JP6897517B2 - Mist lotion - Google Patents

Description

The present invention relates to a mist lotion containing natural water having a specific hardness.

The water used for the lotion is mainly tap water collected from a river and purified, and ion-exchanged water from which impurities such as metal ions have been removed with an ion-exchange resin is generally used. The components removed by the ion exchange resin may include natural moisturizing factors (NMF) such as calcium ions and magnesium ions. NMF plays an important role in maintaining healthy skin, and in addition to mineral salts such as calcium ion and magnesium ion, organic acids such as amino acids, pyrrolidone carboxylic acid (and its salts), urea and lactic acid (and their salts). It is known that when the amount of NMF contained in the stratum corneum decreases, including salt) and the like, the moisturizing function is lowered and the skin tends to become dry.

It is widely recognized that mineral salts such as calcium ions and magnesium ions are effective for moisturizing the skin in cosmetics using sea mud rich in mineral salts (Patent Document 1). Clay packs containing clay minerals, so-called mud packs, are known as dosage forms that effectively utilize mineral salts. The clay pack is used by applying the paste directly to the skin, or by applying a pack sheet obtained by applying the paste on a sheet such as a non-woven fabric sheet to the skin. However, when a mineral salt (particularly a mineral salt having a divalent value or higher) is added to the lotion, the substances dissolved in water may be bonded to each other to form a substance insoluble in water. Therefore, when natural water rich in mineral salts is used as a lotion, the mineral salts contained in the natural water may cause the generation of insoluble matter, and in particular, when used, it is sprayed in the form of a mist container or the like. There is a risk that it cannot be applied to so-called mist mineral water.

As a technique for preventing the precipitation of useful components contained in the cosmetic water, for example, in order to stably dissolve the L-ascorbic acid phosphate magnesium salt, a nonionic surfactant of HLB 15 to 20 and a sodium salt of an organic acid are used. A blended lotion composition (Patent Document 2) has been proposed. However, although nonionic surfactants and sodium salts of organic acids are effective in preventing the generation of insoluble substances, lotions containing them may cause a decrease in usability such as stickiness. Therefore, there is a demand for a highly stable lotion while maintaining a good feeling of use and a moisturizing effect.

Japanese Unexamined Patent Publication No. 2001-233722 Japanese Unexamined Patent Publication No. 7-277940

In view of the above circumstances, the present invention may have excellent storage stability (particularly excellent at low temperature storage stability) in which insoluble matter is unlikely to be generated while containing natural water, and may cause makeup loss. The purpose is to provide a non-greasy, mist-use lotion that gives the skin a smooth and fluffy feel.

As a result of diligent research to solve the above problems, the present inventors have conducted intensive research and found that a constituent unit based on natural water having a specific hardness, 2- (meth) acryloyloxyethyl phosphorylcholine, and a constituent unit based on (meth) acrylic acid alkyl ester. It has been found that the above-mentioned object can be achieved by combining a predetermined amount of a copolymer containing and phenoxyethanol.

That is, the present invention has the following features.
[1] (a) 60 to 99.5% by mass of natural water having a hardness of 10 to 400 mg / L.
Equation (I):

[In the formula, R ¹ indicates a hydrogen atom or a methyl group, and * indicates a binding site with another structural unit. ]
A structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine represented by, and formula (II) :.

[In the formula, R ² indicates a hydrogen atom or a methyl group, R ³ indicates an alkyl group, and * indicates a binding site with another structural unit. ]
0.005-2% by mass of copolymer containing a structural unit based on (meth) acrylic acid alkyl ester represented by (c) 0.1 to 2% by mass of phenoxyethanol.
Contains,
A mist lotion having a mass ratio (b / c) of (b) and (c) of 0.01 to 3.
[2] The mist lotion according to the above [1], which further contains (d) 0.005 to 0.5% by mass of an acidic mucopolysaccharide.

The mist lotion of the present invention has excellent stability, and also has a good usability and a moisturizing effect.
That is, it has excellent storage stability that does not easily generate insoluble matter (especially excellent storage stability at low temperature), can be used without causing clogging of the mist container, can prevent makeup from collapsing, and is not sticky. It can give the skin a good smooth and fluffy feeling.

Hereinafter, embodiments of the present invention will be described. In the present specification, "(meth) acryloyl" means both "acryloyl" and "methacryloyl", and "(meth) acrylic" means both "acrylic" and "methacryl".

The mist toner (hereinafter, also simply referred to as “toner”) of the present invention contains the following components (a) to (c) as essential components.

[(A) component]
The component (a) used in the present invention is natural water having a hardness of 10 mg / L to 400 mg / L calculated from the contents of calcium salt and magnesium salt.

Natural water is not particularly limited as long as it has the above-mentioned specific hardness. For example, shallow well water and deep water classified in "2. Labeling method" of the Director General of Food Distribution Bureau on March 30, 1990. Well water, spring water, mineral spring water, hot spring water, underflow water, mineral water, etc. can be mentioned. Any of these natural waters may be used alone or in combination of two or more.

The hardness in the present invention is obtained by converting the amount of calcium and magnesium into the amount of calcium carbonate (CaCO ₃ ), expressed in [mg / L], and can be calculated using the following simple formula (1). ..

Hardness [mg / L] = (calcium amount [mg / L] x 2.5) + (macnesium amount [mg / L] x 4.1) ... (1)

In the present invention, the hardness of the component (a) calculated from the above formula (1) is in the range of 10 mg / L to 400 mg / L, preferably 20 mg / L to 200 mg / L, and more preferably 20 mg / L to 200 mg / L. It is 30 mg / L to 100 mg / L. If the hardness is less than 10 mg / L, the smoothness and plumpness may be insufficient, and if it exceeds 400 mg / L, the low temperature stability may decrease, the mist container may become clogged, or the mist container may become sticky. There is a risk that the makeup may come off, and the smoothness and plumpness may be insufficient.

The content of the component (a) is 60 to 99.5% by mass, preferably 80 to 99% by mass, and 90 to 98% with respect to the total amount of the lotion (that is, the total amount of the compositions constituting the lotion). More preferably by mass. If the content of the component (a) is less than 60% by mass, the smoothness and plumpness may be insufficient, and if it exceeds 99.5% by mass, the effect commensurate with the blending amount cannot be obtained.

[(B) component]
The component (b) used in the present invention is
Equation (I):

[In the formula, R ¹ indicates a hydrogen atom or a methyl group, and * indicates a binding site with another structural unit. ]
2- (Meta) acryloyloxyethyl phosphorylcholine-based structural unit represented by (hereinafter, also referred to as “constituent unit of formula (I)”) and formula (II) :.

[In the formula, R ² indicates a hydrogen atom or a methyl group, R ³ indicates an alkyl group, and * indicates a binding site with another structural unit. ]
It is a copolymer containing a structural unit based on the (meth) acrylic acid alkyl ester represented by (hereinafter, also referred to as “constituent unit of formula (II)”).

^{The alkyl group represented by R 3} in the structural unit of the formula (II) may be a linear alkyl group, a branched chain alkyl group, or a cyclic alkyl group, but is a straight chain. An alkyl group or a branched chain alkyl group is preferable, and the number of carbon atoms is preferably 1 to 22, more preferably 2 to 5, and particularly preferably 3 to 4. Specific examples of the structural unit of the formula (II) include methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, and butyl methacrylate. Among them, butyl methacrylate is particularly preferable because of its availability. The structural unit of the formula (II) may be one kind or two or more kinds.

The molar ratio (I / II) of the structural unit of the formula (I) to the structural unit of the formula (II) in the copolymer is preferably 99/1 to 10/90, more preferably 90/10 to 30/70, and 85 / 15 to 50/50 is particularly preferable.

The total content of the structural unit of the formula (I) and the structural unit of the formula (II) in the copolymer is usually 60% by mass to 100% by mass, preferably 70% by mass to 100% by mass, based on the whole copolymer. It is more preferably 80% by mass to 100% by mass.

The structural unit of the formula (II) is a unit in which the ^{alkyl group represented by R 3} in the formula is composed of an alkyl group having more than 22 carbon atoms (that is, a (meth) acrylic acid having an alkyl group having more than 22 carbon atoms. If it is a unit based on an alkyl ester), it may be sticky, the makeup may be disintegrated, and the smoothness and plumpness may be insufficient.

The component (b) may contain a structural unit other than the structural unit of the formula (I) and the structural unit of the formula (II), and such a structural unit includes ethylene, propylene, butene, isobutene, styrene and the like. Olefinic hydrocarbons and their isomers, or various derivatives thereof; ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, vinyl acetic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and their anhydrides. , Esters with alcohols having 1 to 6 carbon atoms (excluding (meth) acrylic acid alkyl esters constituting the structural unit represented by the above formula (II)), or carbonyl group, amino group, cyano group, nitrile group thereof. Ethylunically unsaturated carboxylic acid derivatives introduced with, etc .; Esters of vinyl alcohols and various carboxylic acids, ethers with various alcohols, or vinyl alcohols introduced with carbonyl group, amino group, cyano group, nitrile group, etc. Examples include structural units based on derivatives and the like.

The molecular weight of the component (b) preferably has a mass average molecular weight (Mw) of 5,000 to 2,000,000, more preferably 100,000 to 1,500,000, and particularly preferably 400,000 to 400,000. It is 1,200,000. When the mass average molecular weight (Mw) is within a preferable range, a sufficient effect is likely to be obtained. The mass average molecular weight (Mw) is measured by a gel permeation chromatography (GPC) method (polyethylene glycol equivalent). The mass average molecular weight by the GPC method can be calculated by using a methanol / chloroform mixed solvent (8/2 (volume ratio)) as a sample solution and using a standard polyethylene glycol calibration curve.

The component (b) may be a random copolymer or a block copolymer, but a random copolymer is preferable.

The component (b) is a monomer composition containing at least 2- (meth) acryloyloxyethyl phosphorylcholine and (meth) acrylic acid alkyl ester in the presence of a radical polymerization initiator in the molar ratio (I / II) of the above-mentioned constituent units. ) Can be polymerized by a known method such as solution polymerization in an inert gas atmosphere such as nitrogen, but a commercially available product can also be used. Examples of such commercially available products include "LIPIDURE (registered trademark) -PMB" (2-methacryloyloxyethyl phosphorylcholine-butyl methacrylate copolymer) manufactured by NOF CORPORATION.

In the present invention, the content of the component (b) is 0.005 to 2% by mass as an active ingredient with respect to the entire lotion (that is, the total amount of the compositions constituting the lotion), which is 0.01. ~ 1% by mass is preferable, and 0.02 to 0.5% by mass is more preferable. (B) If the content of the component is less than 0.005% by mass, the low temperature stability, the discharge property from the mist container, and the smoothness and plumpness may be insufficient, and if it exceeds 2% by mass. There is a risk that the low temperature stability will decrease, the mist container will be clogged, sticky, the makeup will come off, and the smoothness and plumpness will be insufficient.

[Ingredient (c)]
The component (c) used in the present invention is phenoxyethanol. It can be obtained by a commonly known method, for example, by reacting phenol with ethylene oxide or by reacting sodium phenoxide with ethylene chlorohydrin. Commercially available products can also be used as phenoxyethanol. For example, the product name "Phenoxitol" [manufactured by Clariant Japan Co., Ltd.] and the like can be mentioned.

In the present invention, the content of the component (c) is 0.1 to 2% by mass and 0.2 to 1% by mass with respect to the total amount of the lotion (that is, the total amount of the compositions constituting the lotion). Is preferable, and 0.3 to 0.6% by mass is more preferable. If the content of the component (c) is less than 0.1% by mass, the low temperature stability may be lowered, the mist container may be clogged, and the smoothness and plumpness may be insufficient. If it exceeds%, there is a risk that the makeup will come off, it will be sticky, and the feeling of plumpness will be insufficient.

In the present invention, the mass ratio (b / c) of the component (b) to the component (c) contained in the cosmetic water is 0.01 to 3, preferably 0.05 to 1, and more preferably 0. .1 to 0.5. If it is less than 0.01, the storage stability at low temperature, makeup loss, smoothness and plumpness, and non-greasy effect may be insufficient. If it exceeds 3, storage stability at low temperature, clogging of mist container, etc. There is a risk that the makeup will come off, the feeling of smoothness and plumpness, and the non-greasy effect will be insufficient.

[(D) component]
The lotion of the present invention may further contain the following component (d) in addition to the above components (a) to (c), whereby the effect of the present invention becomes more remarkable. ..

The component (d) used in the present invention is an acidic mucopolysaccharide, for example, acidic mucopolysaccharides such as hyaluronic acid, chondroitin-4-sulfate, chondroitin-6-sulfate, dermatan sulfate, keratan sulfate, and heparin, and them. Examples include salts and acetylated products of. Hyaluronic acid, chondroitin-4-sulfate, chondroitin-6-sulfuric acid and salts thereof are preferable, and hyaluronic acid and salts thereof are particularly preferable.

Examples of the acid mucopolysaccharide salt include inorganic salts and organic salts, examples of the inorganic salt include alkali metal salts such as sodium salt and potassium salt, and examples of the organic salt include quaternary ammonium salts. .. Preferably, it is a sodium salt or a potassium salt.

As the acidic mucopolysaccharide, a commercially available product can be used. Commercially available products include, for example, "Hyaluronic Acid HA-LQH1" manufactured by Cupy Co., Ltd., "Hyaluronic Acid FCH-200" manufactured by Kikkoman Biochemifa Co., Ltd., and "Hyaluronic Acid FCH-200" manufactured by Maruha Nichiro Foods Co., Ltd. as products of sodium hyaluronate. Nori Sotohara Na hyaluronate "Maruha" and the like can be mentioned.

As the component (d), one kind may be used alone, or two or more kinds may be used in combination.

In the present invention, the content of the component (d) is 0.005 to 0.5% by mass as an active ingredient with respect to the entire lotion (that is, the total amount of the compositions constituting the lotion), which is 0. 008 to 0.2% by mass is preferable, and 0.01 to 0.1% by mass is particularly preferable. When the content of the component (d) is within the above range, it is more preferable in terms of storage stability at low temperature, clogging of the mist container, disintegration of makeup, smoothness and plumpness, and non-greasyness.

The lotion of the present invention may contain ordinary water in addition to the component (a). The ordinary water is ion-exchanged water or distilled water used for ordinary cosmetic water, which is substantially free of minerals and has a hardness of 0 mg / L or less than 1 mg / L. Further, when commercially available products in the form of an aqueous solution or an aqueous dispersion are used as the component (b) and / or the component (d), the lotion of the present invention contains water derived from these products. The water contained in these products is ordinary water such as ion-exchanged water and distilled water, which is substantially free of minerals and has a hardness of 0 mg / L or less than 1 mg / L.

The content of ordinary water in the lotion of the present invention is preferably 0 to 40% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 3% by mass.

The cosmetic water of the present invention may contain the above-mentioned components (a) to (d) and other components other than ordinary water as long as the effects of the present invention are not impaired. Other ingredients are commonly used in cosmetics, such as lower alcohols such as ethanol, diols such as propylene glycol, sugar alcohols and sugar alcohol derivatives, thickeners such as carboxyvinyl polymers, sugars, surfactants. , Organic salts, inorganic salts, pH adjusters, chelating agents, antioxidants, bactericides, blood flow promoters, anti-inflammatory agents, UV absorbers, UV scatterers, vitamins, amino acids such as arginine, pigments, fragrances, etc. Can be blended within a range that does not impair the performance of the present invention.

The "mist lotion" in the present invention is, for example, a lotion that is filled in a pump container (that is, a mist container) provided with a spray mechanism and sprayed in a mist form at the time of use. Since it is applied in the form of a mist that is gentle on the skin, it can be applied evenly over a wide area without touching it, and it is possible to effectively apply lotion even on top of makeup.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and is appropriately modified to the extent that it can be adapted to the above and the following objectives. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.

[Examples 1 to 8 and Comparative Examples 1 to 6]
The components shown in Tables 1 and 2 below were mixed and uniformly dissolved to prepare the lotions of Examples 1 to 8 and Comparative Examples 1 to 6. The numerical values of the compounding components in Tables 1 and 2 are the contents (mass%) of the entire lotion including the remaining ion-exchanged water.

The supplementary explanation of the symbols in Table 1 is as follows.
* 1 "Natural water 1" Hardness: 50 mg / L
* 2 "Natural water 2" Hardness: 300 mg / L
* 3 "Natural water 3" Hardness: 25 mg / L
* 4 "LIPIDURE (registered trademark) -PMB", manufactured by Nichiyu Co., Ltd .; molar ratio (MPC) of the structural unit (MPC) based on 2-methacryloyloxyethyl phosphorylcholine and the structural unit (BMA) based on butyl methacrylate. An aqueous solution containing 5% by mass of a copolymer (mass average molecular weight = about 600,000) having a / BMA) of 4/1 The content in the table is the content of the copolymer (polymer) per total lotion. is there.
* 5 "Hyaluronic acid solution HA-LQH1", manufactured by Cupy Co., Ltd .; An aqueous solution containing 1% by mass of sodium hyaluronate and 0.15% by mass of methylparaben The content in the table is the content of sodium hyaluronate per lotion. Is.

The prepared lotions of Examples 1 to 8 and Comparative Examples 1 to 6 had (1) low temperature stability, (2) dischargeability from a mist container, (3) makeup breakage, (4) smoothness, and (5). The plumpness and (6) stickiness were evaluated by the following methods.

(1) Low temperature stability A low temperature storage test (storage temperature: 0 ° C., storage period: 4 weeks) was performed by filling a mist container (capacity 30 ml, main body: PET, tube: PE, pump head: PP) with lotion. .. Then, the temperature was returned to room temperature, the lamp was held over a fluorescent lamp, and the contour was judged according to the following criteria.

<Criteria>
⊚: When the solution is transparent and uniform.
◯: When the solution is extremely slightly turbid.
Δ: When there is clear turbidity in the entire solution.
X: When an insoluble component is generated and precipitation is observed.

(2) Dischargeability from mist container The lotion was packed in a mist container (main body: PET, tube: PE, pump head: PP) and sprayed daily at room temperature in an amount of 3 ml for 10 consecutive days. Then, the judgment was made according to the following criteria.

<Criteria>
⊚: When spraying can be performed smoothly until the end of the test.
◯: When a small amount of precipitate is seen around the spray port, but the spray can be smoothly performed until the end of the test.
Δ: When it may not be possible to spray smoothly even once due to clogging during the test.
X: When clogging occurs during the test and it becomes necessary to remove the precipitate by hand.

(3) Makeup collapse 20 women (23 to 55 years old) were used as panelists, made up with a commercially available solid foundation, and 0.5 ml of lotion filled in a mist container was applied to the entire face, and the skin after 1 hour. The condition of was evaluated according to the following criteria, and was judged according to the following criteria based on the total score of 20 evaluation points.

<Evaluation criteria>
2 points: I felt that my makeup was not broken.
1 point: I felt that my makeup was a little broken.
0 points: I felt that my makeup was broken.
The total score of 20 people was calculated and judged as follows.

<Criteria>
⊚: Total score of 35 points or more = Toner that does not easily lose makeup.
◯: Total score of 20 points or more and less than 35 points = Toner that does not easily lose makeup.
Δ: The total score is 10 points or more and less than 20 points = a lotion that slightly loses makeup.
X: Total score is less than 10 points = Toner that loses makeup.

(4) Smoothness 20 women (23-55 years old) were used as panelists, and after washing their faces, 0.5 ml of lotion filled in a mist container was applied to the entire face, and the smoothness felt the next morning was evaluated according to the following criteria. Then, based on the total score of 20 evaluation points, the judgment was made according to the following criteria.
It was.

<Evaluation criteria>
2 points: I felt that there was a smooth feeling.
1 point: I felt that it was a little smooth.
0 points: I didn't feel smooth.

<Criteria>
⊚: Total score of 35 points or more = Toner that feels very smooth.
◯: The total score is 20 points or more and less than 35 points = a lotion that gives a slightly smooth feeling.
Δ: The total score is 10 points or more and less than 20 points = a lotion that does not feel smooth and smooth.
X: Total score is less than 10 points = Toner that does not feel smooth.

(5) Plumpness 20 women (23-55 years old) were used as panelists, and after washing their faces, 0.5 ml of lotion filled in a mist container was applied to the entire face, and the plumpness felt the next morning was evaluated according to the following criteria. Then, based on the total score of 20 evaluation points, the judgment was made according to the following criteria.

<Evaluation criteria>
2 points: I felt it was plump.
1 point: I felt that it was a little plump.
0 points: I didn't feel plump.

<Criteria>
⊚: Total score is 35 points or more = Toner that feels very plump.
◯: The total score is 20 points or more and less than 35 points = a lotion that gives a slightly plump feeling.
Δ: The total score is 10 points or more and less than 20 points = a lotion that does not feel a little plump.
X: Total score is less than 10 points = Toner that does not feel plump.

(6) Stickiness Twenty women (23-55 years old) were used as panelists, and after washing their face, 0.5 ml of lotion filled in a mist container was applied to the entire face, and the stickiness felt after blending was evaluated according to the following criteria. Then, based on the total score of 20 evaluation points, the judgment was made according to the following criteria.

<Evaluation criteria>
2 points: I felt it was not sticky.
1 point: I felt it was not sticky.
0 points: I felt sticky.

<Criteria>
⊚: Total score of 35 points or more = very non-greasy lotion.
◯: Total score is 20 points or more and less than 35 points = non-sticky lotion.
Δ: Total score of 10 points or more and less than 20 points = slightly sticky lotion.
X: Total score is less than 10 points = sticky lotion.

As is clear from the results of Examples 1 to 8, the mist lotion of the present invention has excellent storage stability at low temperatures, can be used in a mist container without causing clogging, and causes makeup to come off. It was a non-greasy lotion with excellent smoothness and plumpness.

On the other hand, in Comparative Example 1, since the component (b) was not contained, the smooth feeling of the next morning and the plump feeling of the next morning were inferior, and the storage stability at low temperature and the discharge property from the mist container were also insufficient. ..

In Comparative Example 2, since the content of the component (c) was below the specified range, the low temperature stability was poor and smooth spraying could not be performed. In addition, the makeup was slightly broken, and good results were not obtained for the feeling of plumpness, smoothness, and stickiness the next morning.

In Comparative Example 3, since ion-exchanged water was used instead of the component (a), the discharge property from the mist container was slightly poor, and good results were not obtained for the smoothness and plumpness of the next morning.

In Comparative Example 4, since the content of the component (a) is below the specified range, the low temperature stability and the discharge property from the mist container are slightly poor, and good results cannot be obtained for the smooth feeling and stickiness of the next morning. It was.

In Comparative Example 5, since the content of the component (a) is below the specified range and the content of the component (b) is above the specified range, the low temperature stability and the discharge property from the mist container are poor, and the makeup is disintegrated. It was easy to make, and the next morning's plumpness and smoothness were not good, and stickiness also occurred.

In Comparative Example 6, since the mass ratio (b / c) of the component (b) and the component (c) exceeds the specified range, the low temperature stability and the discharge property from the mist container are slightly poor, and the makeup is slightly disintegrated. The next morning, the plumpness and smoothness were not good, and stickiness also occurred.

As described in detail above, according to the present invention, the present invention has excellent storage stability, excellent discharge property that does not cause clogging of the mist container, and does not cause makeup disintegration. It is possible to provide a mist lotion that can give a good smoothness and plumpness to the skin without being sticky.

Claims (2)

(A) 60 to 99.5% by mass of natural water having a hardness of 10 to 400 mg / L,
Equation (I):

[In the formula, R ¹ indicates a hydrogen atom or a methyl group, and * indicates a binding site with another structural unit. ]
A structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine represented by, and formula (II) :.

[In the formula, R ² indicates a hydrogen atom or a methyl group, R ³ indicates an alkyl group, and * indicates a binding site with another structural unit. ]
0.005-2% by mass of copolymer containing a structural unit based on (meth) acrylic acid alkyl ester represented by (c) 0.1 to 2% by mass of phenoxyethanol.
Contains,
A mist lotion having a mass ratio (b / c) of (b) and (c) of 0.01 to 3. The mist lotion according to claim 1, further comprising (d) 0.005 to 0.5% by mass of an acidic mucopolysaccharide.