JP7060916B2 - Underwater oil emulsified make-up cosmetics - Google Patents

Description

The present invention relates to an oil-in-water emulsified make-up cosmetic.

Makeup cosmetics are generally used with vegetable oils, hydrocarbons, ester oils, silicone oils, etc .; with surfactants; with polyhydric alcohols, higher fatty acids, higher alcohols, triglycerides, polymer compounds, etc .; with talc, mica, titanium oxide, etc. It consists of powder components such as coloring pigments; and its types are diverse, including solid foundations, liquid foundations, eye shadows, cheeks, lipsticks, eyeliners, mascara, sunscreen emulsions, etc. There are various dosage forms such as / O emulsified type, O / W emulsified type, and aqueous type. In such make-up cosmetics, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, hydrophobic-modified urethane-associated polymer, hydroxyethyl cellulose, xanthan gum are used to adjust the feeling of use such as refreshing feeling, moist feeling, elongation, and spreading. , Water-soluble thickeners such as viscous minerals are used (see, for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 5-97644 Japanese Unexamined Patent Publication No. 2014-40385

Recent base make-up cosmetics tend to contain fine particle powder such as titanium oxide, which is an ultraviolet scattering agent, in order to protect the skin from ultraviolet rays and the like. When such fine particle powder is blended, it is necessary to use a considerable amount of surfactant in order to secure powder dispersibility and storage stability (emulsification stability), and the obtained cosmetics are easily sticky and have a feeling of use. There was a problem in that. If the amount of the surfactant is reduced, the feeling of use is improved, but on the other hand, the powder dispersibility and the storage stability are deteriorated, so that the above amount cannot be reduced, and it is difficult to achieve both the storage stability and the feeling of use. ..

Therefore, an object of the present invention is to contain an inorganic powder such as titanium oxide fine particles, yet have a good usability (for example, no stickiness, a light tactile sensation, spread well, and no kinks), and storage stability is stable. The purpose is to provide an oil-in-water emulsified make-up cosmetic having excellent properties.

As a result of diligent studies to solve the above problems, the present inventors have made an ethylenically unsaturated carboxylic acid monomer crosslinked with an oil, a higher alcohol, a surfactant, an inorganic powder, and a water-soluble cross-linking agent. We have found that an oil-in-water emulsified make-up cosmetic containing at least the polymer of the above has a good usability and excellent storage stability, and has completed the present invention.

That is, the present invention includes, for example, the following subjects.

[1] (A): oil, (B): higher alcohol, (C): surfactant, (D): inorganic powder, (E): ethylene crosslinked by a water-soluble cross-linking agent. An oil-in-water emulsified make-up cosmetic containing a polymer of a sex-unsaturated carboxylic acid monomer.

[2] The water according to the above [1], wherein the ethylenically unsaturated carboxylic acid monomer is at least one selected from the group consisting of acrylic acid, a salt of acrylic acid, methacrylic acid, and a salt of methacrylic acid. Oil-emulsified make-up cosmetics.

[3] From the group consisting of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, N, N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and water-soluble sucrose allyl ether. The underwater oil emulsified make-up cosmetic according to the above [1] or [2], which is at least one selected.

[4] (B): The oil-in-water emulsified type according to any one of the above [1] to [3], wherein the higher alcohol is a linear or branched monohydric alcohol having 12 to 40 carbon atoms. Makeup cosmetics.

[5] The underwater oil emulsification type according to any one of the above [1] to [4], wherein the viscosity at 25 ° C. measured by a BH type viscometer (rotation speed: 20 rpm) is 1000 to 100,000 mPa · s. Makeup cosmetics.

Since the oil-in-water emulsified make-up cosmetic according to the present invention has the above-mentioned constitution, it has a good usability (for example, no stickiness) even though it contains an inorganic powder (inorganic powder) such as titanium oxide fine particles. , Light touch, spreads well, and does not wrinkle), and has excellent storage stability.

Hereinafter, embodiments of the present invention will be described in detail.

The underwater oil-emulsified make-up cosmetic according to the present invention (sometimes referred to as "cosmetic according to the present invention") includes (A): oil, (B): higher alcohol, and (C): surfactant. A polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked with an agent, (D): an inorganic powder, and (E): a water-soluble cross-linking agent (sometimes referred to as "(E): polymer"). It is a cosmetic having the form of an O / W type emulsion containing (is) as an essential ingredient. Hereinafter, each component that can constitute the cosmetic according to the present invention will be described in detail.

[(A): Oil content]
The (A): oil content in the cosmetic according to the present invention is an oily component other than (B): higher alcohol and (C): surfactant. (A): As the oil content, those that can be normally used for cosmetics can be used. For example, in consideration of texture, familiarity, appearance, slipperiness, etc. on the skin, natural oils, hydrocarbons, silicones, etc. can be used. Examples include oil and ester oil.

Examples of the natural oil include olive oil, macadamia nut oil, castor oil, jojoba oil, orange raffy oil, beeswax, lanolin, squalane and the like.

Examples of the hydrocarbon include squalane, liquid paraffin, hydrogenated polyisobutene, hydrogenated polybutene, isododecane, polyethylene wax, polypropylene wax and the like.

Examples of the silicone-based oil include modified silicone oils such as methylpolysiloxane, methylphenylpolysiloxane, cyclic methylsiloxane, and silicone polyether copolymers.

Examples of the ester oil include various fatty acid esters, such as octyldodecyl ester and glycerin ester (for example, triethylhexanoin) of each fatty acid such as oleic acid, erucic acid, myristic acid, and ricinoleic acid. Be done.

(A): Examples of the oil content include oil-soluble ultraviolet absorbers and oil-soluble agents.

(A): The oil components may be used individually or in combination of two or more.

The content of (A): oil in the cosmetic according to the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total amount (100% by mass) of the cosmetic according to the present invention. The content is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount (100% by mass) of the cosmetic according to the present invention. (A): By setting the oil content to 1% by mass or more, the effect as a cosmetic (for example, a moisturizing effect) tends to be higher. On the other hand, (A): By setting the oil content to 20% by mass or less, the stickiness is further suppressed, the feeling of use of the cosmetic is further improved, and the storage stability tends to be further improved.

[(B): Higher alcohol]
(B) in the cosmetic according to the present invention: The higher alcohol is a linear or branched monohydric alcohol having 12 or more carbon atoms. (B): The number of carbon atoms constituting the higher alcohol is preferably 12 to 40, more preferably 14 to 30, and even more preferably 16 to 26. The carbon number is in the above range (B): By using a higher alcohol, the storage stability of the cosmetic tends to be further improved.

Further, (B): the higher alcohol may be either a saturated alcohol (an alcohol having no carbon-carbon unsaturated bond) or an unsaturated alcohol (an alcohol having one or more carbon-carbon unsaturated bonds). Saturated alcohols are preferred from the standpoint of storage stability.

(B): Examples of the higher alcohol include behenyl alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol (cetyl alcohol), myristyl alcohol, cetostearyl alcohol, 2-octyldodecanol, oleyl alcohol and the like. In addition, (B): higher alcohol may be used individually or may be used in combination of 2 or more types.

The content of (B): higher alcohol in the cosmetic according to the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass, based on the total amount (100% by mass) of the cosmetic according to the present invention. % Or more. The content is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount (100% by mass) of the cosmetic according to the present invention. (B): By setting the content of the higher alcohol to 0.1% by mass or more, the storage stability of the cosmetic tends to be further improved. On the other hand, (B): By setting the content of the higher alcohol to 10% by mass or less, the stickiness of the cosmetic is suppressed, and the feeling of use tends to be improved.

[(C): Surfactant]
(C) in the cosmetic according to the present invention: As the surfactant, a surfactant usually used in cosmetics (for example, nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant) Agent) can be used. (C): Examples of the surfactant include sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitol fatty acid ester, modified polyethylene wax, modified polypropylene wax, polyvinyl alcohol, polyethylene oxide, and cellulose ether (hydroxyethyl cellulose, One or more surfactants selected from (ethyl cellulose, etc.), sodium alkylbenzene sulfonate, and polyoxyethylene alkylphenyl ether sulfate are preferably used. (C): The surfactant may be used alone or in combination of two or more.

The content of (C): surfactant in the cosmetic according to the present invention is preferably 0.1% by mass or more, more preferably 0.5, based on the total amount (100% by mass) of the cosmetic according to the present invention. It is mass% or more. The content is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount (100% by mass) of the cosmetic according to the present invention. (C): By setting the content of the surfactant to 0.1% by mass or more, the storage stability of the cosmetic tends to be further improved. On the other hand, (C): By setting the content of the surfactant to 10% by mass or less, it is economically more advantageous and the stickiness is further suppressed, and the feeling of use of the cosmetic tends to be further improved.

[(D): Inorganic powder]
Examples of the (D): inorganic powder in the cosmetics according to the present invention include those usually used for base make-up cosmetics (for example, foundations), for example, those obtained by crushing minerals and having a plate shape. And amorphous inorganic powder. (D): As the inorganic powder, those having an effect of hiding power, adhesive power, and glossiness, for example, talc, mica, aluminum hydroxide, titanium oxide, zinc oxide, kaolin, iron oxide (bengala), yellow Examples thereof include iron oxide and black iron oxide. (D): The inorganic powder may be used alone or in combination of two or more.

The content of (D): inorganic powder in the cosmetic according to the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount (100% by mass) of the cosmetic according to the present invention. be. The content is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount (100% by mass) of the cosmetic according to the present invention. (D): By setting the content of the inorganic powder to 5% by mass or more, the function as a make-up cosmetic (for example, foundation) such as hiding power tends to be further improved. (D): By setting the amount of the inorganic powder to 20% by mass or less, it tends to be more economically advantageous.

[(E): Polymer]
The (E): polymer in the cosmetic according to the present invention is a polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked with a water-soluble cross-linking agent. (E): The polymer preferably has water absorbency, and may be, for example, a water-absorbent resin. That is, (E): the polymer is a water-absorbent resin containing a polymer of an ethylenically unsaturated carboxylic acid monomer preferably crosslinked with a water-soluble cross-linking agent, and more preferably water-absorbent composed of the polymer. It is a sex resin.

As the ethylenically unsaturated carboxylic acid monomer, a water-soluble ethylenically unsaturated carboxylic acid monomer is preferable, and specifically, for example, acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid and the like are preferable. Can be mentioned. The ethylenically unsaturated carboxylic acid monomer may be used alone or in combination of two or more.

(E): In the polymer, the degree of neutralization of the obtained polymer can be easily adjusted by neutralizing the carboxyl group of the ethylenically unsaturated carboxylic acid with an alkali. The degree of neutralization refers to the ratio of the number of moles of neutralized groups to the total number of moles of carboxyl groups (before neutralization) of the ethylenically unsaturated carboxylic acid. Examples of the alkali used for neutralization include sodium hydroxide, potassium hydroxide, triethanolamine, diisopropylamine, ammonia and the like. The neutralization method is not particularly limited, and examples thereof include a method of neutralizing an ethylenically unsaturated carboxylic acid monomer in advance, a method of neutralizing a polymer obtained by polymerization, and the like.

Further, as the water-soluble cross-linking agent, a compound having two or more polymerizable unsaturated groups and / or reactive functional groups (one or both of the polymerizable unsaturated group and the reactive functional group) is preferably mentioned. The reactive functional group is a functional group capable of forming a crosslinked structure by reacting with the carboxyl group (which may also be in the salt state) of the ethylenically unsaturated carboxylic acid monomer. Specific examples thereof include a glycidyl group and an isocyanate group. Examples of the water-soluble cross-linking agent having two or more glycidyl groups include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether. Examples of water-soluble cross-linking agents having two or more polymerizable unsaturated groups include N, N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and water-soluble sucrose allyl ether. The water-soluble cross-linking agent may be used alone or in combination of two or more. Of these, water-soluble sucrose allyl ether is preferable.

The degree of etherification of the water-soluble sucrose allyl ether used as the water-soluble cross-linking agent is preferably 2.0 to 3.5, more preferably 2.2 to 3.2. If the degree of etherification of the water-soluble sucrose allyl ether is too low, the allyl group, which is a functional group involved in the crosslinking reaction, tends to be insufficient, and the crosslinking reaction tends to be difficult to proceed effectively. If the degree of etherification of the water-soluble sucrose allyl ether is too high, the solubility in water decreases, so that the cross-linking reaction between the sucrose allyl ether and the ethylenically unsaturated carboxylic acid monomer is difficult to proceed in the aqueous phase. Tend to be. This degree of etherification is the average value of the molar ratio of allyl ether groups to sucrose. The degree of etherification can be calculated from the amount of acetic anhydride consumed by reacting the hydroxyl groups remaining in the sucrose allyl ether with acetic anhydride in pyridine.

The water-soluble sucrose allyl ether can be obtained, for example, by adding sodium hydroxide as a catalyst to an aqueous sucrose solution, converting sucrose into alkaline sucrose, and then dropping allyl bromide to etherify. can. At this time, by adjusting the amount of allyl bromide in the range of preferably 2 to 6 times mol, more preferably 2 to 5 times mol, of sucrose, a water-soluble allyl sucrose ether can be efficiently obtained. be able to. The reaction temperature for etherification is, for example, about 80 ° C. Usually, the reaction is completed about 3 hours after the dropping of allyl bromide. The water-soluble sucrose allyl ether can be recovered by adding alcohol to the aqueous phase separated from the reaction solution, filtering out the precipitated salts, and then distilling off excess alcohol and water.

(E): The polymer can be obtained, for example, by a method including a step of polymerizing an ethylenically unsaturated carboxylic acid monomer by a suspension polymerization method in the presence of a water-soluble cross-linking agent. Among the suspension polymerization methods, a reverse phase suspension polymerization method in which a polymerization reaction is carried out while dispersing aqueous phase droplets containing an ethylenically unsaturated carboxylic acid monomer, a water-soluble cross-linking agent and water in a hydrophobic solvent. Is preferable.

As the hydrophobic solvent used for the reverse phase suspension polymerization, for example, at least one petroleum-based hydrocarbon solvent selected from aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons is used. Examples of the aliphatic hydrocarbon include n-pentane, n-hexane and n-heptane. Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane. Examples of aromatic hydrocarbons include benzene, toluene and xylene. In particular, at least one hydrophobic solvent selected from n-hexane, n-heptane, cyclohexane and toluene can be preferably used as an industrial general-purpose solvent. The amount of the hydrophobic solvent is, for example, 100 to 200 parts by mass with respect to 100 parts by mass of the aqueous phase containing the ethylenically unsaturated carboxylic acid monomer and the like.

In the case of reverse phase suspension polymerization, the aqueous phase containing an ethylenically unsaturated carboxylic acid monomer and the like and the hydrophobic solvent may each contain other components such as a surfactant and a radical initiator.

Surfactants are mainly used to stabilize suspension during polymerization. The surfactant is not particularly limited as long as it is usually used in reverse phase suspension polymerization. Preferably, sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitol fatty acid ester, modified polyethylene wax, modified polypropylene wax, polyvinyl alcohol, polyethylene oxide, cellulose ether (hydroxyethyl cellulose, ethyl cellulose, etc.), sodium alkylbenzene sulfonate, And one or more surfactants selected from polyoxyethylene alkyl phenyl ether sulfates are used.

The amount of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the ethylenically unsaturated carboxylic acid monomer. If the amount of surfactant is too small, the stability of the suspension state during polymerization may be problematic, and if the amount of surfactant is too large, it tends to be economically disadvantageous.

The radical initiator is not particularly limited as long as it is used for ordinary radical polymerization, but potassium persulfate, ammonium persulfate, sodium persulfate, an azo-based initiator and the like are preferably used. For example, 2,2'-azobis (2-methylpropionamidine) dihydrochloride can be preferably used.

The amount of the radical initiator is preferably 0.01 to 0.5% by mass, more preferably 0.02 to 0.2% by mass, based on the ethylenically unsaturated carboxylic acid monomer. If the amount of the radical initiator is too small, the polymerization reaction tends to be difficult to proceed, or the reaction tends to take a long time. If the amount of the radical initiator is too large, the chain length of the produced polymer tends to be short, and the viscosity of the aqueous liquid of the polymer (for example, the water-absorbent resin) tends to decrease.

In the case of reverse phase suspension polymerization, the size of the droplets containing the ethylenically unsaturated carboxylic acid monomer and the like is closely related to the size of the obtained polymer particles. Although it depends on the conditions such as the reaction vessel and the production scale, for example, when a 2 L flask is used as the reaction vessel, a polymer of an appropriate size can be polymerized by performing reverse phase suspension polymerization at a stirring speed of 800 to 1000 rpm. It is likely that particles can be obtained. In this way, the size of the polymer particles can be controlled by adjusting the stirring speed during the polymerization reaction. In this way, polymer particles (for example, water-absorbent resin particles) preferably having a medium particle diameter of about 5 to 30 μm can be obtained. The shape of the polymer particles thus obtained is spherical, and this shape is retained even in an aqueous liquid such as cosmetics. Therefore, in cosmetics using this, various properties, touch and usability can be obtained. It is considered to have a positive effect.

Other conditions of the polymerization reaction, such as the polymerization reaction temperature and the reaction time, are also adjusted as appropriate. The polymerization reaction temperature is, for example, 50 to 80 ° C., and the reaction time is, for example, 30 minutes to 3 hours. For example, when a 2 L flask is used as a reaction vessel, the bath temperature can be adjusted to 60 ° C. to start the polymerization reaction. In this case, the start of the polymerization reaction can be confirmed from the fact that the temperature inside the reaction vessel rises to about 70 ° C. due to the heat of polymerization. After that, the polymerization reaction is usually completed by carrying out the aging reaction for about 30 minutes to 3 hours. If the aging time is less than 30 minutes, the reaction may not be completed sufficiently, and the amount of residual ethylenically unsaturated carboxylic acid monomer may increase. After the aging reaction, the product can be obtained, for example, by raising the bath temperature to distill off the water and the hydrophobic solvent in the reaction vessel.

(E): As the polymer, one kind may be used alone, or two or more kinds may be used in combination.

(E): By blending (containing) the polymer, it has excellent storage stability, light elongation and spread, excellent usability such as excellent tactile sensation, and good softness. It is possible to obtain a cosmetic that has a focus effect.

The content of (E): polymer in the cosmetic according to the present invention is preferably 0.02% by mass or more, more preferably 0.03% by mass, based on the total amount (100% by mass) of the cosmetic according to the present invention. % Or more, more preferably 0.05% by mass or more. The content is preferably 2% by mass or less, more preferably 1.8% by mass or less, still more preferably 1.5% by mass or less, based on the total amount (100% by mass) of the cosmetic according to the present invention. be. (E): By setting the content of the polymer to 0.02% by mass or more, the storage stability, usability and soft focus effect of the cosmetic tend to be further improved. On the other hand, (E): By setting the content of the polymer to 2% by mass or less, the occurrence of excessive thickening and twisting is suppressed, and the usability tends to be further improved. It also tends to be more economically advantageous.

The cosmetic according to the present invention may contain other ingredients other than the above. Examples of the other component include (E): an aqueous component other than the polymer (for example, water, a moisturizer, a sequestrant, an antioxidant, a water-soluble ultraviolet absorber, a water-soluble agent, etc.). .. The cosmetic according to the present invention usually contains water. The content of the aqueous component in the cosmetic according to the present invention can be appropriately selected from the range of, for example, 40 to 90% by mass (specifically, 50 to 85% by mass) based on the total amount (100% by mass) of the cosmetic. ..

In the present specification, the content of each component contained in the cosmetic according to the present invention represents a value (dry mass conversion value) of the water-absorbing component when it is not absorbing water.

The cosmetic according to the present invention can be produced according to a method for producing an ordinary oil-in-water emulsified cosmetic. For example, an oily component ((A): oil, (B): higher alcohol, etc.) and an aqueous component (water, (E): polymer, etc.) are stirred and emulsified in the presence of (C): a surfactant. There is a method of making it. (D): Inorganic powder can be blended in a timely manner.

The viscosity of the cosmetic according to the present invention can be appropriately adjusted depending on the type and content of the constituent components, and for example, from the viewpoint of being able to be used satisfactorily as a make-up cosmetic, a BH type viscometer (rotation speed: 20 rpm). The viscosity at 25 ° C. measured by the above is preferably 1000 to 100,000 mPa · s, more preferably 20,000 to 70,000 mPa · s.

The cosmetic according to the present invention can be used as various makeup cosmetics such as foundation, liquid foundation, eye shadow, blusher, lipstick, eyeliner, mascara, and sunscreen emulsion.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

<Synthesis of water-soluble sucrose allyl ether>
Production Example 1
A stirrer, a reflux condenser and a dropping funnel were attached to a 1000 mL separable flask. In this separable flask, 48 g (1.2 mol) of sodium hydroxide was dissolved in 144 g of water. 136.8 g (0.4 mol) of sucrose was added thereto, and the mixture was stirred at 70 to 85 ° C. for 120 minutes to prepare an aqueous alkaline sucrose solution. 145.2 g (1.2 mol) of allyl bromide was added dropwise to this alkaline sucrose aqueous solution over 1.5 hours (during the dropping, the temperature of the aqueous solution was 70 to 85 ° C.), and then 80. The sucrose was allyl etherified by aging at ° C. for 3 hours. After cooling to room temperature, 440 g of water was added, and excess oil was separated with a separating funnel to obtain a crude sucrose allyl ether aqueous solution. Hydrochloric acid was added to this crude sucrose allyl ether aqueous solution to adjust the pH to 6 to 8, and then water was removed using a rotary evaporator until the mass of the aqueous solution reached 480 g. Then, 200 g of ethanol was added to precipitate salts such as sodium bromide, which is a by-product, and the precipitate was removed from the aqueous solution by filtration. Further, excess water was removed from the aqueous solution using an evaporator to obtain 166 g of purified water-soluble sucrose allyl ether having an etherification degree of 2.4.

<Synthesis of a polymer (water-absorbent resin) of an ethylenically unsaturated carboxylic acid monomer cross-linked with a water-soluble cross-linking agent>
Manufacturing example 2
A stirrer, a reflux condenser and a dropping funnel were attached to a 500 mL separable flask. 72 g of acrylic acid and water were placed in this separable flask to prepare 90 g of an 80% by mass acrylic acid aqueous solution. While cooling and stirring this acrylic acid aqueous solution, 54 g of a 30% by mass sodium hydroxide aqueous solution was added dropwise. Further, 56 g of ion-exchanged water, 0.32 g of the water-soluble sucrose allyl ether obtained in Production Example 1 as a water-soluble cross-linking agent (0.35% by mass based on the initially prepared acrylic acid aqueous solution), and an initiator. Add 0.04 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) as an aqueous solution of ethylenically unsaturated carboxylic acid monomer. Prepared.
Separately, 330 g of n-heptane was placed in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and sorbitan monostearate (Nichiyu Co., Ltd.), which is a surfactant, was added. , Nonion SP-60R) 2.7 g was added, and this was dispersed and dissolved in n-heptane. The previously prepared aqueous ethylenically unsaturated carboxylic acid monomer solution was added thereto. Next, the bath temperature is maintained at 60 ° C. and stirring is performed while nitrogen gas is blown into the solution to replace the nitrogen in the system in order to remove the atmosphere in the reaction vessel, the raw materials and the oxygen present in the solvent. Polymerization was carried out by the reverse phase suspension polymerization method over 1 hour while stirring at a speed of 1000 rpm. After completion of the polymerization, water and n-heptane were distilled off to obtain 90 g of a water-absorbent resin powder which is a polymer of acrylic acid and a sodium salt thereof and which is a polymer crosslinked with water-soluble sucrose allyl ether. rice field.

<Synthesis of carboxyvinyl polymer>
Production example 3
45 g (0.625 mol) of acrylic acid, 1.32 g of pentaerythritol allyl ether, 150 g of n-hexane and 2,2 in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. '-Azobis (methylisobutyrate) 0.081 g (0.00035 mol) was charged to prepare a reaction solution. After stirring the reaction solution to uniformly mix the raw materials, nitrogen gas was blown into the solution in order to remove the oxygen present in the atmosphere of the reaction vessel, the raw materials and the solvent. Then, the reaction solution was kept at 60 to 65 ° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the produced slurry was heated to 90 ° C. to distill off n-hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain 42 g of a white fine powder carboxyvinyl polymer powder. Got

<Cosmetics: Preparation of liquid foundation (milky lotion)>
Example 1
A liquid foundation containing the following components in each ratio was prepared. Specifically, a mixture of components 1 to 3 (oil phase (oily component)) is heated to 80 ° C., then component 4 (surfactant) is added, and a mixture of components 5 to 8 (water) prepared at 80 ° C. The phase (aqueous component)) is added and emulsified using a homomixer under the condition of 5000 r / min for 5 minutes, and then the component 9 (inorganic powder mixture) is further stirred under the condition of 13000 r / min for 5 minutes. ) Was mixed. Then, component 10 (water-absorbent resin) was added, and the mixture was stirred uniformly under the conditions of 13000 r / min for 5 minutes to obtain a liquid foundation. The viscosity of this liquid foundation measured by the following procedure was 37,000 mPa · s.
(Composition of liquid foundation)
Ingredient 1: Cetanol 3.0% by mass
Ingredient 2: Triethylhexanoin 10.0% by mass
Ingredient 3: Squalene 5.0% by mass
Ingredient 4: Self-emulsifying glyceryl monostearate 3.0% by mass
Ingredient 5: PEG-200 5.0% by mass
Ingredient 6: 1,3-butanediol 5.0% by mass
Ingredient 7: 2-Phenoxyethanol 0.5% by mass
Ingredient 8: Purified water Residual Ingredient 9: Inorganic powder mixture 10.0% by mass
Ingredient 10: Water-absorbent resin (prepared in Production Example 2) 0.05% by mass

(Component 9: Composition of Inorganic Powder Mixture)
Talc 37.9% by mass
Mica 12.0% by mass
Aluminum hydroxide treated Titanium oxide (97% titanium oxide) 40.0% by mass
Titanium oxide 3.0% by mass
Kaolin 2.0% by mass
Iron oxide (Bengala) 0.7% by mass
Yellow iron oxide 4.0% by mass
Black iron oxide 0.4% by mass

Example 2
In Example 1, a liquid foundation having a viscosity of 50,000 mPa · s measured by the following procedure was obtained in the same manner as in Example 1 except that the amount of component 10 (water-absorbent resin) was changed to 0.4% by mass. rice field. In addition, the amount of purified water used was reduced by the amount of the increase of the component 10 with respect to Example 1.

Comparative Example 1
In Example 1, a liquid foundation having a viscosity of 18500 mPa · s measured by the following procedure was obtained in the same manner as in Example 1 except that component 10 (water-absorbent resin) was not used. In addition, the amount of purified water used was increased by the amount of non-use of component 10 with respect to Example 1.

Comparative Example 2
A liquid foundation containing the following components in each ratio was prepared. Specifically, after heating the mixture (oil phase) of components 1 to 3 to 80 ° C., the component 4 (surfactant) is added, and the mixture (aqueous phase) of components 5 to 9 prepared at 80 ° C. is added. , Emulsified under the condition of 5000 r / min for 5 minutes using a homomixer, and then the component 10 was mixed while stirring under the condition of 13000 r / min for 5 minutes. Further, component 11 was added, and the carboxyvinyl polymer was neutralized while stirring under the conditions of 13000 r / min for 5 minutes to obtain a liquid foundation having a viscosity of 44,200 mPa · s measured by the following procedure.
(Composition of liquid foundation)
Ingredient 1: Cetanol 3.0%
Ingredient 2: Triethylhexanoin 10.0%
Ingredient 3: Squalene 5.0%
Ingredient 4: Self-emulsifying glyceryl monostearate 3.0%
Ingredient 5: PEG200 5.0%
Ingredient 6: 1,3 butanediol 5.0%
Ingredient 7: 2-Phenoxyethanol 0.5%
Ingredient 8: Carboxyvinyl polymer (prepared in Production Example 3) 0.05%
Ingredient 9: Purified water Residual Ingredient 10: Inorganic powder mixture (same as that used in Example 1) 10.0%
Ingredient 11: 6% NaOH aqueous solution 0.3%

Comparative Example 3
A liquid foundation was obtained in the same manner as in Example 1 except that cetanol (component 1) was not used. The viscosity of the liquid foundation measured by the following procedure was 800 mPa · s. In addition, the amount of purified water used was increased by the amount of non-use of cetanol (component 1) with respect to Example 1.

Comparative Example 4
A liquid foundation was obtained in the same manner as in Example 2 except that cetanol (component 1) was not used. The viscosity of the liquid foundation measured by the following procedure was 78,000 mPa · s. In addition, the amount of purified water used was increased by the amount of non-use of cetanol (component 1) with respect to Example 2. The obtained liquid foundation was close to a sloppy powder and did not have a creamy smooth property.

<Evaluation of liquid foundation>
(Storage stability)
The stability (storage stability) of the liquid foundations obtained in Examples and Comparative Examples was evaluated by confirming the state after storage in a constant temperature bath at 50 ° C. for 7 days. The condition was visually confirmed.
Good storage stability (○): Separation of water phase and oil phase was not observed Poor storage stability (×): Separation of water phase and oil phase was observed.

(Usage)
Regarding the liquid foundations obtained in the examples and comparative examples, a total of 10 testers, 5 males and 5 females, gave a feeling of use during application [lightness (light touch), ease of spreading, no stickiness, film residual feeling. , Shaking property] was evaluated. Specifically, 10 people evaluated each element of usability [lightness, ease of spreading, non-stickiness, film residual feeling, kinking] on a scale of 1 to 5 based on the following criteria. The points were totaled. If the total score is 201 points or more, it is evaluated as ○ (excellent in usability), if it is 190 points or more and 200 points or less, it is evaluated as △ (inferior in usability), and if it is 189 points or less, it is evaluated as × (extremely inferior in usability). bottom.
Excellent 5 points
Good 4 points
Normal 3 points
Slightly inferior 2 points
Inferior 1 point Regarding the feeling of film residue, the feeling of use is so good that there is no film residue. Further, regarding the kinks, the usability is so good that there is no kinks.
The liquid foundation obtained in Comparative Example 3 has an extremely low viscosity and is extremely inferior in usability (that is, not worthy of being usable as a cosmetic) without the above-mentioned evaluation of usability. Was an obvious cosmetic.

(viscosity)
BH type viscometer manufactured by Toki Sangyo, 20 rpm
Measurement temperature: 25 ° C
The following rotors were used depending on the viscosity.
50-500 mPa · s: No. 1
200-2,000 mPa · s: No. 2
500-5,000 mPa · s: No. 3
1,000-10,000 mPa · s: No. 4
2,000-20,000 mPa · s: No. 5
5,000-50,000 mPa · s: No. 6
20,000-200,000 mPa · s: No. 7

(Soft focus effect)
The soft focus effect was evaluated for the liquid foundations obtained in Examples and Comparative Examples. Specifically, after applying the liquid foundation to the back of the hand, the concealing properties of wrinkles and pores, and the presence or absence of shine were visually confirmed. The evaluation of the soft focus effect was carried out according to the following criteria.
Good soft focus effect (○): No shine, high concealment of wrinkles and pores Poor soft focus effect (△): Concealment of wrinkles and pores, but shine Soft focus effect Extremely poor (×): Low concealment of wrinkles and pores regardless of the presence or absence of shine The liquid foundation obtained in Comparative Example 3 was not suitable for use as a cosmetic, so the soft focus effect was not evaluated. rice field.

As shown in Table 1, the cosmetics obtained in the examples had a good usability and excellent storage stability. In addition, all of them had a good soft focus effect.

Claims (4)

(A): Oil content and
(B): Higher alcohol and
(C): Surfactant and
(D): Inorganic powder and
(E): A polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked with a water-soluble sucrose allyl ether having a degree of etherification of 2.0 to 3.5, and a polymer.
An underwater oil-emulsified make-up cosmetic containing. The oil-in-water emulsified make-up according to claim 1, wherein the ethylenically unsaturated carboxylic acid monomer is at least one selected from the group consisting of acrylic acid, a salt of acrylic acid, methacrylic acid, and a salt of methacrylic acid. Up cosmetics. (B): The oil-in-water emulsified make-up cosmetic according to claim 1 or 2 , wherein the higher alcohol is a linear or branched monohydric alcohol having 12 to 40 carbon atoms. The underwater oil-emulsified make-up cosmetic according to any one of claims 1 to 3 , wherein the viscosity at 25 ° C. measured by a BH type viscometer (rotation speed: 20 rpm) is 1000 to 100,000 mPa · s.