CN109069357A - Oil-in-water emulsion type cosmetic preparation - Google Patents

Abstract

The purpose of the present invention is to provide a kind of cosmetics, it is the oil-in-water emulsion type cosmetic preparation that powder is combined in interior oily phase, its have improve water resistance, by in the past no epoch-making characteristic for being improved after ultraviolet protection effect and the contact of water or sweat etc. etc. relatively just coating, and use feeling or cleaning are also excellent.The present invention relates to a kind of oil-in-water emulsion type cosmetic preparations, it is characterized in that, contain: (A) ultraviolet absorbing agent, (B) oil phase thickeners, (C) silicic acid anhydride powder, (D) nonionic surfactant and/or core-crown type microgel, (E) non-volatile oil (including above-mentioned (A) ultraviolet absorbing agent), and total use level of (B) oil phase thickeners and (C) silicic acid anhydride powder is 0.2~20 relative to the ratio ([(B)+(C)]/(E)) of the use level of above-mentioned (E) non-volatile liquid oil.

Description

Oil-in-water emulsion type cosmetic preparation

Technical field

The present invention relates to a kind of oil-in-water emulsion type cosmetic preparations.And then specifically, it is related to a kind of oil-in-water type emulsion Cosmetic is to be combined with the oil-in-water emulsion type cosmetic preparation of powder in inner aqueous phase, with excellent water resistance, by with water or sweat The in the past no characteristic improved after the relatively just coating such as ultraviolet protection effect Deng contact.

Background technique

The injury for protecting the skin from ultraviolet light is one of skin care, the important topic in body care, in order to by ultraviolet light The adverse effect for giving skin is suppressed to irreducible minimum, develops various uv blocking (ultraviolet, ultraviolet light) cosmetics.As 1 kind of sunscreen cosmetic (sun-proof (Sunscreen) cosmetics) of uv blocking cosmetics is by cooperation ultraviolet absorbing agent or ultraviolet Line scattering diluent stops UVA and the UVB to reach skin, protects the skin from the injury (non-patent literature 1) of ultraviolet light.Recently, recognize For the excessively harsh ultraviolet light condition in the outdoor sports such as the swimming pool of not only summer or the skiing of swimming or winter in the sea, It is more important that uv damage is also protected the skin from daily life, it is expected that common skin protection cosmetics also has ultraviolet light Protection effect.

As the dosage form of sunscreen cosmetic, the more preparation using emulsification form has the unstability of emulsification to cause ultraviolet The case where reduction of line defence capability.It is recorded in patent document 1, by cooperating the free fatty acid of carbon number 14~24, improves and protect Stability is deposited, the reduction of the ultraviolet protection ability caused by inhibiting because of long-term preservation.Even if however, it is believed that by ultraviolet protection Ability is maintained to will be before use, if the sunscreen cosmetic for being coated on skin is contacted with water or sweat, ultraviolet absorbing agent or purple Outside line scattering diluent is lost from the cosmetics being coated with, and not can avoid ultraviolet protection effect reduction.

Oil-in-water emulsion is due to obtaining the use thoughts and feelings of water profit, so also it is widely used as sunscreen cosmetic.However, water For oil-in emulsification cosmetic compared with water-in-oil type, most cases water resistance is poor, is easy to produce because of ultraviolet absorbing agent or purple The reduction of ultraviolet protection ability caused by the loss of outside line scattering diluent.It is dissipated additionally, it is known that having matched ultraviolet light in interior oil The water resistance for penetrating the oil-in-water emulsion type cosmetic preparation of the powder of agent etc. is especially poor, if in order to obtain higher ultraviolet protection ability And increasing powder use level, then necessary polygamy cooperation is the oil of its decentralized medium, and result, which also has, gives sticky use feeling The problem of.

Also it has carried out in oil-in-water emulsion type cosmetic preparation, by cooperating film agent to improve water resistance (patent document 2) Trial.But the cosmetics for being coated on skin be exposed to the sweat or seawater etc secreted from skin from external environment The inside and outside various moisture from film such as moisture, so even the high resin or filming agent cooperated to assign water resistance, It is difficult to prevent completely the loss of ultraviolet absorbing agent or ultraviolet light scattering diluent.Additionally, it is believed that being convenient for that ultraviolet light can be prevent completely In the case where the loss of absorbent etc., after ultraviolet protection effect obtained is not more than just coating.

Existing technical literature

Patent document

Patent document 1；Japanese Unexamined Patent Publication 2015-30723 bulletin

Patent document 2；Japanese Unexamined Patent Publication 2004-91377 bulletin

Non-patent literature

Non-patent literature 1；" new cosmeceutical " second edition, a light well man of great physical prowess compile, and 2001, South Mountain hall distribution, the 497th~504 Page

Summary of the invention

Problems to be solved by the invention

The present invention is based on the oil-in-water emulsion type sunscreen preparation in exploitation with efficient ultraviolet protection effect In research process, find for the first time by with the contact of water or sweat etc., do not reduce ultraviolet protection effect, what effect improved instead shows As.The oil-in-water emulsion type cosmetic preparation of target of the invention have by with contact with moisture, the raisings such as ultraviolet protection effect In the past no novel innovative characteristic.

The solution to the problem

The inventors of the present invention further investigate in order to solve the above problems and repeatedly, as a result, it has been found that: powder has been matched in oil inside In the oil-in-water emulsion type cosmetic preparation at end, cooperate oil phase thickeners, and by above-mentioned oil phase thickeners and silicic acid anhydride powder Total use level and non-volatile oil use level ratio adjustment in particular range, so that water resistance and stability mention Height, and above-mentioned novel innovative characteristic is played, so far complete the present invention.

That is, the present invention is to provide a kind of oil-in-water emulsion type cosmetic preparation, which is characterized in that contain:

(A) ultraviolet absorbing agent；

(B) oil phase thickeners；

(C) silicic acid anhydride powder；

(D) nonionic surfactant and/or core-hat (Core-Corona) type microgel；With

(E) non-volatile liquid oil (including above-mentioned (A) ultraviolet absorbing agent)；And

(E) total use level of (B) oil phase thickeners and (C) silicic acid anhydride powder is relative to non-volatile liquid oil The ratio ([(B)+(C)]/(E)) of use level is 0.2~20.

The effect of invention

The present invention is that the ultraviolet protection effect by being set as above-mentioned composition, after contacting with water or sweat etc. is rigid compared with by cosmetics It is significantly improved after being coated on skin.That is, oil-in-water emulsion type cosmetic preparation of the invention be have by in previous oil-in-water Type emulsification cosmetic become the contact of the moisture etc. for the reason of effect is deteriorated and the raisings such as ultraviolet protection effect with it is previous The innovative sunscreen cosmetic of the diametical characteristic of common sense.In addition, film homogenization of being made up and being contacted with water, therefore be coated with There is the optical characteristics of the skin of cosmetics to become close to plain face, also plays transparent feel and increase, feel beautiful U.S. face effect.

In turn, the excellent in stability of oil-in-water emulsion type cosmetic preparation of the invention, even if not high cooperation filming agent etc. is made up The water resistance of film also improves.Therefore, no overlay film sense, extension when use (when application) is good, and general cleaning can also be used Material or soap are simply shed.That is, the present invention can provide a kind of in addition to special ultraviolet protection effect and U.S. face effect, use Property and cleaning also excellent oil-in-water emulsion type cosmetic preparation.

Specific embodiment

As described above, oil-in-water emulsion type cosmetic preparation of the invention contain (A) ultraviolet absorbing agent, (B) oil phase thickeners, (C) silicic acid anhydride powder, (D) nonionic surfactant and/or core-crown type microgel and (E) non-volatile liquid oil Point.It is exemplified below for the oil-in-water emulsion type sunscreen preparation as a mode of the invention and is described in detail.

(A) ultraviolet absorbing agent

Be matched in oil-in-water emulsion type cosmetic preparation of the invention (A) ultraviolet absorbing agent (hereinafter sometimes referred to simply as " at Point A ") it can be set as selected from being generally mated at least one of the ultraviolet absorbing agent in sunscreen cosmetic back and forth.

Ultraviolet absorbing agent (ingredient A) used in the present invention is not particularly limited, and as concrete example, can enumerate: to first Oxygroup cinnamic acid 2- ethylhexyl, 2,4- be bis--{ [4- (2- ethyl hexyl oxy) -2- hydroxyl]-phenyl } -6- (4- methoxyphenyl) 1,3,5- triazine, Octocrilene, dimethyl polysiloxane diethylbenzylidene malonate, poly-1 5, tert-butyl methoxyl group Dibenzoyl methane, Uvinul T 150, the own ester of diethylamino hydroxybenzoyl benzoylbenzoic acid, double ethylhexyloxyphenol first Phenyl triazine, oxybenzone -3, Tinuvin 360, Phenylbenzimidazolesulfonic acid, Hu Mo The organic uv absorbers such as willow ester, ethylhexyl salicylate.

The use level of ultraviolet absorbing agent (ingredient A) in oil-in-water emulsion type cosmetic preparation of the invention is in sunscreen cosmetic In the case where, it is 1 mass % or more relative to cosmetics total amount, is more preferably 1~40 mass %, further preferably 2~30 Quality %.On the other hand, the ultraviolet absorbing agent (ingredient A) in the present invention also constitutes non-volatile liquid oil (ingredient sometimes E a part (or whole)).For example, in by the non-volatile liquid oil other than cooperation ultraviolet absorbing agent, using steady It surely, can also be by ultraviolet light in the case that the ultraviolet light scattering diluent being maintained in interior oily phase ensures sufficient ultraviolet protection ability The use level of absorbent is set below 6 mass %, for example, be set as 5 mass % or less, 3 mass % or less or 2 mass % with Under.

(B) oil phase thickeners

(B) oil phase thickeners (hereinafter sometimes referred to simply as " ingredient B ") are the substances of the viscosity of adjustable oily phase, such as preferably For dextrin fatty acid ester, sucrose fatty ester, the hydrocarbon ils of solid or semisolid, organo-clay mineral or fatty acid or Its salt etc. particularly preferably cooperates two or more in these.

Dextrin fatty acid ester is dextrin or the ester for restoring dextrin and higher fatty acids, as long as commonly used in cosmetics person It can use with no particular limitation.Dextrin or reduction dextrin are preferably 3~100 using the average sugared degree of polymerization.In addition, as paste The composition fatty acid of smart aliphatic ester, it is preferable to use the saturated fatty acid of carbon number 8~22.Specifically, can enumerate: palmitinic acid Dextrin, oleic acid dextrin, stearic acid dextrin, myristic acid dextrin, (palmitinic acid/2 ethyl hexanoic acid) dextrin etc..

Sucrose fatty ester is the saturation or unsaturated that its fatty acid preferably uses straight-chain or branched 12 to 22 person of carbon number.Specifically, can enumerate: sucrose octanoate, sucrose phthalate, Surfhope SE Cosme C 1216, sucrose miristic acid Ester, sucrose palmitate, sucrose stearate, sucrose oleate, sucrose erucate etc..

The hydrocarbon ils of solid or semisolid can be enumerated for the hydrocarbon of solid or semisolid as concrete example under room temperature (25 DEG C): Vaseline, hydrogenated palm oil, rilanit special (castor wax), hydrogenated palm kernel oil, rilanit special, hydrogenation peanut (peanut) Oil, hydrogenated rapeseed oil, hydrogenation camellia oil, oil with hydrogenated soybean, hydrogenated olive oil, hydrogenation Australia nut oil, hydrogenated sunflower oil, hydrogen Change wheat-germ oil, hydrogenation rice germ oil, hydrogenated rice bran oil, cotmar, hydrogenation avocado oil, wax class etc..

Organo-clay mineral are the one kind with the colloidality hydrated aluminium silicate of three-decker, and representativeness is to utilize season Ammonium salt type cationic surfactant makes Modification of Clay Minerals person represented by the following general formula (1).

(X,Y)_2-3(Si,Al)₄O₁₀(OH)₂Z_1/3·nH₂O (1)

(wherein, X=Al, Fe (III), Mn (III), Cr (III), Y=Mg, Fe (II), Ni, Zn, Li, Z=K, Na, Ca)

As concrete example, can enumerate: dimethyl distearyl ammonium lithium montmorillonite (distearyl dimethyl amine lithium montmorillonite), Dimethyl alkylammonium lithium montmorillonite, benzyl dimethoylstearyl ammonium lithium montmorillonite, chloro distearyl dimethyl ammonium handle silicic acid Magnalium etc..As commercially available product, preferably Bentone27 (benzyl dimethoylstearyl ammonium chloride treatment lithium montmorillonite: The manufacture of Elementis Japan company) and Bentone38 (distearyl dimethyl ammonium chloride handles lithium montmorillonite: ElementisJapan company manufacture).

It is solid person that fatty acid, which can be used under room temperature, such as can enumerate myristic acid, palmitinic acid, stearic acid, docosane Acid etc..In addition, the salt as fatty acid, can enumerate calcium salt, magnesium salts, aluminium salt of these fatty acid etc..

(C) silicic acid anhydride powder

Powder (being also referred to as " ingredient C " sometimes below) in the present invention is in previous sunscreen cosmetic etc. as purple The powder that outside line scattering diluent, usability powder, colorant cooperate, the powder comprising surface-hydrophobicized processing.Ultraviolet light scattering diluent does not have It is particularly limited to, preferably microgranular metal oxide, such as zinc oxide, titanium oxide, iron oxide, cerium oxide, oxygen can be enumerated Change the powder such as tungsten.As usability powder, colorant, such as talcum, mica titanium can be enumerated etc..

As surface-hydrophobicized inorganic agent, it can be used and lead to user, such as dimethyl polysiloxane, alkyl in cosmetic field The dextrin fatty acid esters such as the alkoxy silanes such as the silicone such as modified silicone, octyltri-ethoxysilane, Dextrin palmitate, stearic acid etc. Fatty acid, silica etc..In these, particularly preferably the alkoxy silanes such as octyltri-ethoxysilane, utilize silica Carry out the ultraviolet light scattering diluent of surface-hydrophobicized processing.

(D) nonionic surfactant and/or core-crown type microgel

(D1) nonionic surfactant

Nonionic surfactant (hereinafter sometimes referred to " ingredient D1 ") in the present invention can be for selected from using back and forth It is one kind or two or more in the nonionic surfactant of oil-in-water emulsion type cosmetic preparation, wherein HLB is preferably used (Hydrophile Lipophile Balance, hydrophilic/oily ratio) is 6 or more persons.

Stability in preparation and the aspect using the resulting absorbance improvement effect of contact with moisture, it is of the invention in make It includes Crodaret that nonionic surfactant, which is particularly preferably,.As Crodaret Concrete example, can enumerate PEG-10 rilanit special, PEG-20 rilanit special, PEG-25 rilanit special, PEG-30 hydrogenation Castor oil, Cremophor RH40, PEG-50 rilanit special, PEG-60 rilanit special, PEG-80 rilanit special, PEG-100 rilanit special etc..On the other hand, in without in the case where Crodaret, it is preferable to use HLB is 8 or more, be preferably 10 or more, more preferably be 12 or more nonionic surfactant.

The use level of (D1) nonionic surfactant in the present invention is 0.1~10 matter relative to cosmetics total amount %, preferably 0.5~5 mass % are measured, is more preferably 0.8~3 mass %.Have in the use level of ingredient D1 lower than 0.1 mass % When, it is difficult to sufficient stability is obtained, the situation not good enough in terms of usability if cooperating more than 10 mass %.In addition, excellent It is selected as to account for the mode of the 50 mass % or more of ingredient D1 and cooperate Crodaret, preferably ingredient D1 includes polyoxy The mode of ethylene hydrogenation castor oil.

(D2) core-crown type microgel

Core-crown type microgel (hereinafter sometimes referred to " ingredient D2 ") in the present invention is the surface portion in hydrophobicity core The microgel particle of hydrophily base (hat) is arranged in ground.As the core in the present invention-crown type microgel, cross-linking type and non-crosslinked can be used Any one of type.

It, as shown below, can example (acrylate/methacrylic acid methoxy as particularly suitable core-crown type microgel Ester PGE) cross-linked polymer [cross-linking type core-crown type microgel] and acrylamide core-crown type microgel [non-crosslinked type core-hat Type microgel].

1. cross-linking type core-crown type microgel [(acrylate/methacrylic acid methoxy ester PGE-90) cross-linked polymer)]

Cross-linking type core-crown type the microgel of which is that monomer shown in following formula (1)~(3) can be made in specific condition Lower free radical polymerization and obtain.

R₁It is the alkyl of carbon number 1~3, n is 8~200 number.X is H or CH₃。

The huge monomer of polyethylene oxide shown in above-mentioned formula (1) for example can be used Aldrich sale commercially available product or The commercially available products such as the Blemmer (registered trademark) that You company sells.The molecular weight (i.e. the value of n) of polyethylene oxide portion is necessary for N=8~200.

As such huge monomer, for example, can enumerate You company manufacture Blemmer (registered trademark) PME-400, Blemmer (registered trademark) PME-1000, Blemmer (registered trademark) PME-4000 etc..

R₂It is the alkyl of carbon number 1~3.

R₃It is the alkyl of carbon number 1~12, the more preferably alkyl for carbon number 1~8.

It is commercially available that for example Aldrich or Tokyo chemical conversion company can be used to sell for hydrophobic monomer shown in formula (2) Product.

The concrete example of hydrophobic monomer as formula (2), can enumerate: methyl acrylate, ethyl acrylate, acrylic acid third Ester, butyl acrylate, amyl acrylate, Hexyl 2-propenoate, heptylacrylate, 2-ethyl hexyl acrylate, decyl acrylate, acrylic acid ten Dialkyl ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, metering system Sour pentyl ester, hexyl methacrylate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, decyl-octyl methacrylate, methacrylic acid Dodecyl ester etc..Especially preferably use methyl methacrylate, butyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester.

These hydrophobic monomers are general raw materials, can also be easy to obtain as general industry raw material.

R₄With R₅Separately indicate the alkyl of carbon number 1~3, m is 0~2 number.

Cross-linkable monomer shown in formula (3) can be used as commercially available product or industrial raw material obtains.The cross-linkable monomer is preferred For hydrophobicity.

The value of m is preferably 0~2.Specifically, it is preferable that for the ethylene glycol dimethyl propylene sold using Aldrich Acid esters (below sometimes referred to as EGDMA (ethylene glycoldimethacrylate)), You company sells Blemmer (registered trademark) PDE-50 etc..

Cross-linking type core-crown type the microgel of which is to make above-mentioned monomer certainly under conditions of (a1) below~(e1) The winner by base polymerization.

(a1) represented by the addition mole of the huge monomer of above-mentioned polyethylene oxide/above-mentioned hydrophobic monomer addition mole Molar ratio be 1:10~1:250.

(b1) additive amount of the additive amount of above-mentioned cross-linkable monomer relative to above-mentioned hydrophobic monomer is 0.1~1.5 matter Measure %.

(c1) hydrophobic monomer shown in formula (2) be will have the alkyl of carbon number 1~8 methacrylic acid derivative 1 Kind or the monomer composition of two or more mixing.

(d1) polymer solvent is water-organic solvent mixed solvent, as organic solvent, in using polyalcohol the case where Under, it is one kind or two or more in dipropylene glycol, 1,3-BDO, isoprene.

(e1) the solvent composition of water-organic solvent mixed solvent is the water: organic in terms of 20 DEG C of mass ratio or capacity ratio Solvent=90~10:10~90.

It should be noted that in the present invention, by " additive amount of above-mentioned cross-linkable monomer is relative to above-mentioned hydrophobic monomer Additive amount " be defined as " crosslink density (quality %) ".It is foundation for core of the invention-crown type microgel crosslink density (b1) condition, additive amount of the additive amount of above-mentioned cross-linkable monomer relative to above-mentioned hydrophobic monomer, it is necessary to be 0.1~1.5 Quality %.Each condition is described in further detail below.

Condition (a1)

The addition mole of the huge monomer of polyethylene oxide and hydrophobic monomer is in the huge monomer of polyethylene oxide: hydrophobic monomer It is polymerizable in the range of=1:10~1:250 (molar ratio).Above-mentioned addition mole is preferably 1:10~1:200, more preferably for 1:25~1:100.

If the mole of hydrophobic monomer is lower than 10 times relative to the mole of the huge monomer of polyethylene oxide, then it is polymerize Polymer become water-soluble, do not form core-crown type microgel.In addition, if mole relative to the huge monomer of polyethylene oxide, The mole of hydrophobic monomer is more than 250 times, then the dispersion stability of the huge monomer of polyethylene oxide becomes inadequate, and utilization is insoluble Property the aggregation of hydrophobic monomer resulting hydrophobic polymer, precipitating.

Condition (b1)

By being copolymerized cross-linkable monomer, the microgel that the hydrophobic polymer of core can be made to be crosslinked polymerize.

If the additive amount of cross-linkable monomer is lower than 0.1 mass % of the additive amount of hydrophobic monomer, crosslink density is lower, Microgel dissolves when swelling.In addition, the mutual aggregation of micro-gel particles is generated if additive amount is more than 1.5 mass %, it can not Make the suitable micro-gel particles polymerization of narrow particle size distribution.The additive amount of cross-linkable monomer be preferably 0.2~1.0 mass %, compared with It preferably 0.2~0.8 mass %, is most preferably 0.2~0.5 mass %.

Condition (c1)

Hydrophobic monomer shown in formula (2) is necessary for having the 1 of the methacrylic acid derivative of the alkyl of carbon number 1~8 Kind or the monomer composition of two or more mixing.If carbon number is 0 (monomer of no end ester bond), there is monomer to become over hydrophilic, nothing Method successfully carries out the case where emulsion polymerization.On the other hand, if carbon number is 9 or more, there are steric hindrance when becoming polymerization, Wu Fashun The case where constructing cross-linked structure sharply.

Condition (d1)

Polymer solvent is necessary for water-organic solvent mixed solvent.As organic solvent, ethyl alcohol, propyl alcohol, fourth can be used Alcohol, polyalcohol etc. preferably can dissolve shown in hydrophobic monomer shown in formula (2) and formula (3) in the case where using polyalcohol Cross-linkable monomer person.As for polyalcohol of the invention, it is necessary to be dipropylene glycol, 1,3-BDO, isoprene.

The case where being not necessarily to the purification steps such as dialysis, polymer fluid is directly used as raw material body can be manufactured to industrialness in consideration Under, the solvent mixed with water is not ethyl alcohol or propyl alcohol, butanol equal to irritating organic solvent is worried when being coated on skin, preferably For the polyalcohol that can be matched with cosmetics with versatility.

Condition (e1)

The solvent composition of water-organic solvent mixed solvent as polymer solvent is necessary in terms of 20 DEG C of mass ratio, Water: organic solvent=90~10:10~90.The solvent composition of water-organic solvent mixed solvent is preferably water: organic solvent= 90~10:10~90 (20 DEG C of capacity ratios), are more preferably water: organic solvent=80~20:20~80 (20 DEG C of capacity ratios).

Polymer solvent is in order to equably dissolve hydrophobic monomer, it is necessary to add organic solvent.The mixing ratio of organic solvent is 10~90 capacity ratios.In the case that the mixing ratio of organic solvent is lower than 10 capacity ratios, the solvability of hydrophobic monomer becomes It is extremely low, and polymerize in the state of being dripped with monomer, become huge piece, does not generate microgel.In addition, if the mixing of organic solvent It is poly- without emulsifying than more than 90 capacity ratios, then not generating the lotion using the resulting hydrophobic monomer of hydrophobic interaction It closes, microgel can not be obtained.

Use polyalcohol as organic solvent and core-crown type microgel for obtaining be polymer solvent is water-polyalcohol mixing Solvent is free of ethyl alcohol, can be easily obtained to the user of sensitive skin also without the cosmetics of skin irritation.

Polymerization initiator for polymerization system can be used common for the commercially available poly- of water-soluble hot radical polymerization Close initiator.In the polymerization system, may be polymerized without controlling stirring condition particularly severely also, can get polymerize it is micro- The very narrow person of the size distribution of gel particle.

2. non-crosslinked type core-crown type microgel [acrylamide core-hat]

The non-crosslinked type core-crown type microgel being preferably used in the present invention is to make list shown in following formula (4)~(6) Body free radical polymerization and core-crown type particle dispersion liquid for obtaining under the conditions of specific.

R₁It is the alkyl of carbon number 1~3, n (molecular weight of polyethylene oxide portion) is 8~200 number.X is H or CH₃。

The huge monomer of polyethylene oxide represented by above-mentioned formula (4) is preferably that acrylic acid derivative or methacrylic acid are derivative Object.Such as Blemmer (the registrar that the commercially available product of Aldrich sale or You limited liability company can be used to sell Mark) etc. commercially available products.As example, it is possible to use PME-400, PME- as methoxy poly (ethylene glycol) monomethacrylates 1000, PME-4000 (the n value in formula (1) is respectively n=9, n=23, n=90, all You limited liability company manufactures).

R₂Indicate the alkyl of carbon number 1~3, R₃Indicate the substituent group of the alkyl comprising carbon number 1~12.

Hydrophobic monomer represented by above-mentioned formula (5) be preferably acrylic acid derivative or methacrylic acid derivative (also referred to as For " acrylate derivative monomer "), such as methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid fourth can be used Ester, amyl acrylate, Hexyl 2-propenoate, heptylacrylate, 2-ethyl hexyl acrylate, decyl acrylate, dodecylacrylate, first Base methyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, methyl Hexyl 2-propenoate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, decyl-octyl methacrylate, lauryl methacrylate Deng.Wherein, particularly preferably methyl methacrylate (alias: methyl methacrylate), butyl methacrylate (alias: first Base butyl acrylate), 2-Propenoic acid, 2-methyl-, octyl ester.

These hydrophobic monomers are general raw materials, also can be used as general industry raw material and easily obtain.Such as it can also be used Aldrich or the commercially available product of Tokyo chemical conversion company sale.

R₄Indicate the alkyl of H or carbon number 1~3, R₅And R₆Indicate H or the alkyl comprising carbon number 1~18, preferably 1~12 Substituent group.

Hydrophobic monomer represented by above-mentioned formula (6) is preferably acrylamide derivative or methacrylamide derivatives (also referred to as " acrylamide derivative monomer ").Such as preferably use N-tert-butyl acrylamide, N, N- dimethyl allene acyl Amine, N- [3- (dimethylamino) propyl] acrylamide, t-butylmethacrylamide, octyl acrylamide, octyl methyl third Acrylamide, octadecyl acrylamide etc..Wherein, particularly preferably N-tert-butyl acrylamide, N,N-DMAA, N- [3- (dimethylamino) propyl] acrylamide.

These hydrophobic monomers can be used as commercially available product or industrial raw material obtains.

Constituting core of the invention-crown type particle copolymer is the condition according to following (a2)~(d2), by arbitrary Radical polymerization makes huge monomer represented by above-mentioned formula (4) and is selected from hydrophobic monomer represented by above-mentioned formula (5) and (6) In one kind or two or more copolymerization and winner.

(a2) the addition mole of the huge monomer of above-mentioned polyethylene oxide/(above-mentioned acrylate derivative monomer and/or propylene Amide derivatives monomer) addition mole represented by molar ratio be 1:10~1:250.

(b2) huge monomer shown in above-mentioned formula (4) is that there is repetitive unit to spread out for the acrylic acid of 8~200 polyethylene glycol groups Biology or methacrylic acid derivative,

Acrylate derivative monomer shown in above-mentioned formula (5) is the substituent group with the alkyl comprising carbon number 1~12 Acrylic acid derivative or methacrylic acid derivative,

Acrylamide derivative monomer shown in above-mentioned formula (6) is the substituent group with the alkyl comprising carbon number 1~12 Acrylamide derivative or methacrylamide derivatives,

(c2) polymer solvent is water-alcohol mixed solvent, and alcohol is selected from ethyl alcohol, dipropylene glycol, 1,3-BDO, isoprene In it is one kind or two or more.

(d2) the solvent composition of water-alcohol mixed solvent is the water in terms of 20 DEG C of mass ratio: alcohol=90~10:10~90.

Each condition is described in further detail below.

Condition (a2)

The above-mentioned huge monomer of polyethylene oxide and above-mentioned hydrophobic monomer are (that is, acrylate derivative monomer and/or propylene The summation of amide derivatives monomer) addition mole in the huge monomer of polyethylene oxide: hydrophobic monomer=1:10~1:250 It is polymerizable in the range of (molar ratio).Above-mentioned addition mole is preferably 1:10~1:200, is more preferably 1:25~1:100.

If the mole of hydrophobic monomer is lower than 10 times relative to the mole of the huge monomer of polyethylene oxide, it is polymerize Polymer becomes water-soluble, does not form core-crown type particle.In addition, if the mole of hydrophobic monomer is relative to polycyclic oxygen second The mole of the huge monomer of alkane is more than 250 times, then the dispersion stability of the huge monomer of polyethylene oxide becomes inadequate, and utilization is insoluble The aggregation of hydrophobic monomer resulting hydrophobic polymer, precipitating.

Condition (b2)

Condition (b2) includes 3 conditions of following (b2-1)~(b2-3).

(b2-1)

Huge monomer represented by formula (4) be have repetitive unit be 8~200 polyethylene glycol groups acrylic acid derivative or Methacrylic acid derivative.If repetitive unit be 7 hereinafter, if having the case where can not obtaining the particle being stably dispersed in solvent, If having Particle pollution more than 200 and while being matched with cosmetics becoming unstable situation.

(b2-2)

Acrylate derivative monomer shown in above-mentioned formula (5) is the substituent group with the alkyl comprising carbon number 1~12 Acrylic acid derivative or methacrylic acid derivative.If carbon number is 0 (monomer of no end ester bond), there is that monomer is excessively hydrophilic, It can not be successfully the case where carrying out emulsion polymerization.On the other hand, if carbon number is 13 or more, preferred use feeling can not be obtained by having Situation.

(b2-3)

Acrylamide derivative monomer shown in above-mentioned formula (6) is the substituent group with the alkyl comprising carbon number 1~18 Acrylamide derivative or methacrylamide derivatives.

The hydrophobic monomer of which is necessary for that acrylate derivative monomer and formula represented by above-mentioned formula (5) will be selected from (6) the one kind or two or more mixed monomer composition in the acrylamide derivative monomer represented by.

In which, as hydrophobic monomer, methacrylate and butyl methacrylate are particularly preferably used Two kinds or methacrylate, N-tert-butyl acrylamide, N, N- dimethacrylamide and N- [3- (dimethylamino) third Base] four kinds of acrylamide.In the combination of these hydrophobic monomers, in turn, as huge monomer, it is preferable to use methoxyl group is poly- Ethylene glycol methacrylate.

It is not limited to this, but the combination as most preferred in which huge monomer and hydrophobic monomer, can enumerated:

The repetitive unit of polyethylene glycol groups is 8~90, is most preferably 15 methoxy poly (ethylene glycol) monomethacrylate Ester, methacrylate and butyl methacrylate,

The repetitive unit of polyethylene glycol groups is 8~200, is most preferably 90 methoxy poly (ethylene glycol) monomethacrylate Ester, methacrylate, N-tert-butyl acrylamide, N, N- dimethacrylamide and N- [3- (dimethylamino) propyl] third Acrylamide, t-butylmethacrylamide, octyl acrylamide, octyl methyl acrylamide, octadecyl acrylamide.

Condition (c2)

Polymer solvent is necessary for water-alcohol mixed solvent.As alcohol, hydrophobicity shown in formula (5) and (6) preferably can dissolve Monomer person.It is therefore preferable that being one kind or two or more in ethyl alcohol, dipropylene glycol, 1,3-BDO, isoprene.

Condition (d2)

The solvent of water-alcohol mixed solvent as polymer solvent forms in terms of 20 DEG C of mass ratio or capacity ratio, preferably Water: alcohol=90~10:10~90, further preferably water: alcohol=80~20:20~80.It is lower than 10 capacity in the mixing ratio of alcohol Than in the case where, the case where thering is the solvability of hydrophobic monomer to become extremely low, not generating particle.In addition, in the mixing ratio of alcohol In the case where more than 90 capacity ratios, there is the lotion not generated using the resulting hydrophobic monomer of hydrophobic interaction, without Emulsion polymerization, the case where particle can not be obtained.

Above-mentioned core-crown type the microgel being preferably used in the present invention is using as the high molecular polycyclic oxygen of nonionic The stabilized microgel of ethane chain, to the dispersion stabilization in its water it can be expected that acid resistance or alkali resistance.Additionally, it is believed that above-mentioned micro- Gel is the regularization in solvent of the huge monomer of hydrophily and hydrophobic monomer, and generation partial size is approximately fixed, and core crosslinking, Or noncrosslinking core-crown type polymer-network method.

Core-crown type microgel use level in cosmetics of the invention is relative to cosmetics total amount, it is often preferred that 0.01~10 mass % (purity).When use level is lower than 0.01 mass % (purity), has and become difficult to obtain stable makeup The case where product.If use level is more than 10 mass % (purity), there is the sight of stability in the long-term preservation just under hot conditions The poor situation of not good enough situation or use feeling for point.

Above-mentioned core-crown type microgel is to be formed to have to emulsify oil-phase component and water-phase component, in being scattered in water-phase component In oil-phase component oil droplet on adsorb core-crown type microgel emulsifier made of structure O/W emulsion composition.Such as Upper core-crown type microgel the emulsifier is that emulsifying ability is excellent, becomes the extremely excellent water packet of stability if being used as emulsifier Oil type emulsification composition.Moreover, behavior of the core-crown type microgel to the biggish hydrophobicity powder of the specific gravity being present in oily phase It can get sufficient intensity.

(E) non-volatile liquid oil

Oil-in-water emulsion type cosmetic preparation of the invention contains (E) non-volatile liquid oil.

" non-volatile liquid oil " in so-called this specification is referred in room temperature (25 DEG C), normal pressure (1 atmospheric pressure (9.8×10⁴Pa volatility (for example, the oil for being about 200 DEG C or more comprising the boiling point under normal pressure) is not shown under)), in room temperature, There is mobility, non-solid liquid oil includes nonvolatile oil (hydrocarbon ils, ester oil other than silicone oil and silicone oil under normal pressure Deng).

(E) non-volatile liquid oil in the present invention also includes the ultraviolet radiation absorption for being equivalent to the oiliness of mentioned component A Agent.Therefore, the present invention includes that (1) non-volatile liquid oil (ingredient E) includes the non-volatile liquid other than ultraviolet absorbing agent The mode of state oil and (2) ingredient E only include the mode of ultraviolet absorbing agent.

It is contained in ingredient E and in the non-volatile liquid oil other than ultraviolet absorbing agent, such as includes hydrocarbon Oil, vegetable oil, ester oil, the polyether polyols of high molecular weight, silicone oil.

It as concrete example, can enumerate: palm oil, linseed oil, camellia oil, Australia nut oil, corn oil, olive oil, crocodile Pear oil, camellia caul-fat, castor oil, safflower oil, apricot kernel oil, cinnamon oil, Jojoba Oil, grapefruit, apricot kernel oil, rapeseed oil, sesame Oil, sunflower oil, wheat-germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea oil, evening primrose oil, egg The liquid fats such as butter, liver oil, three polyglycereol, tricaprylin, three different tripalmitins；Cetyl octanoate etc. is pungent The lauric acid such as tricaprylates, the lauric acid hexyl esters such as acid esters, three -2 ethyl hexanoic acid glyceride, new penta 4 ester of four -2 ethyl hexanoic acids It is the palmitates such as myristinates, the octyl palmitates such as ester, isopropyl myristate, myristic acid octyldodecyl, hard The different palmitinic acids such as the isostearates such as stearates, the isopropyl isostearates such as resin acid isohexadecane base ester, different octyl palmitate The dibutoxyethyl sebacates such as the di adipates such as the oleates such as ester, Isodecyl oleate, diisopropyl adipate, diethyl sebacate, apple The ester oils such as the different stearyl ester of tartaric acid two；The hydrocarbon ils such as liquid paraffin, saualane；Polybutylene polyoxypropylene diols, polydimethylsiloxanes The silicone oil such as alkane.

The ratio of [total use level of ingredient B and ingredient C]/[use level of ingredient E]

Cosmetics of the invention are oil-in-water emulsion type cosmetic preparations, contain powder in interior oily phase.In such oil-in-water In the emulsion of powder-type, if the viscosity of interior oil phase is larger, have the tendency that being difficult to obtain stable emulsion.However, in this In invention, by total use level of (B) oil phase thickeners of oily phase in constituting and (C) silicic acid anhydride powder with (E) is non-waves The ratio ([B+C/E]) of the use level of hair property liquid oil (including (A) ultraviolet absorbing agent) is set as in particular range, can be made into Stable emulsion, and play the special-effect improved using the resulting ultraviolet protection ability of contact with moisture.

(B) oil phase thickeners in oil-in-water emulsion type cosmetic preparation of the invention are always matched with (C) silicic acid anhydride powder The ratio ([B+C/E]) of resultant and the use level of (E) non-volatile liquid oil (including (A) ultraviolet absorbing agent) is necessary for In the range of 0.2~20.

In addition, total use level of (B) oil phase thickeners and (C) silicic acid anhydride powder is preferably total relative to cosmetics Amount, is set as 7.5~40 mass %, the use level of (E) non-volatile liquid oil can be in the item of satisfaction [B+C/E]=0.2~20 Appropriate adjustment in the range of part.

It, can be in not interfering effect of the invention in addition to above-mentioned essential component in oil-in-water emulsion type cosmetic preparation of the invention In the range of fruit, cooperation is commonly used in the ingredient of cosmetics as any ingredient.

As the example of any ingredient, volatile oil can be enumerated, the volatile oil that can be matched in the present invention includes to wave The hair property lower alcohols such as hydrocarbon ils and volatile silicone oils, ethyl alcohol.

As long as volatile hydrocarbon oil is to have volatile hydrocarbon under room temperature (25 DEG C) for cosmetics etc. back and forth Oil is not particularly limited.As concrete example, such as Permethyl 99A, isohexadecane, Parleam can be enumerated etc..

Comprising there is volatile silicone oil under room temperature (25 DEG C) for cosmetics etc. back and forth in volatile silicone oils, Such as volatile straight-chain silicone oil (volatility dimethyl polysiloxane) and volatile cyclic silicone oils (poly- methyl of volatility ring Siloxanes).As volatility dimethyl polysiloxane, the low viscosities dimethyl polysiloxanes such as decamethyl tetrasiloxane can be used, As commercially available product, KF-96L-1.5cs, KF-96L-2cs (being Shin-Estu Chemical Co., Ltd's manufacture) etc. can be enumerated. As volatility cyclopolysiloxane, decamethylcyclopentasiloxane (D5) etc. can be enumerated.

As any other ingredient, water-soluble or oil-soluble filming agent can be enumerated.It, can be further by cooperating filming agent It improves to the loss of (A) ultraviolet absorbing agent or (C) silicic acid anhydride powder or because of the resistance fallen that rubs caused by clothes etc. Property.But the range that use level is preferably set as overlay film sense (usability) or cleaning does not reduce.

As filming agent, there is no particular restriction as long as commonly used in cosmetics person, specifically, can enumerate: poly- second Alkene pyrrolidone (PVP, polyvinylpyrrolidone), PVP/ dimethyl aminoethyl methacrylic acid copolymer, PVP/ Icosa alkene copolymer, PVP/ ethyl methacrylate/methacrylic acid copolymer, PVP/ hexadecene copolymer, PVP/VA copolymerization The PVP based coating agent such as object, PVP/ vinyl acetate/itaconic acid copolymer, styrene/PVP copolymer；Ethyl acrylate/propylene Amide/acrylic copolymer, ethyl acrylate/butyl acrylate copolymer, ethyl acrylate/ethyl methacrylate copolymerization Object, ethyl acrylate/methacrylic acid copolymer, ethyl acrylate/methylmethacrylate copolymer, 2-ethyl hexyl acrylate/second Vinyl acetate copolymer, 2-ethyl hexyl acrylate/styrol copolymer, butyl acrylate/vinyl acetate copolymer, acrylic acid fourth Ester/hydroxy ethyl methacrylate copolymer, butyl acrylate/methylmethacrylate copolymer, methoxyethyl acrylate/ Hydroxyethyl Acrylate/butyl acrylate copolymer, polyethyl acrylate, is gathered lauryl acrylate/vinyl acetate copolymer The acrylic acid series filming agent such as butyl acrylate, polystyrene acrylic acid resins；The vinyl acetates based coating such as polyvinyl acetate Agent；Polymethyl methacrylate, methyl methacrylate/butyl acrylate/acrylic acid octanoic acid, diethyl sulfuric acid vinyl pyrrole Alkanone/N, the metha crylics filming agent such as N '-dimethyl ammonio methacrylate copolymer；Vinyl methyl ether/maleic acid The vinyl methyl ethers based coating agent such as methacrylate copolymers, vinyl methyl ether/butyl maleate copolymer；Styrene/methylbenzene The polystyrenes filming agent such as ethylene/indene copolymer；The alkyd resins based coating agent such as hexamethylene methane series alkyd resin；Trimethyl silicane alcoxyl Silicone resins based coating agent such as base silicic acid etc..

It as any other ingredient, can enumerate commonly used in the ingredient of cosmetics, such as whitening agent, moisturizer, anti-oxidant It is agent, oiliness activating agent, surfactant, water phase thickener, usability powder (through except silicic acid anhydride person), colorant, aqueous Activating agent etc..

As usability powder, the colorant of any ingredient, pigment, pearlescent pigment etc. can be used to be generally mated in cosmetic Cosmetic person.Specifically, can enumerate: Inorganic white system pigment (titanium dioxide, zinc oxide), inorganic red system's pigment (iron oxide (colcother), iron titanate), inorganic brown pigment (B- iron oxide), inorganic yellow pigment (iron oxide yellow, sienna), nothing Machine black system pigment (iron oxide black, carbon, titanium suboxide), inorganic purple pigment (manganese violet, cobalt violet), inorganic green pigment (chromium oxide, chromium hydroxide, cobalt titanate), inorganic blue pigment (ultramarine, Prussian blue), pearlescent pigment (aoxidize titanium coated cloud Female, the titanium coated Bismuth Oxychloride of oxidation, the titanium coated talcum of oxidation, coloring aoxidize titanium coated mica, Bismuth Oxychloride, guanin), metal Powder pigments (aluminium powder, copper powder), organic pigment (No. 202 red, No. 205 red, No. 220 red, No. 228 red, red 405 Number, No. 203 orange, No. 204 orange, yellow 205, yellow 401, blue No. 404), zirconium, barium, aluminum lake organic pigment (red 3, No. 104 red, No. 227 red, No. 401 red, No. 205 orange, yellow 4, yellow 202, green 3, indigo plant Color 1), natural pigment (chlorophyll, carotenoids prime system (C- carrotene), carthamin, alkermes, chalcone, lutein, Betanin, flavonols, flavones, anthocyanidin, anthraquinone, naphthoquinones), functional pigment (boron nitride, photochromic pigment, synthesis fluorine gold Mica, iron-containing synthetic fluorophlogopite, particle composite granule (mixing fine powders end)) etc., but it is not limited to these.Usability powder End, colorant can will for example cooperate selected from one kind or two or more combination among the above.

Oil-in-water emulsion type cosmetic preparation of the invention can be manufactured according to conventional method.Such as it can be prepared via a method which: Water phase thickener is arbitrarily dissolved in water composition (comprising nonionic surfactant and/or core-crown type microgel), in A part addition surfactant of oil components dissolved with oil phase thickeners, makes ultraviolet light scattering diluent dissolve or disperse, will It is added in water composition, carries out emulsification treatment using homogeneous blender etc., finally adds remaining oil components and powder, It is stirred mixing (when stirring, can also arbitrarily additional shear power).

Oil-in-water emulsion type cosmetic preparation of the invention is for example preferably used as suncream, ultra light sun block lotion, suntan lotion, imparting Muffin, foundation cream of sun-proof result etc..

The mode of sunscreen cosmetic is illustrated above, but the present invention is not limited to which.For example, by with Cosmetics of the invention are base, cooperation pearling agent, toner (pigment) etc., can be made by with contact with moisture characteristic (transparency, Colour rendering, concave-convex correction effect etc.) generate the new cosmetic cosmetics or skin protection cosmetics changed.The cosmetics of such mode have Have by with sweat or contact with moisture, improve the new features of dressing effect or skin effect instead.No matter the characteristic is purple containing (A) In the sunscreen cosmetic of 1 mass % of ultraviolet absorbers or more, or (A) ultraviolet absorbing agent use level be lower than 1 mass % Cosmetics or cosmetics without ultraviolet absorbing agent in be observed (referring to table 4 and Formulation Example 5 and 6).

That is, the present invention also includes the mode of following oil-in-water emulsion type cosmetic preparation, it is characterised in that:

Containing (A1) 1 mass % ultraviolet absorbing agent below,

(B) oil phase thickeners,

(C) silicic acid anhydride powder,

(D) nonionic surfactant and/or core-crown type microgel, and

(E) non-volatile liquid oil (including above-mentioned (A) ultraviolet absorbing agent)；And

(B) total use level of oil phase thickeners and (C) silicic acid anhydride powder is relative to (E) non-volatile liquid oil The ratio ([(B)+(C)]/(E)) of use level is 0.2~20.

(A)~(E) ingredient in the invention of which is identical as sunscreen cosmetic expositor.Wherein, (A) is ultraviolet The use level of light absorbers be lower than 1 mass %, may be, for example, 0.5 mass % or less, 0.3 mass % or less or 0.1 mass % with Under, it can be free of ultraviolet absorbing agent.

Oil-in-water emulsion type cosmetic preparation of the invention is characterized in that by uniform with contact with moisture makeup film (film thickness) Change.To limit the intent of the present invention, but the inventors of the present invention think, the makeup film on skin perpendicular on skin direction The distribution (density) of ultraviolet absorbing agent is homogenized in entire film, and as a result ultraviolet protection ability improves.Think the phenomenon simultaneously It is not limited to ultraviolet absorbing agent, it helps the uniformity of the distribution of various composition joined together.Therefore, by perspire etc. with Contact with moisture, film become uniformly, so that the optical characteristics (diffuse and internal reflected light) for film of making up becomes close to plain face, It plays transparent feel to increase, and feels the effect of beautiful beauty.

Embodiment

It is exemplified below concrete example and then explains the present invention in detail, but the present invention is not limited to embodiments below.Separately Outside, the use level in embodiment below etc. is as long as no special instructions, then it represents that quality %.

According to the method recorded in paragraph 0078, the oil-in-water type cream with the composition recorded in following table 1~table 4 is prepared Change sunscreen cosmetic.To the sample of each example, the absorbance change before and after emulsion stability and water-bath is measured.

The measurement of emulsion stability

The sample of each example is saved under conditions of 60 DEG C two weeks, visually whether there is or not separation or precipitatings for observation.Utilize following benchmark Measurement result is evaluated.

A: not observing separation and precipitating, relatively stable.

B: separation or precipitating are observed.

The measurement of ultraviolet protection effect

In S plate (the V slot PMMA plate of 5 × 5cm, SPFMASTER-PA01), with 2mg/cm²Amount the examination of each example is added dropwise Sample, and be coated with 60 seconds with finger, after 15 minutes dry, remembered certainly using the U-3500 type of Hitachi Co., Ltd's manufacture Its absorbance (500~280nm) of spectrophotometric determination.It is control with uncoated plate, calculates extinction using formula below It spends (Abs).

Abs=-log (T/To)

T: the transmitance of sample, To: transmitance when uncoated

The plate measured is sufficiently soaked in the water of hardness 50~500, and stirring (utilizes 3-1 horse directly in water Reach, 300rpm) 30 minutes.Thereafter, the drying made 15~30 minutes or so, until surface becomes no water droplet, extinction was measured again Degree calculates Abs change rate (formula below) according to the Abs aggregate-value before and after water-bath and is used as ultraviolet protection ability improvement effect.

Absorbance change rate (%)=(the absorbance aggregate-value after water-bath) before and after water-bath/(absorbance before water-bath is tired Evaluation) × 100

It should be noted that in the case that above-mentioned absorbance change rate is more than 100 (%), being defined as in the present invention Ultraviolet protection effect improves.

[table 1]

According to the result of table 1, be combined with oil phase thickeners ((palmitinic acid/2 ethyl hexanoic acid) dextrin, hydrogenated palm oil or Vaseline) Examples 1 to 4 obtain water-bath before and after absorbance change rate be more than 100%, ultraviolet protection effect raising spy Some effects mismatch the comparative example 1 of oil phase thickeners and have cooperated silicone-based filming agent instead of the comparative example 2 of oil phase thickeners Identical effect is not obtained.

[table 2]

According to shown in table 2 as a result, confirmation will (B) oil phase thickeners and (C) silicic acid anhydride powder total use level and (E) embodiment 5~10 for the range that the ratio [(B+C)/E] of the use level of non-volatile liquid oil is set as 0.2~20 is to obtain Stable sample is obtained, the absorbance change rate before and after water-bath is more than 100%, and ultraviolet protection effect improves.However, ratio [(B+ C)/E] it is more than that 20 comparative example 3 does not obtain stable emulsion, it can not also carry out the measurement of absorbance.

[table 3]

According to shown in table 1~3 as a result, in use Crodaret as nonionic surfactant In the case of, the stable emulsion that its HLB is 14 (tables 1 and 2) or 9 (tables 3) is obtained, the absorbance change rate before and after water-bath also surpasses 100% is crossed, and then water resistance is also excellent.On the other hand, the system without Crodaret is that non-ionic surface is living Property agent HLB be 7 and emulsifiable, but the absorbance change rate before and after water-bath is unsatisfactory for 100% (comparative example 4), uses HLB= The system of 5.5 nonionic surfactant is can not to prepare stable emulsion (comparative example 5).

On the other hand, instead of nonionic surfactant, or in addition to nonionic surfactant, crosslinking is used The core-of the core of type-crown type microgel ((acrylate/methacrylic acid methoxy ester PEG-90) cross-linked polymer) or non-crosslinked type The emulsion stability of the embodiment 12~15 of crown type microgel (acrylamide nuclear cap) is excellent, the absorbance change before and after water-bath Rate is also above 100%, and then water resistance is also excellent.

[table 4]

Confirmed according to result shown in table 4, even if the surface treating agent of silicic acid anhydride powder is changed to silicone (diformazan Based polysiloxane), alkoxy silane (octyltri-ethoxysilane), the rouge such as dextrin fatty acid esters, the stearic acid such as Dextrin palmitate Fat acid and silica, also can get effect of the invention.

With the formula recorded in following table 5, water-in-oil emulsion is prepared using method identical with other embodiments and is made up Product.To the sample of each example, (water-bath) test of perspiring is implemented to 10 functional panelists under the conditions of below.

After being coated with the sample of each example, for, by skin after sixty minutes, being evaluated in the environment of 30 DEG C of temperature, humidity 80% Whether there is transparent feel compared with before perspiration (water-bath) test, if feel beautiful (whether there is or not true feelings).

To above-mentioned perspiration (water-bath) test as a result, utilizing benchmark divided rank below.

8 or more have true feeling in A:10

5 or more and 7 or less have true feeling in B:10

4 or less have true feeling in C:10

[table 5]

As shown in table 5, for meeting the embodiment 22~24 of necessary condition of the invention, in perspiration and and contact with moisture Afterwards, the skin for implementing makeup is more transparent, it appears that beautiful.However, the comparative example 6 and 7 without (B) oil-soluble thickener does not obtain Such true feeling.

It is exemplified below other Formulation Examples of oil-in-water emulsion type cosmetic preparation of the invention.The cosmetics of these Formulation Examples are also newborn Change stability and excellent water resistance, the absorbance change rate in the case where sunscreen cosmetic before and after water-bath are more than 100%, obtains Seem the effect of beautiful equal beauty by water-bath.

1. ultra light sun block lotion of Formulation Example

[table 6]

2. suncream of Formulation Example

[table 7]

3. foundation cream of Formulation Example

[table 8]

Purified water	It is remaining
		Sodium citrate	In right amount
Citric acid	In right amount
		Edetate trisodium	In right amount
Cremophor RH40 (HLB:12)	1.5
		Two oleic acid PEG-8 (HLB:5)	0.2
1,3 butylene glycol	5
		Glycerol	5
Dimethacrylamide/acryloyl dimethyl tauric acid sodium cross-linked polymer	1
		Succinoglycan	0.3
Sorbitol anhydride sesquialter isostearate	0.3
		Lightweight isoparaffin	12
Isostearic acid	1
		Parsol 1789	1
2,4,6- tri- [4- (2- ethyl hexyl oxy carbonyl) phenylamino] 1,3,5- triazine	2
		2,4- is bis--[{ 4- (2- ethyl hexyl oxy) -2- hydroxyl }-phenyl] -6- (4- methoxyphenyl) -1,3,5- triazine	1
The own ester of diethylamino hydroxybenzoyl benzoylbenzoic acid	2
		Dextrin palmitate	3
Sucrose fatty ester	3
		Octyltri-ethoxysilane chloro distearyl dimethyl ammonium handles zinc oxide	10
Pearling agent (mica titanium)	3
		Titanium oxide (pigment)	1
Iron oxide	0.3
		It amounts to	100
B+C	16
		(B+C)/E	2.286

4. foundation emulsion of Formulation Example

[table 9]

Ion exchange water	It is remaining
		Sodium citrate	In right amount
Citric acid (food)	In right amount
		EDTA-3Na.2H2O	In right amount
PEG-60 rilanit special (HLB:14)	2
		1,3 butylene glycol	7
Glycerol	3
		Dimethacrylamide/acryloyl dimethyl tauric acid sodium cross-linked polymer	0.3
Succinoglycan	0.2
		Sodium carboxymethylcellulose	0.1
Lightweight isoparaffin	18
		Sorbitol anhydride sesquialter isostearate	0.2
Isostearic acid SX	1
		Neo Heliopan AV	5
2,4- is bis--[{ 4- (2- ethyl hexyl oxy) -2- hydroxyl }-phenyl] -6- (4- methoxyphenyl) -1,3,5- triazine	2
		Mineral oil	2
Polypropylene glycol	1
		Methyl polysiloxane	4
Dextrin palmitate	3
		Vaseline	3
The silica-coated zinc oxide of dimethyl polysiloxane processing	16
		Phenoxetol	In right amount
Titanium oxide (pigment)	5
		Pearling agent (mica titanium)	3
Iron oxide	1
		Hexamethylene diisocyanate/trihydroxy methyl hexyl lactone cross-linked polymer	1
It amounts to	100
		B+C	22
(B+C)/E	1.47

Formulation Example 5.CC frost

[table 10]

Purified water	It is remaining
		Sodium citrate	In right amount
Citric acid	In right amount
		Edetate trisodium	In right amount
Cremophor RH40 (HLB:12)	1.5
		Two isostearic acid PEG-8 (HLB:5)	0.2
1,3 butylene glycol	3
		Glycerol	8
Dimethacrylamide/acryloyl dimethyl tauric acid sodium cross-linked polymer	1
		Succinoglycan	0.3
Sorbitol anhydride sesquialter isostearate	0.3
		Lightweight isoparaffin	12
Isostearic acid	1
		Dextrin palmitate	2
Sucrose fatty ester	1
		Calcium stearate handles talcum	5
Pearling agent (mica titanium)	3
		Titanium oxide (pigment)	0.5
Iron oxide	0.3
		It amounts to	100
B+C	8
		(B+C)/E	8

6. foundation emulsion of Formulation Example

[table 11]

Ion exchange water	It is remaining
		Sodium citrate	In right amount
Citric acid (food)	In right amount
		EDTA-3Na.2H2O	In right amount
PEG-60 rilanit special (HLB:14)	2
		1,3 butylene glycol	7
Glycerol	3
		Dimethacrylamide/acryloyl dimethyl tauric acid sodium cross-linked polymer	0.3
Succinoglycan	0.2
		Sodium carboxymethylcellulose	0.1
Lightweight isoparaffin	18
		Sorbitol anhydride sesquialter isostearate	0.2
Isostearic acid SX	1
		Decanedioic acid isobutyl ester	5
Mineral oil	2
		Polypropylene glycol	1
Methyl polysiloxane	4
		Dextrin palmitate	3
Vaseline	3
		Phenoxetol	In right amount
Titanium oxide (pigment)	5
		Pearling agent (mica titanium)	3
Iron oxide	1
		Hexamethylene diisocyanate/trihydroxy methyl hexyl lactone cross-linked polymer	1
It amounts to	100
		B+C	6
(B+C)/E	0.75

Claims (6)

1. a kind of oil-in-water emulsion type cosmetic preparation, which is characterized in that contain:

(A) ultraviolet absorbing agent；

(B) oil phase thickeners；

(C) silicic acid anhydride powder；

(D) nonionic surfactant and/or core-crown type microgel；With

(E) non-volatile liquid oil, it includes (A) ultraviolet absorbing agents；And

(B) total use level of oil phase thickeners and (C) silicic acid anhydride powder is relative to (E) the non-volatile liquid oil The ratio ([(B)+(C)]/(E)) of use level is 0.2~20.

2. cosmetics according to claim 1, wherein (B) oil phase thickeners are selected from by dextrin fatty acid ester, Sucrose Fatty Acid Ester It is one kind or two or more in the group of the hydrocarbon ils composition of fat acid esters, organo-clay mineral and solid or semisolid.

3. cosmetics according to claim 1 or 2, wherein the surface treating agent of (C) silicic acid anhydride powder be selected from by It is one kind or two or more in the group that alkoxy silane, dextrin fatty acid ester, fatty acid and silica form.

4. cosmetics according to any one of claim 1 to 3, wherein (D) nonionic surfactant includes polyoxy Ethylene hydrogenation castor oil.

5. cosmetics according to any one of claim 1 to 4, wherein the use level of (A) ultraviolet absorbing agent is 1 matter Measure % or more.

6. cosmetics according to any one of claim 1 to 5, wherein (B) oil phase thickeners and (C) silicic acid anhydride Total use level of powder is 7.5~40 mass %.