JP2008143821A - Emulsion cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic that has excellent stability with time, no powdery feeling, no feeling of dryness and an excellent sense of use. <P>SOLUTION: The emulsion cosmetic comprises (A) hydrophobic powder, (B) a copolymer in which a poly(N-acylalkyleneimine) composed of a repeating unit represented by formula (1) (wherein, R is H, a 1-22C alkyl group, a cycloalkyl group, an aralkyl group or an aryl group; x is a number of 2 or 3) is bonded through a hetero atom-containing alkylene group to at least one of a terminal or side-chain silicon atom of an organopolysiloxane segment or an amino-modified silicone, (C) a nonionic water-soluble polymer containing a polyoxyalkylene chain having an average molecular weight of 300-100,000 in the molecule and (D) an oily component liquid at 25°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an emulsified cosmetic having good temporal stability, no powderiness, little bulkiness, and excellent usability.

  Conventionally, hydrophobic powders have been blended in cosmetics in order to give a smooth and smooth feeling, improve water resistance and makeup feeling, and the like. However, the hydrophobic powder has poor dispersion stability in the composition, and particularly in an oil-in-water composition, there is a problem that the powder aggregates and settles over time. For this reason, attempts have been made to disperse hydrophobic powder more stably.

  For example, a hydrophobic powder-containing oil-in-water emulsion composition (Patent Document 1) containing a surfactant that is liquid at room temperature with an HLB value of less than 7 and a surfactant that is liquid at room temperature with an HLB value of 7 or more, Contains an oil-in-water emulsion composition containing a nonionic surfactant having an HLB of 12 or less, a hydrophobic powder, a water-soluble polymer (Patent Document 2), and a silicone oil of 50% by mass or more based on the total amount of the oil phase. And by adding a specific surfactant such as an oil-in-water emulsion composition containing polyoxyalkylene-modified polysiloxane and / or isostearic acid (Patent Document 3) as a dispersant for the hydrophobized powder. A method for uniformly dispersing powder has been studied.

  However, even if the dispersion state of the hydrophobic powder is good in these compositions, if the hydrophobic powder is white, the hydrophobic powder aggregates and becomes white when the composition is applied onto the skin. Occasionally, it may float or uneven in the finish, and it may not be possible to fully exhibit effects such as UV protection and cosmetic effects. In addition, there is a problem that the feeling of use is bad such as being powdery and bulky, and since the surfactant is used in a large amount, the sustainability of the effect is low.

  On the other hand, poly (N-acylalkylenimine) -modified silicones and amino-modified silicones are known as agents that improve the dispersibility of hydrophobic powders (Patent Documents 4 and 5). When the powder was actually applied onto the skin, the powder aggregated and whitening occurred, resulting in a poor finish.

In addition, polyethylene glycol and polyoxyalkylene-modified saccharides have been reported to improve the stability of emulsions and to suppress aggregation of inorganic powders in cosmetics (Patent Document 6, Patent Document 7, Patent) Document 8, Patent Document 9, and Patent Document 10). However, even if the composition using these can be applied neatly on the skin, it is inferior in water resistance and the like, and there is a problem that the effect and finish do not last for a long time.
JP 2001-89347 A Japanese Patent Laid-Open No. 9-87129 Japanese Patent Laid-Open No. 2004-210698 JP-A-9-227331 JP 2004-217703 A JP 9-151110 A JP 2002-205912 A JP 2003-105191 A JP 2004-203825 A JP 2006-45151 A

  An object of the present invention is to provide an emulsified cosmetic having good stability over time, no powderiness, little bulkiness, and excellent usability.

  When the present inventors use a combination of a hydrophobic powder, a specific silicone polymer or amino-modified silicone, and a specific nonionic water-soluble polymer and oil component, the stability over time is good, and the powder It has been found that a cosmetic can be obtained that has no porosity, has a low feeling of bulkiness, has an excellent feeling of use, has no white float or uneven coating, and has an excellent UV protection effect and durability of the makeup finish.

The present invention includes the following components (A), (B), (C) and (D):
(A) hydrophobic powder,
(B) Poly (N-acylalkyleneimine) comprising a repeating unit represented by the following formula (1) via an alkylene group containing a hetero atom at least one silicon atom at the terminal or side chain of the organopolysiloxane segment ) Is a silicone polymer; or amino-modified silicone

Wherein R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and x represents a number of 2 or 3.
(C) a nonionic water-soluble polymer having a polyoxyalkylene chain having an average molecular weight of 300 to 100,000 in the molecule,
(D) An emulsified cosmetic containing an oily component that is liquid at 25 ° C. is provided.

  The cosmetic composition of the present invention has a hydrophobic powder uniformly dispersed, good temporal stability, no powderiness, little bulkiness, excellent use feeling, and powder when applied to the skin. Does not agglomerate, does not cause white floating or uneven coating, and has an excellent UV protection effect and durability of the makeup finish.

The hydrophobic powder of component (A) used in the present invention includes a hydrophobic powder used in ordinary cosmetics and a powder obtained by hydrophobizing cosmetic powders.
Hydrophobic powders include polyamide resin powder (nylon powder), porous nylon powder, polyester powder, polyethylene powder, polytetrafluoroethylene powder, polypropylene powder, polystyrene powder, polymethylbenzoguanamine powder, polymethylmethacrylate powder, polyurethane Organic resins such as powder, lauroyl lysine, silicone powder, silicone elastomer spherical powder, reticulated methylpolysiloxane powder, butyl acrylate / vinyl acetate copolymer, cyclodextrin, copolymer resin powder of styrene and acrylic acid Cross-linked or non-cross-linked polymer powder such as powder may be mentioned.

The base material used for the hydrophobized powder includes inorganic powder, natural fiber powder, starch powder, pearlescent pigment, organic dye, and the like.
Inorganic powders include talc, kaolin, mica, sericite (sericite), aluminum silicate / magnesium, calcium silicate, aluminum silicate, magnesium silicate, barium silicate, strontium silicate, epoxy-treated aluminum, aluminum Powder, calcium phosphate, anhydrous silicic acid, anhydrous aluminum silicate, pyroferrite clay, bentonite, smectite, montmorillonite, vermiculite, hectorite, zeolite, hydilite, silica, yellow iron oxide, loess, black iron oxide, red iron oxide, black oxide Titanium, low-order titanium oxide, iron titanate, γ-iron oxide, zinc oxide, aluminum oxide, aluminum cobalt oxide, chromium oxide, zirconium oxide, titanium dioxide, titanium oxide sol, iron oxide / titanium dioxide sintered product, cerium oxide , Magnesium oxide, chromium hydroxide, titanium / titanium dioxide sintered product, cobalt titanate, manganese violet, cobalt violet, calcium carbonate, magnesium carbonate, metal tungstate, barium sulfate, calcined calcium sulfate (baked gypsum), oxy Examples include bismuth chloride, calamine, sodium rosinate-treated magnesium oxide, fluorine apatite, hydroxyapatite, ceramic powder, metal soap (such as zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc., and these two types Examples of the composite powder include organic-inorganic composite powders such as acrylic resin-coated aluminum powder and titanium oxide-coated nylon powder.

Examples of the natural fiber powder include silk powder, wool powder, and cellulose powder.
Examples of starch powder include rice, corn, and potato.
Examples of the pearlescent pigment include iron oxide-coated mica titanium, titanium oxide-coated mica, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, colored titanium oxide-coated mica, titanium oxide-coated glass flake, and fish scale foil.
In addition, carbon black, ultramarine, bitumen, Gunjo violet, tar dyes, lakes, and the like can be used.

  As a method for hydrophobizing these powders, methods usually applied to cosmetic powders such as silicone treatment, fatty acid treatment, lauroyllysine treatment, surfactant treatment, metal soap treatment, fluorine treatment, lecithin Treatment, nylon treatment, polymer treatment and the like are included, among which silicone treatment, fatty acid treatment and fluorine treatment are preferable. Specifically, as the silicone treatment, for example, treatment with methylhydrogenpolysiloxane, methylpolysiloxane, trimethylsiloxysilicic acid, silicone resin, etc .; As the fatty acid treatment, for example, treatment with myristic acid, stearic acid, etc .; fluorine Examples of the treatment include treatment with pearl fluoroalkyl phosphate ester, perfluoroalkyl silane and the like. The amount of the hydrophobizing agent used is usually 0.5 to 70% by mass, particularly 1 to 40% by mass, based on the mass of the powder before the treatment.

The shape and particle size of the hydrophobic powder of component (A) are not particularly limited, but an average particle size of 10 μm or less is preferable because a uniform finish without whitening is obtained when applied.
When the hydrophobic powder is used as an ultraviolet protective agent, hydrophobized titanium oxide and hydrophobized zinc oxide are particularly preferable, and the average particle diameter thereof is 0.001 to 1 μm, and the shape thereof is, for example, granular, spherical, spindle Shape, dendritic shape, balloon shape, chestnut shape and the like are preferable. Prior to the hydrophobization treatment, the titanium oxide and zinc oxide powder surface can be pretreated with aluminum oxide, silicon oxide, zirconium oxide or the like to suppress the activity of the powder surface.

  In the present invention, when the hydrophobic powder is a white extender, whitening is suppressed, and particularly when the hydrophobic powder is an ultraviolet protective agent such as zinc oxide or titanium oxide, the ultraviolet protective ability is sufficiently exhibited. be able to. In addition, when the hydrophobic powder is a colored pigment such as iron oxide or a pearl pigment, a uniform and beautiful makeup finish can be obtained without unevenness.

  One or more kinds of the hydrophobic powder of component (A) can be used, and 1 to 60% by mass, particularly 3 to 40% by mass in the total composition, a sufficient UV protection effect and a beautiful finish, And since the sustainability of those effects is acquired, it is preferable.

  Among the components (B) used in the present invention, the silicone polymer is represented by the formula (1) through an alkylene group containing a hetero atom at least one of the terminal or side chain silicon atoms of the organopolysiloxane segment. A poly (N-acylalkylenimine) composed of repeating units, and is a substance that exhibits a viscous liquid state or a solid state at normal temperature and normal pressure.

  Through the alkylene group containing a hetero atom obtained by ring-opening polymerization of 2-substituted oxazolines or 2-substituted oxazines, at least one of the terminal or side chain silicon atoms of the organopolysiloxane segment is represented by the formula (1). In the copolymer formed by bonding poly (N-acylalkylenimine) composed of repeating units represented by formula (1), the weight ratio of the poly (N-acylalkylenimine) segment to the organopolysiloxane segment is 1. / 50 to 20/1, particularly 1/40 to 2/1, and a molecular weight of 5,000 to 500,000, particularly 1,000 to 300,000 are preferred for obtaining high effects in the present invention.

In formula (1), examples of the cycloalkyl group represented by R include those having 3 to 6 carbon atoms; examples of the aralkyl group include phenylalkyl and naphthylalkyl; examples of the aryl group include phenyl, naphthyl and alkyl-substituted groups. And phenyl.
The alkylene group containing a hetero atom present in the bond between the organopolysiloxane segment and the poly (N-acylalkyleneimine) segment has 1 to 3 carbon atoms including nitrogen, oxygen and / or sulfur atoms. Examples thereof include 2 to 20 alkylene groups, and specific examples thereof include groups represented by the following formulae.

  Preferred examples of such silicone polymers include poly (N-formylethyleneimine) modified silicone, poly (N-acetylethyleneimine) modified silicone, poly (N-propionylethyleneimine) modified silicone, poly (Nn-octa). Noylethyleneimine) modified silicone, poly (Nn-dodecanoylethyleneimine) modified silicone, poly (N-formylpropyleneimine) modified silicone, poly (N-acetylethyleneimine) modified silicone, poly (N-acetylpropyleneimine) ) Modified silicone, poly (N-propionylpropyleneimine) modified silicone, poly (Nn-octanoylpropyleneimine) modified silicone, poly (Nn-dodecanoylpropyleneimine) modified silicone, and the like.

  These silicone polymers are prepared by known methods (Japanese Patent Laid-Open Nos. 2-276824, 4-85334, 4-85335, 5-112423, and 7-133352. And Japanese Patent Laid-Open No. 10-95705).

  In addition, among the component (B), examples of the amino-modified silicone include those represented by the following general formula (2).

In the general formula (2), R ¹ is a monovalent organic group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group Alkyl groups such as dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and eicosyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group Halogenoalkyl groups such as 3,3,3-trifluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group and the like; . R ¹ may be one or more selected from these groups, but 90 mol% or more is particularly preferably a methyl group.
R ² is a group represented by the following formula.

Here, R ⁴ is a divalent alkylene group having 1 to 6 carbon atoms, and examples thereof include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, and a trimethylene group is preferable. .
R ⁵ , R ⁷ and R ⁸ each represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, such as a hydrogen atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group. Alkyl groups such as heptyl group, octyl group and decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; Groups in which part or all of the hydrogen atoms are substituted with halogen atoms or hydroxyl groups, such as 3,3,3-trifluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) ethyl group, 2 And halogenoalkyl groups such as-(perfluorooctyl) ethyl group.

Of these, a hydrogen atom is most preferred, but when at least one of R ⁵ , R ⁷ , and R ⁸ is a hydrogen atom, a part or all of the remaining groups are bonded with an acid anhydride, an epoxy compound, or an acrylic compound. It may be a monovalent organic group obtained by the reaction, such as —COCH ₃ , —CH ₂ CH (OH) CH ₂ OH, —CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ OH, or the like.

R ⁶ is a divalent alkylene group having 1 to 4 carbon atoms, and examples thereof include a methylene group, a dimethylene group, a trimethylene group, and a tetramethylene group, and a dimethylene group is particularly preferable.
p is 0 ≦ p ≦ 6, preferably 0 ≦ p ≦ 3. When p exceeds 6, it is difficult to obtain industrially and there may be few advantages in terms of characteristics.
Specific examples of such group R ² include the following.

In the general formula (2), R ³ is the same group as R ¹ or R ² or —OR ⁹ . Here, R < ⁹ > is a hydrogen atom or a C1-C6 alkyl group, for example, a hydrogen atom; alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, are mentioned. Among these, R ³ is preferably a methyl group, a hydroxyl group or a methoxy group.

In the said General formula (2), m is 10 <= m <= 10,000, and 100 <= m <= 2,000 is especially preferable. If m is less than 10, the properties are insufficient, and if it exceeds 10,000, the viscosity becomes high and blending becomes difficult. n is 0.1 ≦ n ≦ 1,000, and 1 ≦ n ≦ 100 is particularly preferable. When n is less than 0.1, the properties are insufficient, and when it exceeds 1,000, the viscosity becomes high and blending becomes difficult.
As the amino-modified silicone, amodimethicone, aminoethylaminopropyl dimethicone, and aminopropyl dimethicone are particularly preferable.

  The component (B) is preferably used in combination with alcohol in order to improve solubility or dispersibility. When the component (B) is blended as an alcohol dispersion, the dissolved state of the polymer compound in the cosmetics becomes good, spreads uniformly on the skin surface together with the component (A) and the component (C), and the effect can be sufficiently exhibited. . As the alcohol used in combination with the component (B), a lower alcohol having 1 to 4 carbon atoms is preferable, and ethanol is particularly preferable among them because of solubility, dispersibility, and handling at the time of blending in cosmetics.

As the component (B), one or more kinds can be used, and a silicone polymer and an amino-modified silicone can also be used in combination.
Component (B) is contained in an amount of 0.1 to 20% by mass, particularly 0.1 to 10% by mass in the whole composition, and there is no stickiness or powderiness, and the cosmetic feel is not impaired. Therefore, it is preferable.
The mass ratio [(B) / (A)] of the component (A) to the component (B) is 0.005 to 3, particularly 0.01 to 2, and more preferably 0.05 to 0.2. It is preferable because white float and uneven coating due to the hydrophobic powder when applied to the skin can be efficiently suppressed.

The water-soluble polymer of component (C) used in the present invention is a nonionic polymer having one or more polyoxyalkylene chains having an average molecular weight of 300 to 100,000, preferably 400 to 70,000 in the molecule. The alkylene group of the polyoxyalkylene chain is preferably a linear or branched one having 1 to 6 carbon atoms, and particularly preferably an ethylene group or a propylene group. The molecule may have a polyoxyethylene chain and a polyoxypropylene chain.
Examples of the water-soluble polymer of component (C) include the following (C-1) to (C-4).

(C-1) Polyethylene glycol or polypropylene glycol having an average molecular weight of 300 to 100,000:
Specifically, polyethylene glycol 600 (PEG-12), polyethylene glycol 1000 (PEG-20), polyethylene glycol 1500 (PEG-30), polyethylene glycol 1540 (PEG-32), polyethylene glycol 2000 (PEG-40), Polyethylene glycol 4000 (PEG-75), polyethylene glycol 6000 (PEG-150), polyethylene glycol 11000 (PEG-240), polyethylene glycol 20000 (PEG-400), highly polymerized polyethylene glycol (PEG-45M, PEG-65M, etc.) Polypropylene glycol (PPG-12, PPG-17, PPG-30, PPG-51, etc.), polyoxyethylene and polyoxypropylene copolymers such as Oxyethylene (160) polyoxypropylene glycol (30), polyoxyethylene (48) polyoxypropylene glycol (35) (poloxamer 215), and the like.

(C-2) Polyoxyalkylene-modified saccharide having a polyoxyalkylene chain having an average molecular weight of 300 to 100,000:
Examples of the polyoxyalkylene-modified saccharide include monosaccharides; oligosaccharides such as disaccharides and trisaccharides; sugar alcohols, etc. Among them, glucose, sorbitol, erythritol, and sucrose are preferable. In particular, a polyoxyalkylene-modified alkyl-modified saccharide modified with a linear or branched alkyl group having 1 to 6 carbon atoms is preferred, and examples thereof include polyoxyalkylene methyl glucoside. More preferably, those having an average alkylene oxide addition mole number of 10 to 50, particularly 10 to 30 are preferred.
More specifically, polyoxyethylene methyl glucoside such as methyl glutes-10 and methyl glutes-20 and polyoxypropylene methyl glucoside such as PPG-20 methyl glucose ester are preferred.

(C-3) Polysaccharide derivative having a polyoxyalkylene chain having an average molecular weight of 300 to 100,000:
A group in which part or all of the hydrogen atoms of the hydroxy group in the polysaccharide or derivative thereof are represented by the following general formula (3)
-E ^1- (OA) _q -E ² -R ¹⁰ (3)
Wherein, E ¹ represents a divalent saturated hydrocarbon group having 1 to 6 carbon hydroxy group or a C oxo group which may be substituted, q is a number of 8-300, the q-number of A The same or different, each representing a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, E ² represents an ether bond or an oxycarbonyl group, and R ¹⁰ is an optionally substituted carbon group having 4 to 30 carbon atoms. Represents an alkyl group of
A polysaccharide derivative substituted with

The hydrocarbon group E ¹ in the general formula (3) may be linear or branched having 1 to 6 carbon atoms, and preferably has 2 or 3 carbon atoms. Specifically, ethylene group, propylene group, trimethylene group, 2-hydroxytrimethylene group, 1-hydroxymethylethylene group, 1-oxoethylene group, 1-oxotrimethylene group, 1-methyl-2-oxoethylene group, etc. Is mentioned.

The divalent hydrocarbon group A in the general formula (3) may be linear or branched having 1 to 6 carbon atoms, and preferably has 2 or 3 carbon atoms. Specific examples include an ethylene group, a propylene group, and a trimethylene group. q is the average number of repeating units of-(OA)-, preferably 8 to 100, particularly preferably 10 to 60, from the viewpoint of thickening effect and dispersion stability, and q A may be the same or different. good. E ² represents an ether bond (—O—) or an oxycarbonyl group (—OCO— or —COO—), and an ether bond is particularly preferable.

The long-chain alkyl group R ¹⁰ in the general formula (3) has 4 to 30 carbon atoms, and is particularly preferably a linear or branched alkyl group having 5 to 25 carbon atoms, and more preferably 6 to 20 carbon atoms. Specific examples include an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an isostearyl group. Among these, a linear alkyl group is preferable from the viewpoint of stability of the emulsion system.

The degree of substitution of the group represented by the general formula (3) in the polysaccharide derivative is in the range of 0.0001 to 1.0, more preferably 0.0005 to 0.5, particularly 0.001 to 0.1 per constituent monosaccharide residue. Is preferred.
As such polysaccharide derivatives, for example, those described in International Publication No. 00/73351 pamphlet and JP-A-2005-336116 can be used. In particular, hydroxyethyl (hydroxypropyl polyethylene glycol dodecyl ether) cellulose (laureth-13 PG-hydroxyethyl cellulose) and the like are preferable.

(C-4) Hydrophobized ethoxylated urethane:
(PEG-8 / SMDI) copolymer, (PPG-12 / SMDI) copolymer, (PPG-51 / SMDI) copolymer, PEG-150 / stearyl alcohol / SMDI copolymer, PEG-150 / decyl alcohol / SMDI copolymer, etc. Commercially available products such as Aculin 46, Aculin 44 (above, Rohm and Haas Japan) can be used.

  Among (C-1) to (C-4), from the viewpoint of handling in production and the touch of the composition, in particular, polyethylene glycol and polypropylene glycol having an average molecular weight of 800 to 70000, and polyoxy having 20 ethylene oxide addition moles. Alkylene methyl glucoside and polyoxyalkylene group-substituted polysaccharide derivatives described in JP-A-2005-336116 are preferred. Furthermore, polyethylene glycol having an average molecular weight of 800 to 70000 is most preferable.

One or more components (C) can be used, and the total composition contains 0.01 to 30% by mass, particularly 0.1 to 25% by mass, has a smooth spread and is uniform on the skin. It is preferable because it is easy to apply.
Moreover, the mass ratio [(C) / (B)] of the component (B) and the component (C) is 0.01 to 200, particularly 0.1 to 50, and further 1 to 20 is the component (A ) Is preferred because it can be more uniformly dispersed.

  The oil component of the component (D) used in the present invention is liquid at 25 ° C., and liquid oil having a viscosity at 25 ° C. of 3000 mPa · s or less is preferable. The viscosity of this liquid oil is a value measured at 1 atm. 25 ° C. with a Brookfield type BM viscometer with a No. 3 spindle and 12 revolutions for 1 minute.

  Specific examples of component (D) include silicone oils such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, higher fatty acid-modified organopolysiloxane, higher alcohol-modified organopolysiloxane, and fluorine-modified organopolysiloxane; Fluorine oil such as fluoropolyether and perfluoroalkyl ether silicone; vegetable oil such as olive oil and jojoba oil; animal oil such as liquid lanolin; hydrocarbon oil such as liquid paraffin and squalane; diisostearyl malate, octyldodecyl lactate, isononanoic acid Fatty acid esters such as isotridecyl, isopropyl isostearate and octyldodecyl myristate; ester oils composed of fatty acids such as neopentyl glycol dicaprate and polyhydric alcohols; Derivatives, and the like ester oils such as amino acid derivatives.

As the component (D), one or more kinds can be used, and it is preferably contained in the total composition in an amount of 10 to 80% by mass, particularly 20 to 60% by mass. When the component (D) is within this range, the hydrophobic powder does not re-aggregate or adhere non-uniformly on the skin during application, and a uniform and beautiful finish can be obtained without unevenness. A feeling of sliminess comes out and the feeling of use is easily lost.
Moreover, the mass ratio [(B) / (D)] of the component (B) and the component (D) is 0.001 to 0.5, particularly 0.005 to 0.4, and further 0.01 to 0.1. It is preferable in that a good usability can be obtained and the powder can be uniformly dispersed in the preparation.

In the present invention, the effect of the present invention is clear when the content ratio of the component (D) in the oil phase excluding the component (A) and the component (B) is 30% by mass or more, particularly 30 to 95% by mass. It is preferable at the point which is exhibited by.
In the oil phase, in addition to the component (A), the component (B), and the component (D), an oil component that is solid or semi-solid at 25 ° C., a surfactant, and an oil-soluble ultraviolet absorber (for example, t- Butylmethoxydibenzoylmethane), oil-soluble active ingredients (eg oil-soluble vitamin C derivatives, stearyl glycyrrhetinate, tocopherol acetate, etc.), film forming agents (eg trimethylsiloxysilicic acid, alkyl-modified silicones, etc.), solvents Of ethanol and the like.

The cosmetic of the present invention may further contain (E) a surfactant. Such a surfactant is not particularly limited as long as it is used in ordinary cosmetics, but a nonionic surfactant is preferable, and a nonionic surfactant having an HLB of 8 or less is particularly preferable.
Specifically, sorbitan fatty acid esters (for example, sorbitan monoisostearate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, etc.), glycerin fatty acid esters (for example mono Glyceryl stearate, glyceryl monoisostearate, glyceryl distearate, glyceryl monostearate, malic acid, etc.), polyglyceryl fatty acid ester (eg, diglyceryl monostearate, hexaglyceryl tristearate), propylene glycol / pentaerythritol fatty acid ester (Eg, propylene glycol monostearate, pentaerythritol stearate), polyethylene glycol fatty acid ester (For example, POE (4) monostearate, POE (2) monooleate, etc.), polyoxyethylene alkyl ether (for example, POE (2) cetyl ether, POE (5) behenyl ether, POE (3) octyl phenyl ether, etc.) ), Polyoxyethylene castor oil / hardened castor oil (for example, POE (3) castor oil, POE (5) hardened castor oil, etc.), modified silicone with a linear, branched or cross-linked silicone chain (for example, polyether-modified) Silicone, polyether-alkyl co-modified silicone, polyglycerin-modified silicone, polyglycerin-alkyl co-modified silicone, etc.), sucrose fatty acid ester and the like.

  As the component (E), one or more kinds can be used, and when contained in an overall composition of 0.01 to 20% by mass, particularly 0.1 to 10% by mass, good usability and stability can be obtained. Therefore, it is preferable.

  The cosmetic of the present invention can contain water, and is preferably contained in the total composition in an amount of 5 to 95% by mass, particularly 10 to 90% by mass.

  In addition to the above components, the cosmetics of the present invention include components used in normal cosmetics, such as powders other than those described above, semisolid or solid oily components, antioxidants, perfumes, preservatives, Cosmetic ingredients, medicinal ingredients, moisturizers, pH adjusters, ultraviolet absorbers, polyhydric alcohols, sugars, amino acids, thickeners, sequestering agents, bactericides, and the like can be included.

  The cosmetic of the present invention can be produced by a usual method, and may be in the form of a W / O type emulsion, an O / W type emulsion, an O / W / O type multilayer emulsion or the like. it can. In particular, when an O / W emulsion is used, a more excellent effect can be obtained.

  The cosmetic of the present invention preferably has a viscosity at 25 ° C. of 100 to 50000 mPa · s because good usability can be obtained and the effects of the present invention can be clearly exhibited. The viscosity is a value measured by a Brookfield type BM viscometer at a rotational speed of 6 rpm or 12 rpm and using a spindle corresponding to the viscosity at 25 ° C. for 1 minute.

Synthesis Example 1 (Production of oxazoline-modified silicone)
3.76 g (0.024 mol) of diethyl sulfate and 65.3 g (0.66 mol) of 2-ethyl-2-oxazoline were dissolved in 140 g of dehydrated ethyl acetate and heated under reflux for 8 hours under a nitrogen atmosphere to react with the terminal reactivity. Poly (N-propionylethyleneimine) was synthesized. A 50% ethyl acetate solution of 500 g (0.024 mol in terms of amino group) of side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 100000, amine equivalent 20500) was added all at once, and the mixture was heated to reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow rubber-like solid (537 g, yield 95%). The weight average molecular weight was 149,000. (N-propionylethyleneimine content 12% by mass)

Synthesis Example 2 (Production of oxazoline-modified silicone)
7.57 g (0.049 mol) of diethyl sulfate and 263.3 g (2.66 mol) of 2-ethyl-2-oxazoline were dissolved in 550 g of dehydrated ethyl acetate, heated under reflux for 8 hours in a nitrogen atmosphere, and terminal reactive. Poly (N-propionylethyleneimine) was synthesized. A 50% ethyl acetate solution of 250 g (0.065 mol in terms of amino group) of side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 60000, amine equivalent 3870) was added all at once and heated to reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow rubber-like solid (505 g, yield 97%). The weight average molecular weight was 88400. (N-propionylethyleneimine content 49 mass%)

Synthesis Example 3 (Production of polyoxyalkylene group-substituted polysaccharide derivative)
A slurry prepared by mixing 80 g of hydroxyethyl cellulose (HEC-QP100MH, manufactured by Union Carbide) having a weight average molecular weight of 1,500,000 and a hydroxyethyl group substitution degree of 1.8, 640 g of 80% isopropyl alcohol, and 5.34 g of 48% aqueous sodium hydroxide solution. A solution was prepared and stirred at room temperature for 30 minutes under a nitrogen atmosphere. In this solution

21.7 g of the compound represented by the above formula was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of isopropyl alcohol and dried at 60 ° C. for one day under reduced pressure to obtain 74.0 g of a polyoxyalkylenated hydroxyethyl cellulose derivative. The degree of substitution of the substituent containing the polyoxyalkylene group in the obtained hydroxyethyl cellulose derivative was 0.004.

Synthesis Example 4 (Production of polyoxyalkylene group-substituted polysaccharide derivative)
A slurry prepared by mixing 80 g of hydroxyethyl cellulose having a weight average molecular weight of 800,000 and a hydroxyethyl group substitution degree of 1.8 (HEC-QP15000H, manufactured by Union Carbide), 640 g of 80% isopropyl alcohol, and 5.34 g of a 48% aqueous sodium hydroxide solution. A solution was prepared and stirred at room temperature for 30 minutes under a nitrogen atmosphere. In this solution

13.7 g of a compound represented by the formula: After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of isopropyl alcohol and dried at 60 ° C. for one day under reduced pressure to obtain 69.0 g of a polyoxyalkylenated hydroxyethyl cellulose derivative. The degree of substitution of the substituent containing the polyoxyalkylene group in the obtained hydroxyethyl cellulose derivative was 0.003.

Examples 1-7 and Comparative Examples 1-7
Emulsified cosmetics having the composition shown in Table 1 are manufactured, the viscosity is measured, storage stability, feeling of use (no powderiness, no bulkiness), no coating unevenness and durability of UV protection effect. evaluated. The results are shown in Table 2.

(Production method)
After fully dissolving and mixing the oil phase components (including component (B), component (D), and component (E)), the powder component (including component (A)) is added and dispersed strongly using a disper. To do. On the other hand, using a propeller stirrer, the water-soluble polymer of component (C) is dissolved in purified water at 60 to 70 ° C., and then the other aqueous phase components are added and mixed. In the case of an oil-in-water composition (O / W type), the water phase component is transferred to an Ajihomo mixer, and the oil phase component containing the powder component is slowly added thereto while stirring at high speed at room temperature. High speed stirring was performed for 30 minutes. In the case of a water-in-oil composition (W / O type), the oil phase component including the powder component is transferred to the Ajihomo mixer, and the aqueous phase component is slowly added thereto while performing high-speed stirring at room temperature. The mixture was further stirred at high speed for 30 minutes. After cooling to room temperature, the fragrance and various extracts were mixed and made uniform. In this way, O / W type and W / O type cosmetics were obtained.

(Evaluation methods)
(1) Viscosity:
When each cosmetic was measured at 25 ° C. using a Brookfield type BM viscometer at a rotational speed of 6 rpm or 12 rpm and a spindle corresponding to the viscosity, a value after 1 minute was shown.

(2) Storage stability:
Each cosmetic was filled in a 50 mL capacity glass bottle and stored at 25 ° C. for 1 week, and then the appearance was visually determined according to the following criteria.
○: Good.
Δ: Powder or oil slightly floats on the surface.
X: Oil separation and powder aggregation are apparently occurring.

(3) Usability:
Ten expert panelists made a sensory evaluation of “no powderiness” and “no roughness” when using each cosmetic, and judged according to the following criteria.
○: Seven or more people evaluated it as good.
(Triangle | delta): Four to six persons evaluated it as favorable.
X: Three or less people evaluated it as favorable.

(4) No coating unevenness:
Each cosmetic is applied to 3 mg / cm ² on a 4 × 10 cm square portion of the human forearm bent side with no color unevenness. Ten L ^* values were measured with a color difference meter (color difference meter CR-300 (Konica Minolta)), and the standard deviation of the L ^* values was determined. Higher values indicate application unevenness and powder agglomeration.

(5) UV protection effect and water resistance test:
In vitro SPF was measured for each cosmetic. That is, each cosmetic is evenly applied to a surgical tape on a quartz glass plate to 2 mg / cm ² , left to dry for 20 minutes, and then the SPF value of the cosmetic is determined using an SPF analyzer (Optometrics). It was measured.
Further, the sample after the SPF value measurement was immersed in a water bath with the glass plate and the coated surface facing up, and the water was kept lightly stirred for 80 minutes while maintaining the water temperature at 37 ° C. After completion, the glass plate was slowly taken out, allowed to stand at room temperature for 30 minutes and dried, and then the SPF value was measured again in the same manner as described above.

Examples 1 and 3 are O / W type emulsified cosmetics, and Example 2 is a W / O type emulsified cosmetics. Both the feeling of use and stability are good, there is no coating unevenness, and the UV protection effect and water resistance of the effect. It was also expensive. On the other hand, Comparative Examples 1 and 3 which do not contain the component (B) with the same powder composition as in Examples 1 and 2, Comparative Examples 2 and 4 which do not contain the component (C), and components ( The comparative example 5 which does not contain B) and a component (C) was inferior to Examples 1-3 in all the evaluation items. That is, it is a powdery and bulky feeling of use, is a cosmetic with poor stability and is easily uneven in coating, has a low UV protection effect, and its effect has been significantly reduced after water immersion treatment. However, the UV protection effect of the W / O type emulsified cosmetic was less deteriorated by the water immersion treatment than the O / W type emulsified cosmetic.
In Comparative Example 6 using a high molecular weight type polyethylene glycol of 350,000 instead of Component (C) and Comparative Example 7 using hydroxyethyl cellulose having no polyoxyalkylene chain, all the evaluation items were inferior, and water resistance Was also low.

Example 8 (Lotion (shaking type))
Lotions (shaking type) having the compositions shown in Table 4 were produced by a conventional method. The mass ratio of component (A) to component (B) [(B) / (A)] is 0.25; the mass ratio of component (B) to component (C) [(C) / (B)] is 6. 40; mass ratio of component (B) and (D) [(B) / (D)] is 0.13; content ratio of component (D) in oil phase excluding component (A) and component (B) is 93% by mass.
The obtained lotion had an excellent feeling of use with no powderiness or bulkiness, and neither oil separation nor powder aggregation was observed. Moreover, the skin after application | coating did not have a nonuniformity or white floating, and was a transparent finish.

Example 9 (O / W type emulsion)
O / W type emulsions having the compositions shown in Table 5 were produced by a conventional method. The mass ratio of component (A) to component (B) [(B) / (A)] is 2.0; the mass ratio of component (B) to component (C) [(C) / (B)] is 2. 0: The mass ratio of the components (B) and (D) [(B) / (D)] is 0.13; the content ratio of the component (D) in the oil phase excluding the components (A) and (B) is 65% by mass.
The obtained emulsion had an excellent feeling of use with no powderiness or bulkiness, and neither oil separation nor powder aggregation was observed. Moreover, the skin after application | coating did not have a nonuniformity or white floating, and was a transparent finish.

Example 10 (W / O type cream)
W / O type creams having the compositions shown in Table 6 were produced by a conventional method. The mass ratio of component (A) to component (B) [(B) / (A)] is 0.4; the mass ratio of component (B) to component (C) [(C) / (B)] is 4. 25; mass ratio of component (B) and (D) [(B) / (D)] is 0.014; content ratio of component (D) in oil phase excluding component (A) and component (B) is 83% by mass.
The obtained cream had an excellent feeling of use with no powderiness or bulkiness, and neither oil separation nor powder aggregation was observed. Moreover, the skin after application | coating did not have a nonuniformity or white floating, and was a transparent finish.

Example 11 (O / W type sunscreen)
O / W type sunscreens having the compositions shown in Table 7 were produced by a conventional method. The mass ratio of component (A) to component (B) [(B) / (A)] is 0.13; the mass ratio of component (B) to component (C) [(C) / (B)] is 1. 50; mass ratio of component (B) and (D) [(B) / (D)] is 0.08; content ratio of component (D) in oil phase excluding component (A) and component (B) is 95% by mass.
The obtained sunscreen had an excellent feeling of use with no powderiness or bulkiness, and neither oil separation nor powder aggregation was observed. Moreover, the skin after application | coating was the finish without a nonuniformity and white floating. Furthermore, the UV protection effect was maintained high even after the immersion treatment, and the water resistance was excellent.

Example 12 (W / O type UV cream)
W / O type UV creams having the compositions shown in Table 8 were produced by a conventional method. The mass ratio of component (A) to component (B) [(B) / (A)] is 0.05; the mass ratio of component (B) to component (C) [(C) / (B)] is 10. 0: Mass ratio of components (B) and (D) [(B) / (D)] is 0.04; The content ratio of component (D) in the oil phase excluding components (A) and (B) is 71% by mass.
The obtained cream had an excellent feeling of use with no powderiness or bulkiness, and neither oil separation nor powder aggregation was observed. Moreover, the skin after application | coating was the finish without a nonuniformity and white floating. Furthermore, the UV protection effect was maintained high even after the immersion treatment, and the water resistance was excellent.

Example 13 (W / O type foundation)
W / O type foundations having the compositions shown in Table 9 were produced by a conventional method. The mass ratio of component (A) to component (B) [(B) / (A)] is 0.43; the mass ratio of component (B) to component (C) [(C) / (B)] is 1. 08; mass ratio of component (B) to (D) [(B) / (D)] is 0.17; content ratio of component (D) in oil phase excluding component (A) and component (B) is 93% by mass.
The obtained foundation had an excellent feeling of use with no powderiness or bulkiness, and neither oil separation nor powder aggregation was observed. Further, the skin after application had a uniform finish with no unevenness or whitening, excellent color development, and was maintained without breaking over time. Furthermore, the UV protection effect was maintained high even after the immersion treatment, and the water resistance was excellent.

Example 14 (mascara)
Mascara having the composition shown in Table 10 was produced. The mass ratio [(B) / (A)] of component (A) to component (B) is 0.03; the mass ratio [(C) / (B)] of component (B) to component (C) is 41. 7: Mass ratio of component (B) to (D) [(B) / (D)] is 0.12; content ratio of component (D) in oil phase excluding component (A) and component (B) is 32% by mass.
The obtained mascara was excellent in use feeling without powderiness and bulkiness, and no oil separation or powder aggregation was observed. Moreover, after coating, it was a uniform finish with no unevenness, excellent color development, and maintained without breaking over time.

(Production method)
After components (1) to (9) are heated and dissolved, components (10) to (15) are added and cooled with good stirring. The components (16) to (19) and (21), which have been heated and dissolved in advance and stirred therein, are added at room temperature and mixed well. Finally, component (20) was added and mixed to obtain mascara.

Claims (4)

The following components (A), (B), (C) and (D):
(A) hydrophobic powder,
(B) Poly (N-acylalkyleneimine) comprising a repeating unit represented by the following formula (1) via an alkylene group containing a hetero atom at least one silicon atom at the terminal or side chain of the organopolysiloxane segment ) Is a silicone polymer; or amino-modified silicone

Wherein R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and x represents a number of 2 or 3.
(C) a nonionic water-soluble polymer having a polyoxyalkylene chain having an average molecular weight of 300 to 100,000 in the molecule,
(D) An emulsified cosmetic containing an oily component that is liquid at 25 ° C.   The mass ratio of component (A) to component (B) [(B) / (A)] is 0.005 to 3, and the mass ratio of component (B) to component (C) [(C) / (B) ] Is 0.01-200, and the content rate of the component (D) in the oil phase except a component (A) and a component (B) is 30 mass% or more, The emulsified cosmetics of Claim 1.   The cosmetic according to claim 1 or 2, wherein the mass ratio [(B) / (D)] of the component (B) and the component (D) is 0.001 to 0.5.   The cosmetic according to any one of claims 1 to 3, further comprising (E) a surfactant.