JP2017197480A - Oil-in-water emulsion type makeup cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-in-water emulsion type makeup cosmetic having good sense of use and excellent storage stability.SOLUTION: There is provided an oil-in-water emulsion type makeup cosmetic which comprises (A) an oil component, (B) a higher alcohol, (C) a surfactant, (D) an inorganic powder and (E) a polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked with a water-soluble crosslinking agent. The ethylenically unsaturated carboxylic acid monomer may be at least one selected from the group consisting of acrylic acid, a salt of acrylic acid, methacrylic acid and a salt of methacrylic acid.SELECTED DRAWING: None

Description

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

  Makeup cosmetics generally include vegetable oils, hydrocarbons, ester oils, silicone oils, etc .; surfactants; polyhydric alcohols, higher fatty acids, higher alcohols, triglycerides, polymer compounds, etc .; talc, mica, titanium oxide, It consists of powder components such as color pigments, and there are various types such as solid foundation, liquid foundation, eye shadow, blusher, lipstick, eyeliner, mascara, sunscreen emulsion, solid type, non-aqueous type, W There are various dosage forms such as / O emulsion type, O / W emulsion type, and aqueous. In such makeup cosmetics, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, hydrophobically-modified urethane-associated polymer, hydroxyethyl cellulose, xanthan gum are used to adjust the feeling of refreshing, moist feeling, elongation, spread and the like. Water-soluble thickeners such as viscous minerals are used (see, for example, Patent Documents 1 and 2).

JP-A-5-97644 JP 2014-40385 A

  In recent base makeup cosmetics, there is a tendency that fine particle powder such as titanium oxide which is an ultraviolet scattering agent is blended in order to protect the skin from ultraviolet rays. When such fine particle powders are blended, it is necessary to use a considerable amount of a surfactant to ensure powder dispersibility and storage stability (emulsification stability), and the resulting cosmetics are easy to stick. There was a problem in terms of. When 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 the above weight reduction is impossible, and it is difficult to achieve both the storage stability and the feeling of use. .

  Therefore, the object of the present invention is that it contains an inorganic powder such as titanium oxide fine particles, but has a good feeling of use (for example, no stickiness, good spread with a light touch, no distortion) and storage stability. The object is to provide an oil-in-water emulsified makeup cosmetic with excellent properties.

  As a result of intensive studies to solve the above problems, the present inventors have found that an ethylenically unsaturated carboxylic acid monomer crosslinked with an oil, a higher alcohol, a surfactant, an inorganic powder, and a water-soluble crosslinking agent. The present invention was completed by finding that an oil-in-water emulsion makeup cosmetic containing at least the above polymer has good usability and excellent storage stability.

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

  [1] (A): Oil, (B): Higher alcohol, (C): Surfactant, (D): Inorganic powder, (E): Ethylene crosslinked by a water-soluble crosslinking agent Oil-in-water emulsified makeup cosmetics, comprising a polymer of a polymerizable unsaturated carboxylic acid monomer.

  [2] The underwater according to [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, a methacrylic acid, and a salt of methacrylic acid. Oil emulsified makeup cosmetics.

  [3] The water-soluble crosslinking agent is selected 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 oil-in-water emulsion makeup cosmetic according to [1] or [2], which is at least one selected.

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

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

  Since the oil-in-water emulsified makeup cosmetic according to the present invention has the above-described configuration, it contains an inorganic powder (inorganic powder) such as titanium oxide fine particles and has a good feeling of use (for example, no stickiness) It spreads with a light tactile sensation and is not twisted) and has excellent storage stability.

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

  The oil-in-water emulsified makeup cosmetic according to the present invention (sometimes referred to as “the cosmetic according to the present invention”) includes (A): oil, (B): higher alcohol, and (C): surface activity. Agent, (D): inorganic powder, and (E): polymer of ethylenically unsaturated carboxylic acid monomer crosslinked with water-soluble crosslinking agent (sometimes referred to as “(E): polymer”). Is a cosmetic having the form of an O / W emulsion. Hereinafter, each component which can comprise the cosmetics which concern on this invention is explained in full detail.

[(A): Oil content]
(A): Oil content in the cosmetic according to the present invention is an oil component other than (B): higher alcohol and (C): surfactant. (A): Oils that can be used in cosmetics can be used. For example, natural oils, hydrocarbons, and silicones are used in consideration of the texture, familiarity, appearance, slipperiness, etc. An oil, ester oil, etc. are mentioned.

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

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

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

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

  (A): Other examples of the oil include oil-soluble ultraviolet absorbers and oil-soluble drugs.

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

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

[(B): higher alcohol]
(B): The higher alcohol in the cosmetic according to the present invention is a linear or branched monohydric alcohol having 12 or more carbon atoms. (B): As carbon number which comprises a higher alcohol, 12-40 are preferable, More preferably, it is 14-30, More preferably, it is 16-26. Carbon number is in the above range (B): By using a higher alcohol, the storage stability of the cosmetic tends to be further improved.

  (B): The higher alcohol may be either a saturated alcohol (alcohol having no carbon-carbon unsaturated bond) or an unsaturated alcohol (alcohol having one or more carbon-carbon unsaturated bonds), From the viewpoint of storage stability, a saturated alcohol is preferable.

  (B): Examples of higher alcohols include behenyl alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol (cetanol), myristyl alcohol, cetostearyl alcohol, 2-octyldodecanol, and oleyl alcohol. Note that (B): higher alcohols may be used alone or in combination of two or more.

  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. Further, 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): When the content of the higher alcohol is 0.1% by mass or more, the storage stability of the cosmetic tends to be further improved. On the other hand, (B): By making content of a higher alcohol into 10 mass% or less, the stickiness of cosmetics is suppressed and there exists a tendency for a usability | use_condition to become better.

[(C): Surfactant]
(C) in the cosmetic according to the present invention: As the surfactant, surfactants usually used in cosmetics (for example, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants) Agent). (C): As the surfactant, sorbitan fatty acid ester, polyglycerol 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, One or more surfactants selected from ethyl cellulose and the like, sodium alkylbenzenesulfonate, and polyoxyethylene alkylphenyl ether sulfate are preferably used. (C): The surfactants 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 at least mass%. Further, 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 making the content of the surfactant 0.1% by mass or more, the storage stability of the cosmetic tends to be further improved. On the other hand, when the content of the surfactant (C) is 10% by mass or less, it is more economically advantageous and the feeling of use of the cosmetic tends to be further improved, for example, stickiness can be further suppressed.

[(D): Inorganic powder]
Examples of (D): inorganic powder in the cosmetics according to the present invention include those usually used in base makeup cosmetics (for example, foundations), such as those obtained by pulverizing minerals in the form of plates. And amorphous inorganic powder. (D): As an inorganic powder, a powder having an effect of concealing, adhering or glossy, for example, talc, mica, aluminum hydroxide, titanium oxide, zinc oxide, kaolin, iron oxide (Bengara), yellow Examples thereof include iron oxide and black iron oxide. (D): The inorganic powders may be used alone or in combination of two or more.

  The content of the inorganic powder (D) 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. is there. Moreover, 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 making content of inorganic powder 5 mass% or more, there exists a tendency for the function as makeup cosmetics (for example, foundation), such as concealment power, to improve more. (D): By making the amount of inorganic powder 20% by mass or less, there is a tendency that it becomes more economically advantageous.

[(E): Polymer]
(E): The polymer in the cosmetic according to the present invention is a polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked by a water-soluble crosslinking agent. (E): The polymer preferably has water absorption, and may be, for example, a water absorbent resin. That is, (E): the polymer is a water-absorbing resin containing a polymer of an ethylenically unsaturated carboxylic acid monomer, preferably crosslinked by a water-soluble crosslinking agent, and more preferably a water-absorbing resin comprising the polymer. 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, a methacrylic acid, a salt of methacrylic acid, and the like are preferable. Can be mentioned. An ethylenically unsaturated carboxylic acid monomer can be used individually by 1 type or in combination of 2 or more types.

  (E): In the polymer, the neutralization degree of the resulting 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 of the ethylenically unsaturated carboxylic acid (before neutralization). Examples of the alkali used for neutralization include sodium hydroxide, potassium hydroxide, triethanolamine, diisopropylamine, and ammonia. The neutralization method is not particularly limited, and examples thereof include a method of previously neutralizing an ethylenically unsaturated carboxylic acid monomer and a method of neutralizing a polymer obtained by polymerization.

  Moreover, as a water-soluble crosslinking agent, the compound which has 2 or more of a polymerizable unsaturated group and / or a reactive functional group (one or both of a polymerizable unsaturated group and a reactive functional group) is mentioned preferably. The reactive functional group is a functional group that can react with a carboxyl group (which may be in a salt state) of the ethylenically unsaturated carboxylic acid monomer to form a crosslinked structure. Specific examples thereof include a glycidyl group and an isocyanate group. Examples of the water-soluble crosslinking agent having two or more glycidyl groups include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether. Examples of the water-soluble crosslinking agent having two or more polymerizable unsaturated groups include N, N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and water-soluble sucrose allyl ether. A water-soluble crosslinking agent can be used individually by 1 type or in combination of 2 or more types. 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 crosslinking 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, there is a tendency that the allyl group, which is a functional group involved in the crosslinking reaction, is insufficient and the crosslinking reaction does not 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 group remaining in 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 to alkaline sucrose, and then etherifying by dropwise addition of allyl bromide. it can. At this time, water-soluble sucrose allyl ether is efficiently obtained by adjusting the amount of allyl bromide to a range of preferably 2 to 6 times mol, more preferably 2 to 5 times mol of sucrose. be able to. The etherification reaction temperature is, for example, about 80 ° C. Usually, the reaction is completed in about 3 hours after the addition of allyl bromide. Water-soluble sucrose allyl ether can be recovered by adding alcohol to the aqueous phase separated from the reaction solution, filtering out precipitated salts, and 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 suspension polymerization in the presence of a water-soluble crosslinking agent. Among the suspension polymerization methods, the reverse phase suspension polymerization method in which a polymerization reaction is carried out while dispersing droplets of an aqueous phase containing an ethylenically unsaturated carboxylic acid monomer, a water-soluble crosslinking agent and water in a hydrophobic solvent. Is preferred.

  As the hydrophobic solvent used for the reverse phase suspension polymerization, for example, at least one petroleum 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. 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 reverse phase suspension polymerization, the aqueous phase containing the ethylenically unsaturated carboxylic acid monomer and the hydrophobic solvent may each contain other components such as a surfactant and a radical initiator.

  Surfactants are mainly used to stabilize the 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 alkylphenyl ether sulfates.

  The amount of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the ethylenically unsaturated carboxylic acid monomer. If the amount of the surfactant is too small, there may be a problem in the stability of the suspension during polymerization, and if the amount of the surfactant is too large, it tends to be economically disadvantageous.

  The radical initiator is not particularly limited as long as it is used for normal radical polymerization, but potassium persulfate, ammonium persulfate, sodium persulfate, azo initiators, 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 with respect to the ethylenically unsaturated carboxylic acid monomer. If the amount of the radical initiator is too small, the polymerization reaction tends not to proceed or a long time is required for the reaction. When the amount of the radical initiator is too large, the chain length of the polymer to be produced is shortened, and the viscosity of the aqueous liquid of the polymer (for example, a water absorbent resin) tends to decrease.

  During the 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 resulting polymer particles. Depending on conditions such as reaction vessel and production scale, for example, when a 2 L flask is used as a reaction vessel, a polymer of an appropriate size can be obtained by carrying out reverse phase suspension polymerization at a stirring speed of 800 to 1000 rpm. It is likely that particles can be obtained. Thus, the size of the polymer particles can be controlled by adjusting the stirring speed during the polymerization reaction. Thus, polymer particles (for example, water-absorbing resin particles) having a median particle diameter of preferably about 5 to 30 μm can be obtained. The shape of the polymer particles obtained in this way is spherical, and this shape is maintained even in an aqueous liquid such as cosmetics. Therefore, in cosmetics using this, various properties, tactile sensations and feelings of use are obtained. It is thought to have a positive effect.

  Other conditions for the polymerization reaction, for example, the polymerization reaction temperature, the reaction time, and the like are appropriately adjusted. 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 polymerization temperature can be started by adjusting the bath temperature to 60 ° C. In this case, the start of the polymerization reaction can be confirmed from the fact that the temperature in the reaction vessel rises to about 70 ° C. by the polymerization heat. Thereafter, the polymerization reaction is usually completed by conducting an aging reaction for about 30 minutes to 3 hours. If the aging time is less than 30 minutes, the reaction may not be sufficiently completed, and the remaining ethylenically unsaturated carboxylic acid monomer may increase. After the aging reaction, for example, the product can be obtained by raising the bath temperature and distilling off the water and the hydrophobic solvent in the reaction vessel.

  (E): A polymer may be used individually by 1 type and may be used in combination of 2 or more type.

  (E): By blending (containing) the polymer, it has excellent storage stability, light elongation and spread are obtained, it has a good feeling of use such as excellent tactile sensation, and a good softness Cosmetics that can provide a focus effect can be obtained.

  The content of the polymer (E) 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 mass% or more. Further, the content is preferably 2% by mass or less, more preferably 1.8% by mass or less, and further preferably 1.5% by mass or less based on the total amount (100% by mass) of the cosmetic according to the present invention. is there. (E): By making the content of the polymer 0.02% by mass or more, the storage stability of the cosmetic, the feeling of use, and the soft focus effect tend to be further improved. On the other hand, (E): By making the content of the polymer 2% by mass or less, excessive thickening and warping are suppressed, and the usability tends to be further improved. Also, it tends to be more economical.

  The cosmetic according to the present invention may contain other components other than those described above. Examples of the other components include (E): aqueous components other than the polymer (for example, water, humectant, sequestering agent, antioxidant, water-soluble ultraviolet absorber, water-soluble drug, etc.). . In addition, the cosmetics according to the present invention usually contain water. Content of the said aqueous component in the cosmetics which concern on this invention can be suitably selected from the range of 40-90 mass% (specifically 50-85 mass%), for example based on the whole quantity (100 mass%) of the said cosmetics. .

  In addition, in this specification, content about each component contained in the cosmetics which concern on this invention represents the value (dry mass conversion value) when not absorbing water about a water absorbing component.

  The cosmetic according to the present invention can be produced in accordance with a conventional method for producing an oil-in-water emulsion type cosmetic. For example, an oil component ((A): oil component, (B): higher alcohol, etc.) and an aqueous component (water, (E): polymer, etc.) are stirred and emulsified in the presence of (C): surfactant. And the like. In addition, (D): Inorganic powder can be mix | blended timely.

  The viscosity of the cosmetic according to the present invention can be adjusted as appropriate depending on the type and content of the constituent components. For example, from the viewpoint that it can be used favorably as a makeup cosmetic, a BH viscometer (rotation speed: 20 rpm) The viscosity at 25 ° C. measured by the above is preferably 1000 to 100,000 mPa · s, more preferably 20000 to 70000 mPa · s.

  The cosmetics according to the present invention can be used as various makeup cosmetics such as foundations, liquid foundations, eye shadows, blushers, lipsticks, eyeliners, mascaras, sunscreen emulsions and the like.

  Hereinafter, the present invention will be described more specifically 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. 136.8g (0.4mol) of sucrose was added here, and it stirred for 120 minutes at 70-85 degreeC, and prepared alkaline sucrose aqueous solution. To this alkaline sucrose aqueous solution, 145.2 g (1.2 mol) of allyl bromide was dropped over 1.5 hours (during the dropping, the temperature of the aqueous solution was set to 70 to 85 ° C.), and then 80 The sucrose was allyl etherified by aging at 3 ° C. for 3 hours. After cooling to room temperature, 440 g of water was added, and excess oil was separated with a separatory funnel to obtain a crude sucrose allyl ether aqueous solution. After adjusting the pH to 6-8 by adding hydrochloric acid to this crude sucrose allyl ether aqueous solution, 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 as a by-product, and the precipitate was removed from the aqueous solution by filtration. Further, excess water was removed from the aqueous solution by using an evaporator to obtain 166 g of purified water-soluble sucrose allyl ether having a degree of etherification of 2.4.

<Synthesis of Polymer (Water Absorbing Resin) of Ethylenically Unsaturated Carboxylic Acid Monomer Crosslinked by Water-soluble Crosslinking Agent>
Production Example 2
A stirrer, a reflux condenser, and a dropping funnel were attached to a 500 mL separable flask. In this separable flask, 72 g of acrylic acid and water were put to prepare 90 g of an 80% by mass acrylic acid aqueous solution. While cooling and stirring the acrylic acid aqueous solution, 54 g of a 30% by mass aqueous sodium hydroxide solution was added dropwise. Further, 56 g of ion-exchanged water, 0.32 g of water-soluble sucrose allyl ether obtained in Production Example 1 as a water-soluble crosslinking agent (0.35% by mass with respect to the aqueous solution of acrylic acid prepared first), and an initiator 2,2′-azobis (2-methylpropionamidine) dihydrochloride (W-50 Pure Chemical Industries, Ltd., V-50) as 0.04 g is added, and an ethylenically unsaturated carboxylic acid monomer aqueous solution is added. Prepared.
Separately, 330 g of n-heptane was put into a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and sorbitan monostearate (NOF CORPORATION) as a surfactant. (Nonion SP-60R) 2.7 g was added, and this was dispersed and dissolved in n-heptane. The ethylenically unsaturated carboxylic acid monomer aqueous solution prepared previously was added here. Next, in order to remove oxygen present in the atmosphere, raw materials and solvent in the reaction vessel, nitrogen gas was blown into the solution to replace the system with nitrogen, and the bath temperature was maintained at 60 ° C. and stirred. While stirring at a speed of 1000 revolutions / minute, polymerization was carried out by the reverse phase suspension polymerization method over 1 hour. After completion of the polymerization, water and n-heptane were distilled off to obtain 90 g of water-absorbent resin powder which was a polymer of acrylic acid and its sodium salt and was crosslinked with water-soluble sucrose allyl ether. It was.

<Synthesis of carboxyvinyl polymer>
Production Example 3
In a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube, 45 g (0.625 mol) of acrylic acid, 1.32 g of pentaerythritol allyl ether, 150 g of n-hexane and 2,2 0.081 g (0.00035 mol) of '-azobis (methylisobutyrate) was charged to prepare a reaction solution. After stirring the reaction liquid and mixing the respective raw materials uniformly, nitrogen gas was blown into the solution in order to remove oxygen present in the atmosphere of the reaction vessel, the raw materials and the solvent. Next, the reaction solution was kept at 60 to 65 ° C. for 4 hours under a nitrogen atmosphere. After completion of the reaction, the resulting 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 white fine powdery carboxyvinyl polymer powder. Got.

<Cosmetics: Preparation of liquid foundation (milky lotion)>
Example 1
Liquid foundations containing the following components in various proportions were prepared. Specifically, after the mixture of components 1 to 3 (oil phase (oil component)) is heated to 80 ° C., component 4 (surfactant) is added, and the mixture of components 5 to 8 prepared at 80 ° C. (water) Phase (aqueous component)) and emulsified using a homomixer at 5000 r / min for 5 minutes, followed by further stirring at 13000 r / min for 5 minutes with component 9 (inorganic powder mixture) ) Was mixed. Thereafter, component 10 (water absorbent resin) was added, and the mixture was stirred and mixed uniformly at 13000 r / min for 5 minutes to obtain a liquid foundation. The viscosity measured by the following procedure of this liquid foundation was 37000 mPa · s.
(Liquid foundation composition)
Ingredient 1: Cetanol 3.0% by mass
Component 2: Triethylhexanoin 10.0% by mass
Ingredient 3: Squalane 5.0% by mass
Ingredient 4: Self-emulsifying type glyceryl monostearate 3.0 mass%
Component 5: PEG-200 5.0 mass%
Component 6: 1,3-butanediol 5.0% by mass
Ingredient 7: 0.5 mass% of 2-phenoxyethanol
Component 8: Purified water remainder Component 9: Inorganic powder mixture 10.0% by mass
Component 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 (titanium oxide 97%) 40.0% by mass
Titanium oxide 3.0% by mass
Kaolin 2.0 mass%
Iron oxide (Bengara) 0.7% by mass
Yellow iron oxide 4.0% by mass
Black iron oxide 0.4% by mass

Example 2
In Example 1, except that the amount of component 10 (water absorbent resin) was changed to 0.4% by mass, 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. It was. It should be noted that the amount of purified water used was reduced by an amount corresponding to the increase in component 10 with respect to Example 1.

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

Comparative Example 2
Liquid foundations containing the following components in various proportions were prepared. Specifically, after heating the mixture of components 1 to 3 (oil phase) to 80 ° C, component 4 (surfactant) is added, and the mixture of components 5 to 9 (water phase) prepared at 80 ° C is added. Then, emulsification was carried out using a homomixer at 5000 r / min for 5 minutes, and then component 10 was mixed with stirring at 13000 r / min for 5 minutes. Furthermore, component 11 was added and the carboxyvinyl polymer was neutralized while stirring at 13000 r / min for 5 minutes to obtain a liquid foundation having a viscosity of 44200 mPa · s measured by the following procedure.
(Liquid foundation composition)
Ingredient 1: Cetanol 3.0%
Ingredient 2: Triethylhexanoin 10.0%
Ingredient 3: Squalane 5.0%
Component 4: Self-emulsifying glyceryl monostearate 3.0%
Component 5: PEG200 5.0%
Ingredient 6: 1,3 butanediol 5.0%
Ingredient 7: 2-phenoxyethanol 0.5%
Component 8: Carboxyvinyl polymer (prepared in Production Example 3) 0.05%
Component 9: Purified water Residue Component 10: Inorganic powder mixture (same as 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. It should be noted that the amount of purified water used was increased from Example 1 by the amount of unused cetanol (component 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 measured by the following procedure of the liquid foundation was 78000 mPa · s. In addition, the amount of purified water used was increased from Example 2 by the amount of unused cetanol (component 1). The obtained liquid foundation was close to a loose powder and did not have a creamy smooth property.

<Evaluation of Liquid Foundation>
(Storage stability)
About the liquid foundation obtained by the Example and the comparative example, stability (storage stability) was evaluated by confirming the state after preserve | saving for 7 days with a 50 degreeC thermostat. The state was confirmed visually.
Good storage stability (○): No separation between water phase and oil phase was observed. Poor storage stability (×): Separation between water phase and oil phase was observed.

(Feeling of use)
About the liquid foundation obtained by the Example and the comparative example, the test feeling [lightness (light tactile sense), easiness of spreading, no stickiness, feeling of film remaining by a total of 10 testers of 5 males and 5 females , Warpability] was evaluated. Specifically, for each element of the feeling of use [lightness, ease of spreading, non-stickiness, feeling of film remaining, goodness], 10-point evaluation of 1 to 5 points is performed by 10 people according to the following criteria, The score was totaled. The case where the total score is 201 points or more is evaluated as ◯ (excellent in feeling of use), the case of 190 points or more and 200 points or less is evaluated as △ (inferior in feeling of use), and the case of 189 points or less is evaluated as x (very inferior in feeling of use). did.
5 points
4 points
Normal 3 points
2 points
Inferior 1 point In addition, about a feeling of film remaining, a feeling of use is so favorable that there is no film remaining feeling. As for the warp, the feeling of use is better as there is no warp.
The liquid foundation obtained in Comparative Example 3 has a very low viscosity and does not require evaluation of the above-mentioned feeling of use, and is extremely inferior to the feeling of use (that is, it is not worthy of being usable as a cosmetic). There was an obvious cosmetic.

(viscosity)
Toki Sangyo BH viscometer, 20rpm
Measurement temperature: 25 ° C
The rotor used the following according to the viscosity.
50-500 mPa · s: No. 1
200-2,000 mPa · s: No. 2
500 to 5,000 mPa · s: No. 3
1,000 to 10,000 mPa · s: No. 4
2,000 to 20,000 mPa · s: No. 5
5,000 to 50,000 mPa · s: No. 6
20,000-200,000 mPa · s: No. 7

(Soft focus effect)
The soft foundation effect was evaluated about the liquid foundation obtained by the Example and the comparative example. Specifically, after applying the liquid foundation to the back of the hand, conditions such as wrinkle and pore concealment and presence / absence of shine were visually confirmed. The soft focus effect was evaluated 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 (×): Regardless of the presence or absence of shine, the concealment property of wrinkles and pores is low Note that the liquid foundation obtained in Comparative Example 3 was not worthy of being usable as a cosmetic, so the soft focus effect was not evaluated. It was.

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

Claims (5)

(A): oil content,
(B): higher alcohol,
(C): a surfactant;
(D): inorganic powder;
(E): a polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked by a water-soluble crosslinking agent;
Oil-in-water emulsified makeup cosmetics.   The oil-in-water emulsion type makeup 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.   The water-soluble crosslinking agent is selected 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 oil-in-water emulsified makeup cosmetic according to claim 1 or 2, which is at least one kind.   (B): The oil-in-water emulsion makeup cosmetic according to any one of claims 1 to 3, wherein the higher alcohol is a linear or branched monohydric alcohol having 12 to 40 carbon atoms.   The oil-in-water emulsified makeup cosmetic according to any one of claims 1 to 4, wherein the viscosity at 25 ° C measured by a BH viscometer (rotation speed: 20 rpm) is 1000 to 100,000 mPa · s.