CN1264291A - Cosmetic compositions - Google Patents

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Publication number
CN1264291A
CN1264291A CN 98807390 CN98807390A CN1264291A CN 1264291 A CN1264291 A CN 1264291A CN 98807390 CN98807390 CN 98807390 CN 98807390 A CN98807390 A CN 98807390A CN 1264291 A CN1264291 A CN 1264291A
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Prior art keywords
acid
weight
oil
compositions
cosmetic composition
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CN 98807390
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Chinese (zh)
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G·E·戴克纳
C·桑
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Procter and Gamble Co
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Procter and Gamble Co
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/368Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/738Cyclodextrins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin

Abstract

Cosmetic composition for topical application to the skin comprising at least one aqueous phase, a cyclodextrin compound and a salicylic acid or salicylic acid derivative, wherein the composition has a pH of 5 or less. The compositions herein provide improved anti-acne/anti-inflammatory activity together with reduced skin irritation.

Description

Cosmetic composition
Invention field
The present invention relates to cosmetic composition, more specifically relate to contain the foundation cream color make-up compositions of pigment and hide flaw agent.
Background of invention
Foundation compositions can be coated in other position of face or health so that the colour of skin and skin matter are even, and can hide pore, flaw, microgroove etc.Foundation compositions also is used for skin care, the oils and fats level of balance skin, and be used to make skin to avoid the adverse effect that Exposure to Sunlight, wind and adverse circumstances cause.The color make-up compositions is generally body or cream frost suspending agent, Emulsion, gel, compacting powder at night, or anhydrous oils and wax based composition.This class beauty treatment color make-up compositions is preprinted in data the 1st volume 51-63 page or leaf (1986) in 14 I.F.S.C.C meetings (Barcelona, 1986) people such as US-A-3444291, US-A-4486405, US-A-4804532, US-A-3978207, US-A-4659562, US-A-5143722 and Nakamura and is stated.
Foundation cream color make-up compositions also is known, and it can provide good covering effect and good skin sense, durability and outward appearance.Simultaneously, need badly a kind of active foundation compositions of topical anti-acne that has is provided.Also need to provide a kind of to the skin gentleness and there is not or do not have substantially the foundation compositions of skin irritation.The known chemical compound that has the anti-acne characteristic when having multiple part to be used for skin.It is commonly used that to have the active molten cutin agent of anti-acne be salicylic acid.Salicylic acid reality is water insoluble, is difficult to it is joined the aqueous phase of Aquo System such as aqueous solution or emulsion composition.Although salicylic acid can discharge in the oil phase that contains pigment by foundation cream emulsified body compositions, because the interaction of salicylic acid and pigment (particularly iron oxides pigment) can cause the compositions variable color.Therefore need discharge the salicylic acid of soluble form by water.
In addition, because acidic skin care agent activity when low pH (free acid that has high concentration in the solution) is very high, therefore need discharge the acidic skin care agent by water under certain pH condition, it is a protonated form under this pH substantially.
Carried out multiple trial for improving salicylic acid at the dissolubility of aqueous phase.A kind of solution is to adopt alcoholic solvent such as ethanol.But there is zest in this based composition, Diazolidinyl Urea.Another helps salicylic acid to comprise the employing solubilisation aids in the method for aqueous phase solubilising, as PVP.For example WO95/04517 discloses a kind of emulsion-type color make-up compositions, wherein contains the acid anti-acne active ingredient that is soluble in the aqueous phase and the pigment or the pigment composition that are scattered in oil phase.Disclosed PVP is as the complexant of salicylic acid hydrotropy.Another method that helps the salicylic acid solubilising is to adopt cyclodextrin compound.Known cyclodextrin compound can form inclusion complex with salicylic acid, is dissolved in Aquo System to help salicylic acid.Following document discloses and has contained cyclodextrin compound and salicylic ointment type compositions: " influence that cyclodextrin and other additive discharge from various ointment substrate salicylic acid " Yakuzaigaku, 50 (4), 341-346 (1990) and " effect that additive discharges from ointment substrate for medicine " Yakuzaigaku, 42 (1), 10-16 (1982).
Although adopt above-mentioned these methods can make salicylic acid be dissolved in the aqueous phase of cosmetic composition, still need to have the anti-acne/anti-inflammatory activity of improvement, have the low cosmetic composition of skin mildness/skin irritation simultaneously.
Be surprised to find that at present pH be 5 or cosmetic composition lower, that contain at least one water in add salicylic acid or salicyclic acid derivatives and cyclodextrin compound and can obtain having the anti-acne/anti-inflammatory activity of improvement and the compositions of low skin irritability.
Basic purpose of the present invention provides a kind of active cosmetic composition of anti-acne with improvement.
Another object of the present invention provides a kind of to the low cosmetic composition that stimulates of skin.
Summary of the invention
The invention provides a kind of cosmetic composition that contains at least one water, aqueous phase contains cyclodextrin compound and salicylic acid or salicyclic acid derivatives, and wherein the pH of said composition is 5 or lower.
Cosmetic composition of the present invention has anti-acne/anti-inflammatory activity, the mildness of improvement, and stimulates skin is low.
Unless otherwise indicated, all content and ratio are all to account for composition total weight.Chain length and degree of alkoxylation are also in weighed average.
Detailed Description Of The Invention
Cosmetic composition of the present invention contains at least one water, cyclodextrin compound and salicylic acid or salicyclic acid derivatives.Cyclodextrin compound
The chief component of cosmetic composition of the present invention is a cyclodextrin compound.Here the term of Cai Yonging " cyclodextrin " (CD) comprises the unsubstituted ring dextrin that contains 6-12 glucose unit, particularly α-, β-, gamma-cyclodextrin and/or its derivant, with their mixture, it can form inclusion complex with salicylic acid or salicyclic acid derivatives.
Known have a multiple cyclodextrin derivative.Typical derivant sees US-A-3426011 people such as (, on February 4th, 1969 authorized) Parmerter; US-A-3453257, US-A-3453258, US-A-3453259, US-A-3453260 (inventor is people such as Parmerter, is to authorize on July 1st, 1969); US-A-3459731 (people such as Gramera, on August 5th, 1969 authorized); US-A-2553191 (people such as Parmerter, on January 5th, 1971 authorized); US-A-3565887 (people such as Parmerter, on February 23rd, 1971 authorized); US-A-4535152 (people such as Szejtli, on August 13rd, 1985 authorized); US-A-4616008 (people such as Hirai, on October 7th, 1986 authorized); US-A-4638058 (people such as Brandt, on January 20th, 1987 authorized); US-A-4746734 (people such as Tsuchiyama, on May 24th, 1988 authorized); And US-A-4678598 (people such as Ogino, on July 7th, 1987 authorized), described patent all is incorporated herein by reference.The example that is applicable to this cyclodextrin derivative has substitution value (DS) different methyl-beta-schardinger dextrin-, hydroxyethyl-and HP-.
Also independent cyclodextrin can be linked each other, for example adopt poly functional reagent to form oligomer, polymer etc.The example of this class material has beta-schardinger dextrin-/epihalohydrin copolymer.
Cyclodextrin mixt also is suitable for, and is used to provide the mixture of coordination compound.The mixture of cyclodextrin can be made easily by the intermediate product in the known cyclodextrin preparation method, and these methods are referring to US-A-3425910 (people such as Armbruster, on February 4th, 1969 authorized); US-A-3812011 (people such as Okada, on May 21st, 1974 authorized); US-A-4317881 (people such as Yagi, authorize March 2 nineteen eighty-two); US-A-4418144 (people such as Okada, authorize November 29 nineteen eighty-three); And US-A-4738923 (people such as Ammeraal, on April 19th, 1988 authorized), described patent all is incorporated herein by reference.
The cyclodextrin compound that preferably is applicable to the present composition has hydroxyl (C 1-C 4) alkyl cyclodextrins, particularly HP-.
The consumption of cyclodextrin compound accounts for the 0.1-20% (weight) of compositions in the cosmetic composition of the present invention, preferably is about 0.8-15% (weight), particularly is about 0.8-12% (weight).
Another key component of the present composition is salicylic acid or salicyclic acid derivatives.Terminology used here " salicyclic acid derivatives " is meant any 2,3 or the 4-OR substituted benzoic acid that is shown below:
Figure A9880739000061
Wherein R is selected from C 1-C 6Alkyl or C 1-C 6Acyl group, preferably wherein R is selected from C 2-C 3Alkyl or C 2-C 3Acyl group.The present invention particularly preferably is salicylic acid.
The consumption of salicylic acid or salicyclic acid derivatives should be the safe and effective amount of anti-acne/anti-inflammatory activity, preferably accounts for the 0.1-10% (weight) of compositions, is more preferably 0.1-5% (weight), especially preferably is about 0.5-2% (weight).
Being used for term of the present invention " safe and effective amount " is meant: in those skilled in the art's reasonable determination range, can make the described chemical compound of this phrase, compositions or other material of the capacity that is obtained being clearly better by the treatment illness, but this amount should be hanged down enough again to avoid undue side effect (for example tangible skin irritation or allergy).The safe and effective amount of chemical compound, compositions or other material is according to following factor and different: the health of the different skin of being nursed, age, biological object, the order of severity of illness, nursing persistent period, the character of continued treatment, used particular compound, compositions or other material, used used for cosmetic topical carrier, and the other factors in those skilled in the art's the knowledge and experience scope.Water
Cosmetic composition of the present invention comprises at least one water.The product forms that is suitable for that contains at least one water comprises: aqueous solution, aqueous dispersion, water-in-oil emulsion, oil-in-water emulsion, polysiloxanes water-in type Emulsion, aqueous gel, cream frost, water preparation, ointment etc.
Cosmetic composition of the present invention is preferably the Emulsion form, and preferably water-in-oil emulsion wherein comprises discontinuous water and successive oil phase.
Emulsion composition of the present invention preferably contains the oil phase of 20-95% (weight) approximately, is more preferably 30-70% (weight), and the water that contains 5-80% (weight) approximately, is more preferably 30-70% (weight).Water preferably contains the water of 40-90% (weight) approximately, is more preferably 60-80% (weight).The total amount of water accounts for the 10-60% (weight) of compositions in the compositions, is more preferably 30-50% (weight).
The pH of cosmetic composition of the present invention is about below 5 or 5, preferably is about below 4 or 4, particularly is about 3.Optional member
Can contain various optional members in the compositions.It below is the non-limiting example of the various compositions that are suitable for.Oil phase
When compositions of the present invention is water-in-oil emulsion, contain successive oil phase in the compositions.Can comprise silicone oil, the organic oils of non-silicone class or their mixture in the oil phase.
In preferred embodiments, the mixture that contains Y 7175 and non-volatile polysiloxanes in the oil phase.The polysiloxanes that is applicable to this has the skin condition characteristic.The content of polysiloxane fluid is about 1-50% (weight).The Y 7175 that is suitable for comprises ring-type or straight chain volatility polysiloxane.Be used for term of the present invention " non-volatile " and be meant that the vapour pressure of this material under 25 ℃, 1 atmospheric pressure is not higher than 0.1 millimetres of mercury.Be used for term of the present invention " volatility " and be meant that this material does not belong to nonvolatile, or the vapour pressure of this material is higher than 0.1 millimetres of mercury under the same conditions.
Description to various Y 7175s sees the article (91, " cosmetics and toilet articles " 27-32 (1976)) that people such as Todd are entitled as " the Y 7175 fluid that is applicable to cosmetics ".
Preferred cyclic polysiloxanes comprises the ring-type dimethyl siloxane chain that on average contains 3-9 silicon atom approximately, preferably contains 4-9 silicon atom approximately.Preferred straight chain polysiloxanes comprises the polydimethylsiloxane that on average contains 3-9 silicon atom approximately.The viscosity of 25 ℃ of following straight chain Y 7175s generally is less than about 5 centistokes, and the viscosity of cyclic polysiloxanes is less than about 10 centistokes.The example that is applicable to silicone oil of the present invention comprises: Dow Corning 344, Dow Corning 245, Dow Corning 345 and Dow Corning 200 (being produced by Dow Corning company); Polysiloxanes 7207 and polysiloxanes 7158 (producing) by Union Carbide company.SF202 (producing) and SWS-03314 (producing) by Stauffer Chemical by General Electric.
The vapour pressure of non-volatile polysiloxanes as mentioned above, preferred 25 ℃ down its average viscosities be about 10-100,000 centipoise is more preferably 100-10,000 centipoise is more preferably the 500-6000 centipoise.But the non-volatile polysiloxanes conditioner that viscosity is lower also is suitable for.
The glass capillary tube viscometer that can adopt Dow Corning test method CTM0004 (on July 20th, 1970) to be proposed is measured viscosity.
Be applicable to that non-volatile polysiloxane fluid of the present invention comprises poly-alkylsiloxane, poly-aryl siloxanes, poly-alkaryl siloxanes, the polysiloxanes that contains the amino functional substituent, polyether siloxane copolymer and their mixture.Be applicable to that siloxanes of the present invention can be substituted and/or through the group end capping of any amount, local with in the cosmetics as long as the gained material still is applicable to, group for example comprises methyl, hydroxyl, oxirane, expoxy propane, amino and carboxyl.But other polysiloxane fluid with skin condition characteristic also is suitable for.The non-volatile poly-alkylsiloxane fluid that is suitable for for example comprises polydimethylsiloxane.These siloxanes are commercially available, for example available from Viscasil (RTM) series of products of General Electric company with available from Dow Corning 200 series of products of Dow Corning company.Preferred its viscosity under 25 ℃ is about 10mm 2S -1-100,000mm 2S -1The poly-alkaryl siloxanes fluids that is suitable for for example also comprises PSI.These siloxanes are commercially available, for example available from the SF1075 aminomethyl phenyl fluid of General Electric company, or available from the Dow Corning 556 cosmetics-stage fluids of Dow Corning company.The polyether siloxane copolymer that is suitable for for example comprises the dimethyl polysiloxane (for example DowCorning DC-1248) of poly(propylene oxide) modification, but oxirane or oxirane mixture and expoxy propane also can use.
The list of references that discloses the polysiloxane fluid that is suitable for comprises US-A-2826551 (Green); US-A-3964500 (Drakoff, on June 22nd, 1976 authorized); US-A-4364837 (Pader) and GB-A-849433 (Woolston).The extensive tabulation (but not being exclusive) of the polysiloxane fluid that is suitable for is provided in " polysiloxane compound " (1984) by Petrarch Systems Inc. distribution in addition.
The preferred non-volatile polysiloxanes that is applicable to this comprises: the polydiorganosiloxanepolyurea-polyoxyalkylene copolymers that contains at least one polydiorganosiloxanepolyurea segment and at least one polyoxyalkylene segment.Wherein the segmental general formula of polydiorganosiloxanepolyurea is as follows:
R bSiO (4-b)/2
The value of b is about 0-3 (comprising end value) in the siloxane unit, each silicon atom on average contains two R groups approximately all siloxane units in copolymer, and R represents to be selected from methyl, ethyl, vinyl, phenyl and makes described polyoxyalkylene segment and the group of the divalent group of polydiorganosiloxanepolyurea segment bonding.The mean molecule quantity of polyoxyalkylene segment is at least about 500, preferably be at least about 1000, wherein contain 0-50% (mol) poly(propylene oxide) unit approximately, peace treaty contains 50-100% (mol) polyoxyethylene unit, be grafted with on the polyoxyalkylene segment or directly or indirectly with polydiorganosiloxanepolyurea segment bonding, any all is not the end groups that are suitable for the end group of described polydiorganosiloxanepolyurea segment bonding; The weight ratio of polydiorganosiloxanepolyurea segment and polyoxyalkylene segment preferably is about 2-8 in the described copolymer.This polymer sees US-A-4268499.
The general formula that preferably is applicable to polydiorganosiloxanepolyurea-polyoxyalkylene copolymers of the present invention is as follows:
Figure A9880739000091
R wherein 1Be selected from C 1-C 5Alkyl, preferable methyl, z is 1-4, and select suitable x and y so that the weight ratio of polydiorganosiloxanepolyurea segment and polyoxyalkylene segment is about 2-8, a: mol ratio (a+b) is about 0.5-1, and R is the chain termination group, specifically is selected from hydrogen; Hydroxyl; Alkyl such as methyl, ethyl, propyl group, butyl, benzyl; Aryl such as phenyl; Alkoxyl such as methoxyl group, ethyoxyl, propoxyl group, butoxy; Benzyloxy; Aryloxy group such as phenoxy group; Alkenyloxy such as ethyleneoxy and pi-allyl oxygen base; Acyloxy such as acetoxyl group, acryloxy and third alkynyloxy group, and amino as dimethylamino.
Be applicable to that more preferably polydiorganosiloxanepolyurea-polyoxyalkylene copolymers of the present invention is shown below:
Figure A9880739000101
X wherein, y and R definition are as above.
Segmental number and mean molecule quantity should be able to make that the weight ratio of polydiorganosiloxanepolyurea segment and polyoxyalkylene segment preferably is about 2.5-4.0 in the copolymer in the copolymer.
The copolymer that is suitable for can be available from Wacker-ChemieGmbH (Geschaftsbereich S, Postfach D-8000 Munich 22) product of commodity Belsil (RTM) by name, and available from Th.Goldschmidt Ltd,. (TegoHouse, Victoria Road, Ruislip, Middlesex, HA4 OYL) Abil (RTM).That specifically preferably be applicable to this is Belsil (RTM) 6031, Abil (RTM) B88183, DC3225C, DC5200, Abil We09, Abil EM90, BY22-008 (Dow Corning) and SF1328 (GE Silicone).The CTFA name of the known polysiloxanes that preferably is applicable to this is a dimethicone copolyol.
Compositions of the present invention preferably contains the oil phase that accounts for composition weight 20-95% (weight) approximately.Preferably contain the non-volatile polysiloxanes that accounts for oil phase 0.01-25% (weight) in the oil phase approximately, be more preferably 0.05-10% (weight).Preferably contain the Y 7175 that accounts for oil phase 75-99.99% (weight) in the oil phase approximately, be more preferably 90-99.95% (weight).
Oil phase in the water-in-oil emulsion of the present invention also can contain one or more non-silicone class organic oils, as natural or artificial oil, be selected from mineral oil, vegetable oil and animal oil, fat and wax class, fatty acid ester, aliphatic alcohol, fatty acid and their mixture, these compositions are suitable for reaching beauty treatment skin moistening characteristic.Be understood that and contain for example the highest the highest about 25%, preferred 10% the oil phase solubility emulsifier component that only is about in the oil phase.These compositions not can be regarded as oil phase component when calculating oil phase content.
The organic oil that is applicable to this for example comprises: the optional C that replaces through hydroxyl 8-C 50Unsaturated fatty acid and ester thereof, C 8-C 30The C of satisfied fatty acid 1-C 24Ester, as isopropyl myristate, isopropyl palmitate, cetin and myristic acid octyl group dodecyl ester (Wickenol142), Cera Flava, saturated and unsaturated fatty alcohol such as the pure and mild spermol of docosane, hydrocarbon such as mineral oil, vaseline and squalane, fatty acid esters of sorbitan is (referring to US-A-3988255, Seiden, on October 26th, 1976 authorized), lanoline and lanolin derivative, animal and plant triglyceride such as almond oil, Oleum Arachidis hypogaeae semen, wheat germ oil, Semen Lini oil, simmondsia oil, Apricot kernel oil, Oleum Juglandis, Petiolus Trachycarpi oil, the pistachio fruit oil, Oleum sesami, Oleum Brassicae campestris, cade oil, Semen Maydis oil, peach kernel oil, seed of Papaver somniferum L. powder, Oleum Pini, Oleum Ricini, soybean oil, American Avocado Tree oil, safflower oil, Oleum Cocois, hazelnut oil, olive oil, Oleum Vitis viniferae, galam butter, sal tree oil and Oleum Helianthi, and the C of dimeric dibasic acid and trimer acid 1-C 24Ester is as dimeric dibasic acid diisopropyl ester, malic acid two iso stearyl esters, dimeric dibasic acid two iso stearyl esters, trimer acid three iso stearyl esters.In the mentioned component, preferred especially mineral oil, vaseline, unsaturated fatty acid and ester thereof, and their mixture.The acidic skin care active component
Contain the additional acidic skin care active component except that salicylic acid or salicyclic acid derivatives in the present composition.
The acidic skin care active component that is suitable for can be selected from hydroxy carboxylic acid.The term acidic skin care active component that is applicable to this is meant any skin care activity composition that contains acid function base (for example carboxylate radical, sulfonate radical).
Hydroxyl monocarboxylic acid shown in the optional following freely chemical structural formula of hydroxy carboxylic acid that is suitable for:
R 1(CR 2OH) m(CH 2) nCOOH
R wherein 1, R 2=H, contain saturated or unsaturated straight or branched or cyclic alkyl, aralkyl or the aryl of 1-25 carbon atom; M=1,2,3,4,5,6,7,8 or 9; N=0 or be up to 23 number.
The hydroxyl monocarboxylic acid can be free acid, lactone or becomes salt form.Lactone form can be intermolecular or the intramolecularly lactone, but the most common be the intramolecularly lactone of sloughing the circulus that one or more hydrones form by hydroxyl and carboxyl.Because the hydroxyl monocarboxylic acid has the organic acid characteristic, they can or form coordination compound with inorganic or organic base (as ammonium hydroxide, sodium hydroxide or potassium hydroxide, or triethanolamine) salify.
Hydroxyl monocarboxylic acid and related compound thereof can exist by stereoisomer form (as D, L and DL form).
Typical R 1And R 2Alkyl, aralkyl and aryl comprise methyl, ethyl, phenyl, isopropyl, benzyl and phenyl.R 1And R 2And (CH 2) nHydrogen atom can replace by non-functional element (as fluorine, chlorine, bromine, iodine, sulfur) or by the group saturated or unsaturated low alkyl group or the alkoxyl of 1-9 carbon atom (as contain).Typical hydroxyl monocarboxylic acid has 2-hydroxyacetic acid (glycolic), 2 hydroxy propanoic acid (lactic acid), 2-methyl 2 hydroxy propanoic acid (methyllactic acid), the 2-hydroxybutyric acid, phenyl 2-hydroxyacetic acid (mandelic acid), phenyl 2-methyl 2-hydroxyacetic acid, 3-phenyl 2 hydroxy propanoic acid (phenyl-lactic acid), 2,3-dihydroxypropionic acid (glyceric acid), 2,3, the 4-trihydroxy-butyric acid, 2,3,4,5-tetrahydroxy valeric acid, 2,3,4,5, the 6-hexonic acid, 2-hydroxy-dodecanoic acid (Alpha-hydroxy lauric acid), 2,3,4,5,6,7-hexahydroxy enanthic acid, diphenyl 2-hydroxyacetic acid (diphenylglycollic acid), 4-hydroxyl mandelic acid, 4-chlorine mandelic acid, the 3-hydroxybutyric acid, 4 hydroxybutyric acid, the 2-hydroxycaproic acid, the 5-hydroxy-dodecanoic acid, sabinic acid, the 10-hydroxydecanoic acid, juniperic acid, 2-hydroxy-3-methyl butanoic acid, 2-hydroxy-4-methyl valeric acid, 3-hydroxyl-4-methoxyl group mandelic acid, 4-hydroxyl-3-methoxyl group mandelic acid, 2-hydroxy-2-methyl butanoic acid, 3-(2-hydroxy phenyl) lactic acid, 3-(4-hydroxy phenyl) lactic acid, six hydrogen mandelic acids, 3-hydroxy-3-methyl valeric acid, the 4-hydroxydecanoic acid, 5-hydroxydecanoic acid and aleuritic acid.
The hydroxy acid that is applicable to another type of the present invention is the hydroxydicarboxylic acid who is shown below:
HOOC(CHOH) m(CH 2) nCOOH
M=1 wherein, 2,3,4,5,6,7,8 or 9; N is 0 or the highest 23 integer.
The hydroxydicarboxylic acid also can be free acid, lactone or becomes salt form.Hydroxydicarboxylic acid and related compound thereof can exist by stereoisomer form (as D, L and DL form).
The hydrogen that links to each other with carbon atom can replace by non-functional element (as fluorine, chlorine, bromine, iodine, sulfur) or by the group saturated or unsaturated low alkyl group or the alkoxyl of 1-9 carbon atom (as contain).
Typical hydroxydicarboxylic acid has 2-hydroxymalonic acid. (hydroxymalonic acid), 2-hydroxyl succinic acid (malic acid), erythrose diacid and threose diacid (tartaric acid), arabinose diacid, ribose diacid, xylose diacid and lyxose diacid, glucosaccharic acid (saccharic acid), galactosaccharic acid (glactaric acid), mannan diacid, gulose diacid, allomucic acid, altrose diacid, idosaccharic acid and talose diacid.
Be applicable to that the 3rd class hydroxy acid of the present invention is to be difficult to the miscellaneous chemical compound of kind represented with the general formula of the first kind described above or second class.Comprise following chemical compound in the 3rd class hydroxy acid:
Hydroxy carboxylic acid shown in the following formula:
R(OH) m(COOH) n
M wherein, n=1,2,3,4,5,6,7,8 or 9, R=H, saturated or unsaturated, the straight or branched that contains 1-25 carbon atom or cyclic alkyl, aralkyl or aryl; Citric acid, 1-Hydroxy-1,2,3-propanetricarboxylic acid., citramalic acid, agaric acid (n-hexadecyl citric acid), quinic acid, alduronic acid comprise glucuronic acid, glucuronolactone, galacturonic acid, galacturonic acid acid lactone, oxypyroracemic acid, phosphohydroxypyruvic acid, ascorbic acid, dihydroascorbate, dihydroxytartaric acid, 2-hydroxyl-2 methylbutanoic acid, 1-hydroxyl-1-cyclopropane-carboxylic acid, 2-hydroxyl hexandial, 5-oxylysine, 3-hydroxyl-2-aminovaleric acid, tropic acid, 4-hydroxyl-2,2-diphenyl butyric acid, 3-hydroxy-3-methylglutaric acid and 4-hydroxyl-3-valeric acid.
The 3rd class hydroxy acid also can be free acid, lactone or one-tenth salt form and also can exist by stereoisomer form (as D, L and DL form).
The hydrogen that links to each other with carbon atom can replace by non-functional element (as fluorine, chlorine, bromine, iodine, sulfur) or by the group saturated or unsaturated low alkyl group or the alkoxyl of 1-9 carbon atom (as contain).
The mixture of hydroxy acid also is applicable to compositions of the present invention.Being used for hydroxy acid of the present invention is intended to reduce wrinkle and improves skin sense and skin appearance.
Other is applicable to that hydroxy acid of the present invention comprises tretinoin and Azelaic Acid.
The content of acidic skin care active component accounts for the 0.1-10% (weight) of composition weight, is preferably 0.1-5% (weight), is more preferably 0.5-3% (weight).
In acidic skin care active component water soluble or the water-alcohol solution, water-alcohol solution for example is to contain C 2-C 6The solution of alcohol, two pure and mild polyhydric alcohol, preferred alcohols is selected from ethanol, dipropylene glycol, butanediol, hexanediol and their mixture.
Compositions of the present invention also contains the solubilizing agent outside the division ring dextrinize compound, is used for the acid skin care activity composition of solubilising and/or salicylic acid or salicyclic acid derivatives.Any solubilizing agent that is usually used in cosmetic composition all is suitable for.The solubilizing agent that preferably is applicable to this is selected from C 4-C 22The polyoxyethylene polyoxypropylene ether of alcohol, the solubilizing agent of pyrrolidone containing, HLB value approximately greater than 15, preferably approximately greater than 18 the non-ionic surface active agent that contains Polyethylene Glycol, and their mixture.
The solubilizing agent that is applicable to pyrrolidone containing of the present invention comprises that molecular weight (viscosity is average) is about 1500-1,500,000, preferably be about 3000-700,000, be more preferably 5000-100,000 polyvinylpyrrolidone or C 1-C 4The alkyl polyvinylpyrrolidone.The example of the solubilizing agent of the pyrrolidone containing that is suitable for has polyvinylpyrrolidone (PVP) and butylation polyvinylpyrrolidone.The solubilizing agent of the most preferred pyrrolidone containing of the present invention is a polyvinylpyrrolidone.PVP can be the product available from the commodity Luviskol (RTM) by name of BASF.The preferred PVP solubilizing agent of the present invention is Luviskol K17, and its viscosity-average molecular weight is about 9,000.Other solubilizing agent that is applicable to pyrrolidone containing of the present invention comprises C 1-C 18Alkyl or hydroxyalkyl ketopyrrolidine such as lauryl ketopyrrolidine.
The content of the solubilizing agent of pyrrolidone containing preferably accounts for the 0.1-10% (weight) of compositions, is more preferably 0.1-5% (weight), particularly about 0.5-2% (weight).
Also contain the additional acid of the 0.01-5% that has an appointment (weight) or its salt in the preferred specific embodiments of the present invention, the pH value after it is water-soluble is less than or equal to the pKa value of respective acids, for example is selected from acid and the salt and their mixture of citric acid, boric acid.These materials are useful in the present invention, and it can combine with the complexant of pyrrolidone containing with acid skin care activity composition/salicylic acid of solubilising or salicyclic acid derivatives.Be applicable to that especially preferably the material that plays this effect of the present invention is a sodium citrate.In preferred specific embodiments, this acid or the dissolubility of its salt under 25 ℃ are at least 5% (weight).
Particularly preferred solubilizing agent is a non-ionic surface active agent in the present composition, is selected from C 4-C 22The polyoxyethylene polyoxypropylene ether of alcohol, and their mixture.This non-ionic surface active agent is useful in the present invention, and it can be used as the solubilizing agent of acidic skin care active component at discontinuous aqueous phase.Be applicable to C of the present invention 4-C 22The polyoxyethylene polyoxypropylene ether of alcohol is shown in following general formula:
Wherein x is about 1-35, preferably is about 1-10, and y is about 1-45, preferably is about 1-30, and R is straight or branched C 4-C 22Alkyl, or their mixture.In preferred specific embodiments, (x+y) more than or equal to 5, be preferably greater than or equal 10, more preferably greater than or equal 15.The ratio of x: y is 1: 1-1: 10.
R examples of groups suitable in the following formula comprises cetyl, butyl, stearyl, spermaceti-stearyl, decyl, lauryl and myristyl.
The example of the polyoxyethylene-polyoxypropylene alcohol ether that is suitable for comprises (adopting the CTFA name): PPG-4-ceteth-20, PPG-4-ceteth-5, PPG-4-ceteth-10 PPG-5-ceteth-20, PPG-8-ceteth-1, PPG-8-ceteth-2, PPG-8-ceteth-5, PPG-8-ceteth-10, PPG-8-ceteth-20, PPG-2-Buteth-3, PPG-2-Buteth-5, PPG-5-Buteth-7, PPG-9-Buteth-12, PPG-28-Buteth-35, PPG-12-Buteth-16, PPG-15-Buteth-20, PPG-20-Buteth-30, PPG-24-Buteth-27, PPG-26-Buteth-26, PPG-33-Buteth-45, PPG-2-Ceteareth-9, PPG-4-Ceteareth-12, PPG-10-Ceteareth-20, PPG-2-Deceth-10, PPG-4-Deceth-4, PPG-6-Deceth-4, PPG-6-Deceth-9, PPG-8-Deceth-6, the different Isodeceth-4 of PPG-2-, PPG-2-Isodeceth-6, PPG-2-Isodeceth-9, PPG-2-Isodeceth-12, PPG-3-Isodeceth-1, PPG-4-lauryl ether-5, PPG-4-lauryl ether-2, PPG-4-lauryl ether-7, PPG-5-lauryl ether-5, PPG-25-lauryl ether-25, PPG-3-Myreth-11, PPG-3-Myreth-3 and PPG-4-Steareth-3.
Be applicable to that preferably polyoxyethylene polyoxypropylene ether of the present invention is the C that contains suc as formula shown in (I) 8-C 16Alcohol ether, wherein x is 2-12, y is that the ratio of 10-30, wherein x: y is about 1: 2-1: 8.
Especially preferably be applicable to this C 4-C 22The polyoxyethylene polyoxypropylene ether of alcohol is shown in following formula (I), and wherein R is a cetyl, and wherein x is about 4-8, and wherein y is about 15-25, x: the ratio of y is about 1: 3-1: 5.The ether that is particularly preferred for the acid skin care activity composition of solubilising is PPG-5-ceteth-20, and it can be purchased by trade name Procetyl AWS.
Solubilizing agent of the present invention preferably accounts for the 0.1-15% (weight) of compositions, is more preferably 1-10% (weight), especially preferably is about 2-8% (weight).
Contain pigment or pigment composition in the preferred embodiments of the invention.The pigment that is applicable to this must be compatible with the acidic skin care active component/salicylic acid/salicyclic acid derivatives that is present in the compositions, and have fabulous overall color stability.The pigment that is applicable to this can be inorganic and/or organic.Term pigment also comprises color or lower material such as the inferior light finishing agent of gloss, also comprises light scattering agent.The example of suitable pigments has ferrum oxide, rutile titanium dioxide, anatase titanium dioxide, iron sesquioxide, ferrous oxide, chromium oxide, chromic oxide gel, manganese violet, acyl glutamic acid ferrum oxide, ultramarine, D﹠amp; C dyestuff, carmine and their mixture.The application of pigment composition generally will be decided on the type (for example foundation cream or kermes) of color make-up compositions.
Can contain a kind of inferior light finishing agent in the foundation compositions at least.The function of inferior light finishing agent is to be used for skin to hide the flaw and reduce skin shinny.This class is applicable to that inorganic dose of cosmetics (promptly list in CTFA cosmetic composition handbook the 3rd edition in) silica dioxide granule of handling as silicon dioxide, hydrated SiO 2, through polysiloxanes, Muscovitum, Pulvis Talci, polyethylene, titanium dioxide, bentonite, hectorite, Kaolin, Chalk, kieselguhr, activated zinc oxide etc. all are suitable for.The concrete inferior light finishing agent of using is the metatitanic acid Muscovitum (through the Muscovitum of coated by titanium dioxide) of low gloss pigment as coating through barium sulfate.Be suitable for and do in the inferior light finishing agent low gloss pigment inorganic component, special preferably talc powder, polyethylene, hydrated SiO 2, Kaolin, titanium dioxide and their mixture.The light scattering agent that is applicable to this is generally granularity and is about 100 microns at the most, preferably is about the inorganic spherical thing of 5-50 micron, for example preparing spherical SiO 2 granule.
Other example of pigment comprises the toner color lake, as FD﹠amp; No. 7 red calcium of C color lake, FD﹠amp; No. 5 yellow aluminum of C color lake, D﹠amp; C No. 9 red barium color lake and D﹠amp; No. 30, C is red.
For the consideration of moistness, skin sense, skin appearance and the Emulsion compatibility, the pigment that preferably is applicable to this is treated pigment.Pigment can be through chemical compound such as aminoacid such as lysine, polysiloxanes, lauroyl, collagen, polyethylene, lecithin and ester oil processing.Preferred pigment be the pigment handled through polysiloxanes,
The pigment that is specially adapted to this is the pigment that is coated with the organosiloxane component, organosiloxane is selected from polysiloxane or silane, and the hydrogen electromotive force that wherein coats pigment is less than about 2.0, it is about 1.0 preferably to be lower than, more preferably from about be lower than 0.5ml, particularly be lower than about 0.1ml H 2/ g coats pigment.The pigment that preferably is applicable to this is particle form.Pigment adds in the oil-continuous phase of the present composition.Used coating is bonded on the surface of pigments by covalent bond, physical absorption or adhesive attraction, preferably by covalent bonding on surface of pigments.The function of coating is that pigment is carried out hydrophobically modified among the present invention, makes it become " can drench " in the continuous silicone of polysiloxanes bag aqueous emulsion in mutually.For reducing the viewpoint that hydrogen discharges and improve product stability, the coating through coating also is applicable to this.
Do not limit although do not wish to accept opinion, be present in the oil phase of water-in-oil emulsion though it is generally acknowledged pigment, the hydrion of aqueous phase can pass the Emulsion interface and enter in the oil phase, and their meetings and pigment coated reaction for example discharge hydrogen there.Yet, adopt the hydrogen electromotive force to be lower than about 2mlH 2/ g coats the pigment through the organosiloxane coating of coating, can reduce the generation of hydrogen.
Adopt following determination of test method to coat the hydrogen electromotive force of pigment:
The coating pigment dispersion that will contain 20g coating pigment places the flask that adds magnetic stirring apparatus, at room temperature stirs the alcoholic solution of the potassium hydroxide that adds 100ml 2%.In second flask, collect the hydrogen that discharges under room temperature and the normal pressure (25 ℃, 1 atmospheric pressure).The active volume algoscopy is measured the hydrogen that discharges thus.
Various organosiloxane components all are applicable to handles pigment of the present invention.Be applicable to that polysiloxane of the present invention is selected from:
(A) material shown in the following formula:
(R 1) 3SiO-(Si(R 2R 3)O) p-Si(R 2R 3)OA 2
Wherein p is 1-1000, is preferably 1-100, A 2Be hydrogen or the alkyl that contains 1-30 carbon atom, R 1Be C 1-C 30Alkyl, methyl preferably, R 2And R 3Be independently from each other C 1-C 30Alkyl and phenyl, preferably R wherein 2And R 3Be methyl, or R wherein 2Be methyl, R 3It is phenyl; Perhaps
(B) material shown in the following formula
(R 1) 3SiO(Si(R 2)(H)-O) i-Si(R 1) 3
Wherein i is 1-1000, is preferably 1-100, wherein R 1And R 2As above face the definition of formula (A).
In preferred embodiments, the organosiloxane component is selected from silane.Silane is selected from the material that is shown below:
(C)A 1SiX 1X 2X 3
Wherein A is alkyl or the alkenyl that contains 1-30 carbon atom, and X 1, X 2And X 3Be independently from each other C 1-C 4Alkoxyl, preferred methoxy or ethoxy, or halogen, preferred chlorine.
Pigment of the present invention can make as shown in the formula the pigment shown in (I) after the silane treatment shown in following formula (C):
P-O-Si(OH)(A)-[-O-Si(OH)(A)-] 0-100-OH
Wherein P is the atom of surface of pigments, and each A is respectively alkyl or the alkenyl that contains 30 carbon atoms at most.Except that the polysiloxane chain that stretches out surface of pigments, the many adjacent polysiloxane chain shown in the formula (I) can by oxygen atom be cross-linked to form along surface of pigments stretch contain at most 100-Si (OP)-polysiloxane chain of O repetitive.The example of straight or branched alkyl has methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, and the rest may be inferred to octadecyl." alkenyl " comprises the carbochain that contains one or more pairs of keys; This examples of groups comprises ethylidene, propylidene, acryloyl group, methacryl and unsaturated fatty acid residue, as oil base (C 17C 33-), inferior oil base (C 17C 31-) and Caulis et Folium Lini base (C 17C 29-).
Pigment of the present invention can make as shown in the formula the pigment shown in (2) after the polysiloxane shown in the following formula (A) is handled:
P-O-(Si(R 2R 3)O) p-Si(R 1) 3????(2)
Wherein p is 1-1000, is preferably 1-100, R 1, R 2And R 3As definition in the following formula (A), and P is the atom of surface of pigments.
When pigment of the present invention after the polysiloxane shown in the following formula (B) is handled, can make as shown in the formula the pigment shown in (3):
(R 1) 3SiO-[Si(R 2)(-OP)-O-] p-Si(R 1) 3??(3)
Wherein each P is the atom of surface of pigments, and p is 1-1000, is preferably 1-100, R 1And R 2As definition in the following formula (B), wherein be up to (Si-O) repetitive of 100 by oxygen atom and surface of pigments bonding.
Pigment (or mixture of two or more pigment) can be added in the blender with exsiccant micronization form, add the polysiloxanes component again and mix and coat.The content of organosilicon coating preferably accounts for through the 0.01-5% of the pigment of silicone covering (weight), is more preferably 0.1-4% (weight), especially preferably is about 0.5-2% (weight).
For reducing the viewpoint that hydrogen discharges, improves product stability, most preferred coating pigment is Cardre 70429.
The total concentration that coats pigment can account for the 0.1-25% (weight) of total composition, preferably be about 1-15% (weight), be more preferably 8-12% (weight), its exact concentration is somewhat dependent upon and is used for the shade that foundation cream color cosmetic or the selected specific pigment composition of rouge will reach.The titanium dioxide that contains 2-20% (weight) in the preferred composition approximately is most preferably 5-10% (weight).
Particularly preferred component is wetting agent or wetting agent mixture in the present composition.The content of wetting agent of the present invention or wetting agent mixture accounts for the 0.1-30% (weight) of compositions, preferably is about 1-25% (weight), is more preferably 1-10% (weight).The wetting agent that is suitable for is selected from glycerol, and is 300 25 ℃ of following viscosity, 000-1, the polyglycereol methacrylic acid ester lubricant of 100,000 centipoises; Its proportion under 25 ℃ is 1-1.2g/ml, and pH is 5.0-5.5; Bound water content is 33-58%; Free water content is 5-20%.
Can add to the small part wetting agent in the oil phase of water-in-oil emulsion.Preferably contain the wetting agent that accounts for compositions 0.1-10% (weight) in the oil phase approximately, be more preferably 0.1-3% (weight).Wetting agent can add in the oil phase with the mixture of granule oleophylic or hydrophobic carrier or the form that is present in wherein.
Polyglycereol methacrylic acid ester lubricant with desirable characteristics is sold with trade name " Lubrajel " by Guardian chemical company." Lubrajel DV " in " Lubrajels ", " Lubrajel MS " and " Lubrajel CG " are preferred for the present invention.This class gellant of selling by these trade names contains 1% propylene glycol approximately.
Other wetting agent that is suitable for comprises sorbitol, pantothenylol, propylene glycol, dipropylene glycol, butanediol, hexanediol, alkoxylate glucose derivant such as Glucam (RTM) E-20, hexanetriol and glucose ether, and their mixture.
The pantothenylol moisturizing agent is selected from D-panthenol ([R]-2,4-dihydroxy-N-[3-hydroxypropyl]-3, the 3-amide dimethyl butyrate), DL-pantothenylol, calcium pantothenate, Lac regis apis, the general coordination compound of separating thetin (panthetine), general thetin (pantotheine), pantoyl ether, pangamic acid, pyridoxol, pantoyl lactose and vitamin B.
The preferred wetting agent of the present invention is a glycerol.From chemically, glycerol is 1,2, the 3-glycerol, and be commercial product.
Preferred ingredient in the present composition except that organic amphiphilic surfactant has the polyol ester skin conditioning agent.
The polyol ester that preferably contains 0.01-20% (weight) in the compositions of the present invention approximately is more preferably 0.1-15% (weight), especially preferably is about 1-10% (weight).Polyol ester accounts for that the content of oil phase is about 1-30% (weight) in the compositions, is more preferably 5-20% (weight).
The polyol ester that preferably is applicable to this is non-occlusion liquid or liquefiable polyol carboxylate.This class polyol ester is derived from polyhydric alcohol group or part and one or more hydroxy-acid groups or part.In other words, contain part and the one or more part that is derived from carboxylic acid that is derived from polyhydric alcohol in these esters.These carboxylates also can be derived from carboxylic acid.These carboxylates are also referred to as the liquid polyol fatty acid ester, because those skilled in the art often exchange use with term carboxylic acid and fatty acid.
Be applicable to that preferably liquid polyol polyester of the present invention comprises some polyhydric alcohol, particularly saccharide or sugar alcohol, it is by at least 4 fatty acid group esterifications.Therefore, but the polyhydric alcohol initiation material must contain the hydroxyl of 4 esterifications at least.The example of preferred polyhydric alcohols has saccharide, comprises monosaccharide and disaccharide, and sugar alcohol.The example that contains the monosaccharide of 4 hydroxyls has xylose and arabinose, and the sugar alcohol of the xylose of self-contained 5 hydroxyls of deriving, i.e. xylitol.The monosaccharide erythrose is not suitable for the present invention, and because of it only contains 3 hydroxyls, but derived from the sugar alcohol of erythrose, promptly erithritol contains 4 hydroxyls, therefore is suitable for.The monosaccharide that contains 5 hydroxyls that is suitable for has galactose, fructose and sorbose.Derived from sucrose and glucose and sorbose hydrolyzate contain 6 hydroxyls sugar alcohol (for example Sorbitol) also be suitable for.The disaccharide examples of polyhydric alcohols that is suitable for comprises maltose, lactose and sucrose, and they all contain 8 hydroxyls.
The polyhydric alcohol that is preferred for preparing the used polyester of the present invention is selected from: erithritol, xylitol, sorbitol, dextrose plus saccharose.Special preferably sucrose.
At least the polyhydric alcohol initiation material that contains 4 hydroxyls at least 4 hydroxyls with the fatty acid generation esterification that contains 8-22 carbon atom.That the example of this class fatty acid comprises is sad, capric acid, lauric acid, myristic acid, myristoleic acid, Palmic acid, palmitic olefinic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, arachidonic acid, behenic acid and erucic acid.Fatty acid can be derived from natural or synthetic fatty acid; It can be saturated or undersaturated, comprises position isomer and geometric isomer.But, mix that the fatty acid at least about 50% (weight) should be undersaturated in the polyester molecule for obtaining to be applicable to liquid polyester of the present invention.Oleic acid and linoleic acid and their mixture are especially suitable.
Be applicable to that polyol fatty acid polyesters of the present invention should contain 4 fatty acid ester groups at least.All hydroxyls that are not polyhydric alcohol all must be by fatty acid esterification, but not esterified hydroxyl is no more than 2 in the preferred polyester.Most preferably basic all hydroxyls are all by fatty acid esterification in the polyhydric alcohol, and promptly polyol moiety is esterified substantially fully.Be used for the fatty acid of polyhydric alcohol molecule esterification identical or blended, but as mentioned above, must guarantee the unsaturated fatty acid ester group fundamental quantity so that its can liquefy.
For above each point is described, sucrose-fatty three esters just are not suitable for the present invention, because it does not contain 4 required fatty acid ester group.Sucrose four fatty acid esters then are suitable for, but not preferred, because of it contains plural no esterification hydroxyl.Sucrose six fatty acid esters are preferred, because of its contained no esterification hydroxyl is no more than 2.Particularly preferred all hydroxyls are all comprised liquid sugar eight substituted fatty acid esters by fatty acid-esterified chemical compound.
The non-limiting example that below contains being applicable to of 4 fatty acid ester group special polyol fatty acid poleysters of the present invention at least comprises: glucose four oleates, soya fatty acid (unsaturated) glucose tetra-ester, mixing soya beans fatty acid oil mannose four esters, oleic acid galactose four esters, linoleic acid arabinose four esters, four linoleic acid xylose esters, five oleic acid gala sugar esters, four oleic acid sorbitol esters, unsaturated soya fatty acid sorbitol six esters, the five oleic acid esters of xylitol, four oleic acid sucrose ester, five oleic acid sucrose ester, six oleic acid sucrose ester, seven oleic acid sucrose ester, eight oleic acid sucrose ester and their mixture.
As mentioned above, the fatty acid in the particularly preferred polyol fatty acid ester contains 14-18 carbon atom approximately.
The complete fusing point that preferably is applicable to this liquid polyol fatty acid ester is less than about 30 ℃, preferably is less than about 27.5 ℃, more preferably from about is lower than 25 ℃.Complete fusing point described here is measured by differential scanning calorimetry (DSC).
The polyol fatty acid polyesters that is applicable to this can be made by the whole bag of tricks well known by persons skilled in the art.These methods comprise: the transesterification that polyhydric alcohol and fatty acid methyl ester, ethyl ester or glyceride carry out through various catalyst actions; The acylation of polyhydric alcohol and fat acyl chloride; The acylation of polyhydric alcohol and fatty acid anhydride; And the acylation of polyhydric alcohol and fatty acid itself.Referring to US 2831854; US 4005196 (Jandacek, on January 25th, 1977 authorized); US 4005196 (Jandacek, on January 25th, 1977 authorized).
Color make-up compositions of the present invention also can contain crosslinked hydrophobic acrylate of graininess or methacrylate copolymer.This copolymer is particularly conducive to and alleviates reflective and press down oil, helps simultaneously to provide and effectively moistens benefit.Crosslinked hydrophobic polymer is preferably the copolymer lattice form, and wherein at least a active component evenly fully disperses and is trapped in the copolymer lattice.Perhaps hydrophobic polymer can be the porous particle form, and its surface area (N2-BET) is about 50-500m 2/ g, preferred 100-300m 2/ g wherein is absorbed with active component.
The consumption of crosslinked hydrophobic polymer is about 0.1-10% (weight), preferably mixes in the outside oil phase that contains polysiloxanes.Active component can be one or more skin-friendliness oils, skin-friendliness wetting agent, emollient, moisturizing agent and sunscreen or its mixture.Polymer is a powder form, and this powder is a blend of granules whose system.The powder particle system can form lattice, and less than about 1 micron unit grain, granularity is about the unit grain agglomerate of the consolidation of 20-100 micron (average diameter) comprising average diameter.Granularity is about bunch collection agglomerate of the consolidation agglomerate of 200-1200 micron (average diameter).
Dusty material of the present invention can be used as the carrier of active component, and it can be called as crosslinked " post-absorption " hydrophobic polymer lattice widely.This powder preferably contains to be held back and is scattered in wherein active component, and active component can be solid, liquid or gas form.Lattice is a particle form, is free-pouring dispersion solid particle when load has active component.The active component that can contain scheduled volume in the lattice.The structural formula of polymer is as follows:
Figure A9880739000231
Wherein the ratio of x: y is 80: 20, and R ' is-CH 2CH 2-, and R " is-(CH 2) 11CH 3
The hydrophobic polymer that is applicable to this is highly cross-linked polymer, is more preferably highly cross-linked polymethacrylate copolymer, as (Miland.Michigan is USA) with trade name POLYTRAP (RTM) product sold by Dow Corning company.It is extra light free-pouring white powder, and its granule can absorb high-load lipophile liquid and some water seeking liquids, still can keep the powder free-flowing properties simultaneously.Mealy structure is made of the unit grain lattice less than 1 micron, and the granularity of consolidation agglomerate is the 20-100 micron, and the granularity of loose bunch of integrated bulky grain of consolidation agglomerate or agglomerate is about the 200-1200 micron.Can contain 4 times of fluids, emulsion, dispersion or molten solids in the polymer powder to its weight.
Can adopt rustless steel mixing kettle and mixing spoon that active component is adsorbed onto on the polymer powder, wherein active component be added in the powder, adopt mixing spoon gently active component to be mixed with polymer powder.Be the absorption low viscosity fluid, the fluid adding can be loaded with in the resealable container of polymer, rock then until reaching certain denseness.Also can adopt more accurate fusion equipment such as ribbon or bipyramid drum mixer.The active component that preferably is applicable to this is a glycerol.The weight ratio of preferred wetting agent and carrier is about 1: 4-3: 1.
The highly cross-linked polymethacrylate copolymer that is suitable for is Microsponges5640.It is generally crosslinked hydrophobic polymer spheroidal particle form, and the aperture is about the 0.01-0.05 micron, and surface area is 200-300m 2/ g.The wetting agent content of its load preferably as mentioned above.
Also contain hydrophilic gelling agent in the compositions of the present invention, its content preferably is about 0.01-10% (weight), is more preferably 0.02-2% (weight), particularly is about 0.02-0.5% (weight).The viscosity of gellant preferably is at least about 4000mPa.s (1% aqueous solution, 20 ℃ are adopted Brookfield RVT down), more preferably is at least about 10, and 000mPa.s particularly is at least 50,000mPa.s.
The hydrophilic gelling agent that is suitable for generally is described to water solublity or colloidal state water-soluble polymer, comprising cellulose ether (hydroxyethyl-cellulose for example, methylcellulose, hydroxypropyl emthylcellulose), polyvinyl alcohol, season hydroxyethyl-cellulose-10, guar gum, hydroxypropyl guar gum and xanthan gum.
The hydrophilic gelling agent that is suitable for has acrylic acid/alkyl acrylate copolymer, and by the CVP Carbopol ETD2050 of B.F.Goodrich company with the sale of trade name Carbopol resin.These resins mainly are made of colloidal state water-soluble poly alkenyl polyether cross linked polymer, and this cross linked polymer is cross-linked to form by acrylic acid and 0.75-2.00% (weight) cross-linking agent (for example polyene propyl group sucrose or polyene propyl group tetramethylolmethane).The example comprises Carbopol934, Carbopol 940, Carbopol 950, Carbopol 980, Carbopol 951 and Carbopol 981.Carbopol 934 is acrylic acid and the crosslinked water-soluble polymer of about 1% sucrose polyallyl ether, and wherein each sucrose molecule in the sucrose polypropylene-base ether on average contains 5.8 pi-allyls approximately.Can trade name Carbopol 1382, (the CTFA name: acrylate/10-30 alkyl acrylate cross-linked copolymer) the hydrophobically modified acrylic crosslinking polymer with amphiphilic nature that is purchased also is applicable to the present invention for Carbopol 1342 and Pemulen TR-1.The mixture of the crosslinked acrylic acid polymer of polyalkenyl polyethers crosslinked acrylic acid polymer and hydrophobically modified also is applicable to the present invention.Other is applicable to that gellant of the present invention has oleogel such as trihydroxy tristerin and hydroxy stearic acid magnalium.Gellant of the present invention is particularly conducive under the room temperature and the condition of heating fabulous stability is provided.
Preferred this gellant that contains acidic-group is through neutral.The nertralizer of the hydrophilic gelling agent that being applicable to neutralizes in the present invention contains acidic-group comprises: sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine and triethanolamine.
Also can contain emollient in the color make-up compositions of the present invention.The emollient that is applicable to the present composition comprises natural and synthetic oils, is selected from mineral oil, vegetable oil and animal oil, fat and wax, fatty acid ester, aliphatic alcohol, aklylene glycol and polyalkylene glycol ethers and ester, fatty acid, and their mixture.
The emollient that is applicable to this for example comprises: the optional C that replaces through hydroxyl 8-C 50Unsaturated fatty acid and ester thereof, C 8-C 30The C of satisfied fatty acid 1-C 24Ester; as isopropyl myristate; isopropyl palmitate; cetin and myristic acid octyl group dodecyl ester (Wickenol142); Cera Flava; saturated and unsaturated fatty alcohol such as the pure and mild spermol of docosane; hydrocarbon such as mineral oil; vaseline and squalane; fatty acid esters of sorbitan is (referring to US-A-3988255; Seiden; on October 26th, 1976 authorized); lanoline and lanolin derivative such as ethoxylation lanonol; hydroxyl sulfonation acetylated lanolin; cholesterol and derivant thereof; animal and plant triglyceride such as almond oil; Oleum Arachidis hypogaeae semen; wheat germ oil; Semen Lini oil; simmondsia oil; Apricot kernel oil; Oleum Juglandis; Petiolus Trachycarpi oil; the pistachio fruit oil; Oleum sesami; Oleum Brassicae campestris; cade oil; Semen Maydis oil; peach kernel oil; seed of Papaver somniferum L. powder; Oleum Pini; Oleum Ricini; soybean oil; American Avocado Tree oil; safflower oil; Oleum Cocois; hazelnut oil; olive oil; Oleum Vitis viniferae and Oleum Helianthi, and the C of dimeric dibasic acid and trimer acid 1-C 24Ester is as dimeric dibasic acid diisopropyl ester, malic acid two iso stearyl esters, dimeric dibasic acid two iso stearyl esters, trimer acid three iso stearyl esters.
Preferred emollient is selected from hydro carbons, as 2-Methylpentadecane, mineral oil, vaseline and squalane, lanolin alcohol and stearyl alcohol.These emollient can use separately or use with form of mixtures, and its consumption accounts for the 1-30% (weight) of composition total weight, preferably is about 5-15% (weight).
Also can contain supplementary element in the said composition, for example the spice of Shi Yonging, sunscreen, antiseptic, electrolyte such as sodium chloride, protein, antioxidant, chelating agen and water-in-oil emulsifier.
The another kind of optional components of color make-up compositions is one or more UV absorbent.UV absorbent often is called as sunscreen, and its concentration accounts for the 1-12% (weight) of composition total weight.The consumption of preferred UV absorbent is 2-8% (weight).More preferably its concentration in compositions is about 4-6% (weight).Be applicable to preferred especially benzophenone-3, octyldimethyl PABA (Padimate O), Parsol MCX and their mixture in this UV absorbent.
The another kind of optional but preferred ingredients additional chelating agen that is one or more among the present invention, preferably its consumption accounts for the 0.02-0.10% (weight) of composition total weight.The concentration of preferred sequestrant accounts for the 0.03-0.07% (weight) of composition total weight.Be applicable to that the chelating agen in the compositions has EDTA four sodium.
Another kind in the foundation compositions of the present invention optional but preferred ingredients is one or more antiseptic.Preferred its consumption accounts for the 0.05-0.8% (weight) of composition total weight, is preferably 0.1-0.3% (weight).The antiseptic that is applicable to this comprises sodium benzoate and propyl p-hydroxybenzoate and their mixture.
Another kind of optional but preferred ingredients is by Dow Corning company limited (AvcoHouse, Castle Street, Reading RG1 7DZ, UK) DryFlow of Xiao Shouing.
Cosmetic composition of the present invention can be foundation cream, rouge, the agent of the screening flaw, compacting powder, emollient cream and forms such as moistening liquid, painted emollient cream and moistening liquid, is preferably foundation cream and hides flaw agent.
Shown in the following table is the embodiment of cosmetic composition of the present invention.
1 2 3 4 5 6 7 8
The A phase % (weight) % (weight) % (weight) % (weight) % (weight) % (weight) % (weight) % (weight)
Cyclohexyl methyl siloxanes (DC2-1330) 0.0 0.0 7.59 16.75 5.25 11.99 0.0 0.0
Cyclohexyl methyl siloxanes DC245 9.85 8.65 0.0 0.0 0.0 0.0 10.04 10.04
Cyclohexyl methyl siloxanes/dimethyl siloxane 0.0 0.0 17.20 10.00 18.50 10.00 0.0 0.0
Polyol (90: 10) (DC3225C)
Cyclohexyl methyl siloxanes/dimethyl siloxane 10.00 15.00 0.0 0.0 0.0 0.0 15.00 15.00
Polyol (90: 10) (BY 22-008)
SEFA Semen Gossypii acid esters 1 0.00 0.00 2.00 0.00 2.00 4.00 0.00 0.00
The B phase
Microsponge?5640 2 0.5 0.75 0.75 0.00 0.50 0.75 0.75 0.75
Muscovitum 0.00 0.00 0.00 0.10 0.10 0.10 0.00 0.00
Titanium dioxide (Cardre 70429) 3 8.25 8.25 8.25 8.25 8.25 8.25 8.25 8.25
Zinc oxide and dimethyl siloxane 0.00 0.00 4.00 4.00 0.00 4.00 0.00 0.00
The C phase
Dryflow 4 2.5 2.50 0.00 0.00 0.00 0.00 2.5 2.5
The D phase
Yellow ferric oxide 2.10 2.10 2.00 2.10 2.10 2.10 1.60 1.60
Red ferric oxide 0.90 0.90 0.24 0.90 0.60 0.90 0.47 0.47
Black Rouge 0.60 0.60 0.12 0.60 0.30 0.60 0.09 0.09
Cyclohexyl methyl siloxanes (DC 2-1330) 0.0 0.0 1.00 1.00 1.00 1.00 0.0 0.0
Cyclohexyl methyl siloxanes DC245 1.00 1.00 0.0 0.0 0.0 0.0 1.00 1.00
The E phase
Durachem 5 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Waxenol 6 0.00 0.00 0.30 0.00 0.00 0.00 0.00 0.00
The F phase
Cyclohexyl methyl siloxanes (DC2-1330) 0.0 0.0 1.00 1.00 1.00 1.00 0.0 0.0
Cyclohexyl methyl siloxanes DC245 1.00 1.00 0.0 0.0 0.0 0.0 1.00 1.00
Thixin?R 7 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30
Propyl p-hydroxybenzoate 0.00 0.00 0.25 0.00 0.00 0.00 0.00 0.00
The G phase
The tridecandioic acid ethyl 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00
The H phase
Salicylic acid 1.00 0.5 1.75 1.95 1.50 1.50 1.00 1.50
Hydroxypropyl 10 8.00 4.00 8.00 8.00 12.00 8.00 4.00 8.00
Procetyl?AWS 11 0.00 0.00 0.00 0.00 0.00 0.00 3.00 3.00
Glycerol 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00
Water 2.00 2.00 2.00 2.00 2.00 2.00 0.00 0.00
The I phase
Water To 100
EDTA four sodium 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
Sodium citrate 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30
Sodium chloride 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30
Citric acid 0.5 1.00 0.00 0.00 0.50 0.00 0.50 0.50
Polyvinylpyrrolidone (Luviskol K17) 8 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Methyl parahydroxybenzoate 0.00 0.00 0.20 0.00 0.00 0.00 0.00 0.00
The J phase
Zinc oxide 0.00 0.00 0.42 0.42 0.00 0.28 0.00 0.00
Arginine 12 0.00 0.00 0.325 0.65 0.65 0.65 0.00 0.00
Total amount 100 100 100 100 100 100 100 100
1. by Procter﹠amp; Gamble sells
2. (Reading RG1 7DZ UK) sells for Avco House, Castle Street by Dow Corning company limited.
3. (NJ07090 USA) sells for 70 Tyler Pl., South Plainfield by Cardre Incorporated.
4. (Reading RG1 7DZ UK) sells for Avco House, Castle Street by Dow Corning company limited.
5. (Middlesex UB7 7RA UK) sells for Tavistock Road, Wets Drayton by the Astor-Stag company limited.
6. (NJ07002 USA) sells for 40 Avenue A, Bayonne by Caschem Inc..
7. trihydroxy tristerin, by the Rheox company limited (Barons Court, Manchester Road, Wilmslow, SK9 1BQ UK) sells.
8. by BASF (Earl Road, Cheadle Hulme, Cheadle, Cheshire, SK86QB) sale.
9. (39 Old Ridgebury Road Danbury) sell by Union Carbide.
10. (Indiana USA46320) sells for 1100 Indianapolis Boulevard, Hammond by Cerestar u s company.
11. sell by Croda chemistry company limited (Cowick Hall, Snaith, Goole, NorthHumberside, DN14 9AA).
12. sell by Degussa company limited (Winterton House, Winterton Way, Macclesfield, Cheshire SK11 OLP).
The preparation of example I-VI can prepare as follows.Listed various components are classified in the table, according to following step each are formed to divide to mix, and add each group membership of residue then.
The first step, through shear-mixed with the mixture stir about of A phase component 15 minutes to homogenizing.Mix through high speed shear, gradually B phase material is added A mutually in, with about 30 minutes of batch mixes.Add the C phase, the gained mixture was ground about 15 minutes.
Add the D phase component then, grind the gained mixture to fully disperseing.
After this in batching, add wax phase E, stir down batching is heated to 85 ℃ until the wax fusion, be cooled to 50 ℃ under stirring.In batching, add F phase pre-composition, homogenize 10 minutes then.Stir down batching is cooled to room temperature.G is added in the batching about 10 minutes of homogenize.
Prepare water by the following method.Mix the I phase component until dissolving.Mix the H phase component until dissolving through high speed shear.Mixed solution is to clarification.With I be added to H mutually in and mix, under agitation add the J phase then.
Under the stirring at low speed processing condition, water is slowly added in the oil phase at last.Add all waters, high speed shear is prepared burden about 5 minutes to increase the viscosity of final products.
Gained color make-up compositions is made to be packaged.
The cosmetic composition of embodiment has the anti-acne/anti-inflammatory activity of improvement, and skin irritation is low.

Claims (11)

1. the local skin compositions that applies some make up wherein contains at least one water, also contains cyclodextrin compound and salicylic acid or salicyclic acid derivatives, and wherein the pH of compositions is below 5 or 5.
2. the cosmetic composition of claim 1, wherein the pH of compositions is below 4 or 4.
3. claim 1 or 2 cosmetic composition, cyclodextrin compound wherein is selected from: alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, hydroxyl C 1-4Alkyl-beta-schardinger dextrin-and their mixture.
4. the cosmetic composition in arbitrary claim among the claim 1-3, wherein cyclodextrin compound is a HP-.
5. the cosmetic composition in arbitrary claim among the claim 1-4 wherein contains salicylic acid in the compositions.
6. the cosmetic composition in arbitrary claim among the claim 1-5 wherein contains salicylic acid or the salicyclic acid derivatives of 0.1-10% (weight) approximately, preferably is about 0.1-5% (weight).
7. the cosmetic composition in arbitrary claim among the claim 1-6 wherein contains the cyclodextrin compound of 0.1-20% (weight) approximately, preferably is about 0.8-15% (weight).
8. the cosmetic composition in arbitrary claim among the claim 1-7 wherein contains the pigment of 0.1-30% (weight) approximately, preferably is about 0.1-25% (weight), is more preferably 1-15% (weight).
9. the cosmetic composition in arbitrary claim among the claim 1-8, wherein compositions is Emulsion form, preferably water-in-oil emulsion.
10. the cosmetic composition of claim 9, wherein salicylic acid or salicyclic acid derivatives are dissolved in the aqueous phase of Emulsion.
11. the cosmetic composition of claim 9 or 10 wherein contains the non-volatile polysiloxanes that accounts for oil phase 0.01-25% (weight) approximately in the oil phase, and the Y 7175 that accounts for oil phase 75-99.99% (weight).
CN 98807390 1997-06-12 1998-06-12 Cosmetic compositions Pending CN1264291A (en)

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Cited By (2)

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CN100342841C (en) * 2004-04-28 2007-10-17 莱雅公司 Cosmetic compositions comprising at least one salt, at least one cyclodextrin, and at least one surfactant, and uses thereof
CN113712836A (en) * 2020-12-30 2021-11-30 深圳市巴斯星科技有限公司 Anti-inflammatory acne-removing skin care composition and preparation method and using method thereof

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002201355A (en) * 2000-10-26 2002-07-19 Shiseido Co Ltd Water-in-oil type emulsion composition and emulsion cosmetic using the same
ITMI20010162A1 (en) * 2001-01-30 2002-07-30 Intercos Italiana LIGHT AND HANDLABLE SOLID COSMETIC PRODUCT
US7122174B2 (en) 2002-09-30 2006-10-17 L'oreal S.A. Compositions comprising at least one silicone compound and at least one amine compound, and methods for using the same
WO2018237218A1 (en) 2017-06-23 2018-12-27 The Procter & Gamble Company Composition and method for improving the appearance of skin
CA3102288A1 (en) 2018-07-03 2020-01-09 The Procter & Gamble Company Method of treating a skin condition
CN115843238A (en) 2020-06-01 2023-03-24 宝洁公司 Method for improving penetration of vitamin b3 compounds into the skin
US10959933B1 (en) 2020-06-01 2021-03-30 The Procter & Gamble Company Low pH skin care composition and methods of using the same
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Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59181212A (en) * 1983-03-30 1984-10-15 Nitto Electric Ind Co Ltd Acrylic plaster
EP0211392B1 (en) * 1985-08-06 1991-03-27 Kao Corporation Liquid shampoo composition
JPS63101317A (en) * 1986-10-15 1988-05-06 Kao Corp Base for external drug and external dermatic agent using same
JPS63188609A (en) * 1987-01-30 1988-08-04 Sansho Seiyaku Kk External preparation preventing coloring
AU616571B2 (en) * 1988-10-28 1991-10-31 Shiseido Company Ltd. Cosmetic composition containing inclusion product with hydroxyalkylated cyclodextrin
SE466134B (en) * 1990-11-22 1992-01-07 Kabi Pharmacia Ab GEL-PHARMACEUTICAL LIQUID COMPOSITION AND APPLICATION THEREOF IN PHARMACEUTICAL COMPOSITIONS
US5324718A (en) * 1992-07-14 1994-06-28 Thorsteinn Loftsson Cyclodextrin/drug complexation
FR2705350B1 (en) * 1993-05-13 1995-07-07 Oreal New derivatives of mono (6-amino 6-deoxy) cyclodextrin substituted in position 6 by an alpha-amino acid residue, their preparation process and their uses.
US5302373A (en) * 1993-06-10 1994-04-12 Church & Dwight Co., Inc. Liquid mouthwash containing a particulate bicarbonate suspension
US5750140A (en) * 1994-05-20 1998-05-12 Novo Nordisk A/S Transdermal delivery of tiagabine
JPH08310925A (en) * 1995-05-17 1996-11-26 Arimino Kagaku Kk Clathrated preservative for shampoo
EP0803243B1 (en) * 1996-04-24 2003-03-19 Pfizer Inc. Cyclodextrins and phenolic compounds in dental products
EP1006993B1 (en) * 1996-10-24 2004-10-13 The Procter & Gamble Company Methods and compositions for reducing body odor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100342841C (en) * 2004-04-28 2007-10-17 莱雅公司 Cosmetic compositions comprising at least one salt, at least one cyclodextrin, and at least one surfactant, and uses thereof
CN113712836A (en) * 2020-12-30 2021-11-30 深圳市巴斯星科技有限公司 Anti-inflammatory acne-removing skin care composition and preparation method and using method thereof

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WO1998056343A1 (en) 1998-12-17
EP0996415A1 (en) 2000-05-03
JP2001515512A (en) 2001-09-18

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