisfactory rough texture due to the clay mineral, and improving dischargeability from a container after storage.
In the present invention, the number-average particle size is measured using an image analysis method. Specifically, when a clay mineral is observed using an optical microscope (Nikon, ECLIPSE LV100POL), 20 to 50 clay minerals are randomly selected, and the maximum long diameters are measured by direct observation and then number-averaged.
As component (A), commercially available products such as Ghassoul M, a Moroccan lava clay (number average particle size: 100 μm, swelling rate: 8 cm ³ /2 g) (manufactured by Ghassoul Japan Jamila), Matera Powder 60 μm Under, a rhyolite powder (number average particle size: 60 μm, swelling rate: 4 cm ³ /2 g) (manufactured by Matera), and Sucra Beauty MX, a Tanakura clay (granulated with agar) (Tanakura clay content: 94%, number average particle size: 1000 μm, swelling rate: 4 cm ³ /2 g) (manufactured by Dainippon Kasei Co., Ltd.), can be used.

One or more types of component (A) may be used, and the content is preferably 2 to 8% by mass, more preferably 2.5 to 7% by mass, and even more preferably 4 to 5.5% by mass of the total composition, from the viewpoints of improving the spreadability of the cleanser composition when applied to the skin with water, not immediately lathering when massaged onto the skin, providing a satisfactory massage sensation with a creamy or gel-like cleanser composition, providing a good texture due to the clay minerals, and improving the ease of dispensing from the container after storage.

Component (B) is a cationic polymer having a weight average molecular weight of 30,000 to 1,000,000.
The cationic polymer is not limited as long as it is one that is used in ordinary detergent compositions, and examples thereof include cationized cellulose, cationized starch, cationized guar gum such as O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride, cationized tara gum, cationized locust bean gum, cationized fenugreek gum, cationized xanthan gum, polymers of diallyldialkyl quaternary ammonium salts, diallyldialkyl quaternary ammonium salt/acrylamide copolymers, diallyldialkyl quaternary ammonium salt/acrylic acid copolymers such as dimethyldiallylammonium chloride/acrylic acid copolymers, diallyldialkyl quaternary ammonium salt/acrylamide/acrylic acid copolymers, vinylimidazolium trichloride/vinylpyrrolidone copolymers, hydroxyethyl cellulose/dimethyldiallylammonium chloride copolymers, copolymers, vinylpyrrolidone/quaternized dimethylaminoethyl methacrylate copolymers, polyvinylpyrrolidone/alkylaminoacrylate copolymers, polyvinylpyrrolidone/alkylaminoacrylate/vinylcaprolactam copolymers, vinylpyrrolidone/methacrylamidopropyl trimethylammonium chloride copolymers, alkylacrylamide/acrylate/alkylaminoalkylacrylamide/polyethylene glycol methacrylate copolymers, adipic acid/dimethylaminohydroxypropyl ethylenetriamine copolymers (Sandoz Corporation, USA, Caltaretin), vinylpyrrolidone/quaternized vinylimidazole copolymers such as vinylpyrrolidone/methylvinylimidazolinium methyl sulfate copolymers, and cationic polymers described in JP-A-53-139734 and JP-A-60-36407.

Among these, from the viewpoints of not immediately foaming when massaged onto the skin, providing a satisfactory massage sensation from the creamy or gel-like cleanser composition, and improving the pleasant roughness provided by the clay minerals, it is preferable to include at least one or more selected from cationized guar gum, diallyldialkyl quaternary ammonium salt/acrylic acid copolymer, and vinylpyrrolidone/quaternized vinylimidazole copolymer; more preferable to include at least one or more selected from O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride, dimethyldiallylammonium chloride/acrylic acid copolymer, vinylpyrrolidone/methylvinylimidazolinium methyl sulfate copolymer; even more preferable to include at least one or more selected from dimethyldiallylammonium chloride/acrylic acid copolymer and vinylpyrrolidone/methylvinylimidazolinium methyl sulfate copolymer; and even more preferable to include vinylpyrrolidone/methylvinylimidazolinium methyl sulfate copolymer.

The cationic polymer of component (B) does not immediately lather when massaged onto the skin, provides a satisfactory massage sensation with the cream or gel cleanser composition, and has a weight-average molecular weight of 30,000 to 1,000,000, preferably 50,000 to 400,000, more preferably 150,000 to 300,000, and even more preferably 19.5 to 250,000, from the viewpoints of enhancing the pleasant roughness of the clay minerals.

In addition, examples of commercially available cationic polymers that can be used for component (B) include LUVIQUAT ULTRACARE AT 1 (manufactured by BASF, weight-average molecular weight: 200,000), RHABALL GUM CG-M (manufactured by DSP Gokyo Food & Chemical Co., Ltd., weight-average molecular weight: 100,000), and MERQUAT 295 (manufactured by Lubrizol Advanced Materials, weight-average molecular weight: 190,000).

One or more types of component (B) may be used, and the content is preferably 0.01 to 0.5% by mass, more preferably 0.03 to 0.3% by mass, and even more preferably 0.08 to 0.15% by mass of the total composition, from the viewpoints of improving the spreadability of the cleanser composition when applied to the skin with water, not immediately lathering when massaged onto the skin, providing a satisfactory massage sensation with a creamy or gel-like cleanser composition, providing a good texture due to the clay minerals, and improving the ease of dispensing from the container after storage.

In the present invention, the mass ratio (A)/(B) of component (A) to component (B) is preferably 10 to 500, more preferably 20 to 300, and even more preferably 35 to 100, from the viewpoints of improving the spreadability of the cleanser composition when applied to the skin with water and spread, not immediately lathering when massaged onto the skin, providing a satisfactory massage sensation with a creamy or gel-like cleanser composition, providing a good texture due to the clay minerals, and improving the ease of dispensing from the container after storage.

The fatty acids and salts thereof as component (C) used in the present invention are those represented by the above general formula (1).
In the general formula (1), R ¹ represents a linear or branched alkyl or alkenyl group having 9 to 23 carbon atoms.
In general formula (1), the number of carbon atoms in ^R1 is preferably 11 to 17, and more preferably 11 to 15, from the viewpoints of improving the spreadability of the cleanser composition when it is applied to the skin and spread, not immediately lathering when massaged onto the skin, providing a satisfactory massage feeling with a creamy or gel-like cleanser composition, providing a good rough texture due to the clay mineral, and improving dischargeability from a container after storage at room temperature and at low temperatures. Furthermore, a straight chain is preferred from the viewpoints of improving a good rough texture due to the clay mineral, dischargeability from a container at room temperature and at low temperatures after storage, and storage stability at high temperatures.
Specific examples include salts of lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, arachidic acid, behenic acid, etc. Among these, from the viewpoints of improving the spreadability when the cleanser composition is applied to the skin with water and spread, not immediately foaming when massaged on the skin, providing a satisfactory massage feeling with a creamy or gel-like cleanser composition, providing a good roughness due to the clay minerals, and improving the dischargeability from a container after storage, it is preferable to include at least one or two or more selected from lauric acid, myristic acid, palmitic acid, and stearic acid, and more preferably to include at least one or two or more selected from lauric acid, myristic acid, and palmitic acid.
Examples of X include a hydrogen atom; 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. From the viewpoints of improving the spreadability of the cleanser composition when it is applied to the skin with water and spread, not immediately foaming when massaged onto the skin, providing a satisfactory massage feeling with a creamy or gel-like cleanser composition, imparting a good roughness due to the clay mineral, and improving the ease of discharge from a container after storage, alkali metals are preferred, and potassium is more preferred.

The fatty acid salt of component (C) can be present in the composition, for example, by mixing an unneutralized fatty acid with a neutralizing agent in the composition to form the fatty acid salt.
The neutralizing agent is a compound exhibiting basicity, and examples thereof include sodium hydroxide, potassium hydroxide, triethanolamine, basic amino acids, etc. Among these, from the viewpoints of improving the spreadability of the cleanser composition when it is applied to the skin with water and spread, not immediately foaming when massaged onto the skin, providing a satisfactory massage feeling due to the creamy or gel-like cleanser composition, providing a good rough feeling due to the clay minerals, and improving the dischargeability from the container after storage, it is preferable to contain at least one or more neutralizing agents selected from potassium hydroxide and sodium hydroxide, and more preferably to contain at least potassium hydroxide.

The neutralization rate of component (C) is preferably 75 to 88%, more preferably 77 to 87%, and even more preferably 79 to 86%, from the viewpoints of improving the spreadability of the cleanser composition when applied to the skin with water, not immediately lathering when massaged onto the skin, providing a satisfactory massage sensation with the cream or gel-like cleanser composition, providing a good texture due to the clay minerals, and improving the ease of dispensing from the container after storage.

One or more types of component (C) may be used, and the content is preferably 20 to 32% by mass, more preferably 23 to 31% by mass, and even more preferably 25 to 29% by mass, of the total composition as fatty acids, from the viewpoints of improving the spreadability of the cleanser composition when applied to the skin with water, not immediately lathering when massaged onto the skin, providing a satisfactory massage sensation with a creamy or gel-like cleanser composition, providing a good texture due to the clay minerals, and improving the ease of dispensing from the container after storage.

In the present invention, the mass ratio (A)/(C) of component (A) to component (C) is preferably 0.07 to 0.45, more preferably 0.08 to 0.3, and even more preferably 0.14 to 0.25, from the viewpoints of improving the spreadability of the cleanser composition when applied to the skin with water and spread, not immediately lathering when massaged onto the skin, providing a satisfactory massage sensation due to the cream or gel-like cleanser composition, providing a good texture due to the clay minerals, and improving the ease of dispensing from the container after storage.

The detergent composition of the present invention may further contain (D) a polyoxyalkylene alkyl glucoside, which can improve the dischargeability from the container after storage.
In the polyoxyalkylene alkyl glucoside, the alkyl group constituting the polyoxyalkylene alkyl glucoside may be an alkyl group having 1 to 4 carbon atoms, such as a methyl group or an ethyl group. From the viewpoint of improving the ejection properties from a container after storage, those containing a methyl group or an ethyl group are preferred, and those containing a methyl group are more preferred.
Examples of the polyoxyalkylene group constituting the polyoxyalkylene alkyl glucoside include a polyoxyethylene group, a polyoxypropylene group, and a polyoxybutylene group. From the viewpoint of improving the ejection properties from a container at room temperature and at low temperatures after storage, those containing a polyoxyethylene group or a polyoxypropylene group are preferred, and those containing a polyoxyethylene group are more preferred.
Furthermore, the average number of moles of polyoxyalkylene groups added constituting the polyoxyalkylene alkyl glucoside is preferably 1 to 40, more preferably 5 to 25, even more preferably 8 to 15, and even more preferably 10, from the viewpoint of improving the ejection property from the container after storage.

The polyoxyalkylene alkyl glucoside of component (D) is preferably a polyoxyethylene alkyl glucoside, more preferably a polyoxyethylene methyl glucoside having an average number of added moles of polyoxyethylene groups of 8 to 15, even more preferably a polyoxyethylene methyl glucoside having an average number of added moles of polyoxyethylene groups of 10.
As component (D), commercially available products such as Macbiobride MG-10E (manufactured by NOF Corporation), which is polyoxyethylene methyl glucoside having an average number of added moles of 10 polyoxyethylene groups, can be used.

Component (D) can be used alone or in combination of two or more types. From the viewpoint of improving dischargeability from the container after storage, the content is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and even more preferably 3 to 6% by mass of the total composition.

In the present invention, water constitutes the balance of the components, and its content is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 8 to 20% by mass of the total composition.

The detergent composition of the present invention may contain, in addition to the above-mentioned components, components commonly used in detergent compositions, such as surfactants other than component (C), powders other than component (A), polymeric compounds other than component (B), polyhydric alcohols other than component (D), oily components, pH adjusters, disinfectants, anti-inflammatory agents, preservatives, chelating agents, pearlizing agents, fragrances, cooling agents, UV absorbers, antioxidants, plant extracts, etc., within the scope of the present invention, provided that the effects of the present invention are not impaired.

The detergent composition of the present invention can be produced according to a conventional method, for example, by the following steps.
Step 1: A step of mixing a polyhydric alcohol, other aqueous components, and an alkaline agent.
Step 2: Adding fatty acid heated to 70 to 90°C to the mixture of step 1 heated to 70 to 90°C and mixing uniformly.
Step 3: A step of adding a clay mineral and a cationic polymer in that order to the mixture obtained in step 2 and mixing them.
Step 4: Cooling the mixture obtained in step 3 to a temperature in the range of 20 to 35°C.

The cleanser composition of the present invention has a viscosity at 20°C of preferably 200 to 4000 Pa·s, more preferably 300 to 3000 Pa·s, even more preferably 500 to 2000 Pa·s, still more preferably 600 to 1800 Pa·s, and particularly preferably 800 to 1200 Pa·s, from the viewpoints of improving spreadability when the cleanser composition is applied to the skin and spread, not immediately foaming when massaged onto the skin, providing a satisfactory massage feeling due to a creamy or gel-like cleanser composition, providing a good rough texture due to the clay minerals, and improving dischargeability from a container after storage.
In the present invention, the viscosity is measured under the following conditions.
Measuring equipment: Spindle viscometer (manufactured by Toki Sangyo Co., Ltd.),
Measuring jig: T-F,
Rotation speed: 5 rpm,
Measurement time: 60 seconds,
Measurement temperature: 20℃

The cleaning composition of the present invention is preferably stored in a jar, tube, or other container. Even when stored in a tube, it remains easily dispensed during use.

The detergent composition of the present invention can be used as a skin cleanser composition, and can be used, for example, as a handwash, face wash, cleanser, body soap, scalp cleanser, etc. Among these, it is particularly suitable as a face wash, and is suitable for use as a pack or for massage. When massaging, the clay mineral provides a suitable rough texture, allowing the user to experience the effects of the clay mineral.
To use the cleanser composition of the present invention, it is preferable to apply water to the skin, then apply the cleanser composition to the area without diluting it with water, massage the skin with the cleanser composition in a state where it does not foam, and then massage the skin several times to create a foam.
It is also preferable to apply the cleanser composition to the skin without diluting it with water after applying water to the skin, massage the skin without lathering the cleanser composition, and then lather the composition and wash the skin.

Examples 1 to 5 and Comparative Example 1
Detergent compositions having the compositions shown in Table 1 were prepared.
The resulting cleanser compositions were evaluated for roughness, applicability to wet skin, number of massages required to produce foam, and dischargeability from the container (20°C). Viscosity was also measured. The results are shown in Table 1.

(Manufacturing method)
Step 1: Polyoxyethylene methyl glucoside, other aqueous ingredients, and potassium hydroxide were mixed.
Step 2: To the mixture of step 1 heated to 70 to 90°C, fatty acid heated to 70 to 90°C was added and mixed uniformly.
Step 3: The clay mineral and cationic polymer were added to the mixture obtained in step 2 and mixed.
Step 4: The mixture obtained in step 3 was cooled to a temperature in the range of 20 to 35° C. to obtain a detergent composition.

(Evaluation method)
(1) Roughness:
Five expert evaluators took 2 g of each detergent composition and massaged a 4 x 10 cm area on the inside of their forearms with their index and middle fingers at a rate of one stroke per second. The roughness felt by the fingers due to the clay minerals was evaluated according to the following criteria. The results are shown as the average scores of the five evaluators.
5: There is a strong sense of roughness.
4: Feels rough.
3: Slightly rough feeling.
2: Slightly rough feeling.
1: No roughness is felt.

(2) Application to wet skin:
Five expert evaluators wetted their entire faces with 20 g of water, took 2 g of each cleanser composition in each hand (4 g in total), and massaged half of their faces with one hand, using both hands simultaneously five times in a circular motion, spreading the composition over the face. The ease of spreading was evaluated according to the following criteria. The results are shown as the average scores of the five evaluators.
5: Very easy to spread (easy to apply).
4: Easy to spread (apply).
3: Slightly easy to spread (slightly difficult to apply).
2: Not very easy to spread (somewhat difficult to apply).
1: Difficult to spread (difficult to apply).

(3) Number of massages until foam forms:
Five expert evaluators wetted their entire faces with 20 g of water, dispensed 2 g of each cleanser composition into each hand (4 g in total), and massaged half of their faces with one hand, using both hands simultaneously in a circular motion. Each circular massage was counted as one massage, and the number of massages required to produce foam was evaluated. The optimal number of massages required to produce a noticeable massage and an appropriate number of foams was 16 to 24. Foaming refers to the state in which the cleanser composition has clearly turned white when viewed from the face during the massage. The results are shown as the average of the number of massages performed by the five evaluators.

(4) Dischargeability from container (20°C)
50 g of each detergent composition was filled into a tube with a hole diameter of 8φ, a tube diameter of 35φ, and a tube length of 10 cm, and left to stand in a thermostatic chamber at 20°C for one month. After one month, the detergent composition in the tube was removed from the thermostatic chamber, and five expert evaluators ejected the detergent composition from the tube and evaluated its ejection properties according to the following criteria. The results are shown as the average scores of the five evaluators.
5: The tube can be pushed smoothly to dispense.
4: The tube can be pushed fairly smoothly and the liquid can be dispensed.
3: It is a little heavy, but it can be dispensed by pushing the tube.
2: The tube is pressed quite hard and only a small amount can be dispensed.
1: Even when the tube is pressed quite hard, it cannot be dispensed.

(5) Viscosity:
The viscosity was measured using a spindle viscometer (manufactured by Toki Sangyo Co., Ltd.) under the following measurement conditions.
The viscosity was measured 24 hours after production, taking into consideration that the physical properties of the detergent composition would be stabilized.
Measuring jig: T-F,
Rotation speed: 5 rpm,
Measurement time: 60 seconds,
Measurement temperature: 20℃

Claims (5)

The following components (A), (B), and (C):
(A) 2 to 8 mass% of at least one or more clay minerals selected from Moroccan lava clay, rhyolite powder, and Tanakura clay ;
(B) a cationic polymer having a weight-average molecular weight of 30,000 to 1,000,000;
(C) General formula (1):
R ¹ -COOX (1)
(wherein ^R1 represents an alkyl group or alkenyl group having 9 to 23 carbon atoms, and X represents a hydrogen atom, an alkali metal, ammonium, ammonium derived from an alkanolamine, or a basic amino acid)
20 to 32% by mass of fatty acids represented by the formula:
wherein the clay mineral of component (A) has a swelling ratio in water of 1 to 50 cm ³ /2 g, the clay mineral of component (A) has a number average particle size of 30 to 2000 μm, the mass ratio of component (A) to component (B), (A)/(B), is 10 to 500, and the viscosity at 20°C is 200 to 4000 Pa·s . 2. The cleaning composition according to claim 1, comprising at least Moroccan lava clay as component (A). The cleanser composition according to claim 1 or 2, which is a skin cleanser composition. 4. The cleaning composition according to claim 1, wherein X in general formula (1) is a hydrogen atom or an alkali metal. The cleaning composition according to any one of claims 1 to 4, wherein the content of component (B) is 0.08 to 0.15 mass%.