CA2195961A1 - Cosmetic make-up compositions - Google Patents
Cosmetic make-up compositionsInfo
- Publication number
- CA2195961A1 CA2195961A1 CA002195961A CA2195961A CA2195961A1 CA 2195961 A1 CA2195961 A1 CA 2195961A1 CA 002195961 A CA002195961 A CA 002195961A CA 2195961 A CA2195961 A CA 2195961A CA 2195961 A1 CA2195961 A1 CA 2195961A1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
- A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Cosmetics (AREA)
Abstract
A make-up composition in the form of a water-in-oil or oil-in-water emulsion comprising silicone oil selected from volatile silicones, non-volatile silicones and mixtures thereof, optionally humectant, at least one coated or uncoated iron-oxide type pigment and a TiO2-coated platelet-type interference pigment material having a TiO2 layer thickness of from about 120 nm to about 160 nm or a whole number multiple thereof. The make-up composition exhibits improved moisturisation, together with improved skin feel and appareance and colour correction benefits.
Description
WO96103961 ~ 9596t l~ JJsl. ~
COSMETIC MA~E-UP COMPOSITIONS
Field of thP TnvPntinr~
The present invention relates to cosmetic make-up co., 1'~~ liO-.~ and more particularly, to pi~rnPnt.qci f~,...,.l~l;,..l make-up co- .p..~ I;onc having improved m~ n~tion e~,.,Li~ ,.. ,., arp~ ior~ ;rc, skin feel and ap~ e, together with colour .,u~ Li~_ cl~ fi..L~s.
R~ ~,....,A ofthP TnvPntinn ~ A folln~i~tiorl com~citi~ n can be applied to the face and other parts Of the body to even skin tone and texture and to hide pores, i~ f~,L-"b, fine lines and the like. A fol~n~l~tic)rl Li'~ ~7 ~ ;u~ . is also applied to ,. ~o;~ the skin, to balance the oil level of the skin and to provide protection against the adverse effects of sunlight, wind and the harsh environrnent.
Make-up cV~ o~ nc are generally available in the form of liquid or crearn su~ O~-C Pmlllcionc, gels, pressed powders or &iL,y~l-vu. oil and wax cv~..po~ll;onC
US Patent No. 3,444,291 discloses a method of filling and ~--,.-,un~ g skin cavities by applying a ~VI--pO~ Jll which includes 65 to 75 parts by weight of a microcrvstalline wax and about 25 to 35 parts of a mineral oil. The composition includes a colourant, preferably a coal tar dye, for ~ example, D &C Red No. 17, which matches the colour of the user's skin.
A ~ .adalsle, flowable and greaseless cosmetic cover-up composition is taught in US Patent ~o 4,486,405. That composition is ~,ha~ d by WO 96/039fi2 ~ P. ~ C
the presence of a first and a second alkoxylated surfactant present in sl~hst lnti ll Iy the same c~n~c~ alion.
US Patent No. 4,804~532 recites a facial cosmetic powder which utilizes crystalline silica in much lower con~c:..L.~lion than that employed in the then prior art co" ~ nc This powder, used as a blush or a facial coating, is said to be effective in hiding skin wrinkles, lines and pores.
The cUIll~JOailioll is a mixture of a colour phase and a diluent phase. The colour phase is formed by blending crystalline silica with lonr~ntc The resultant colour phase is mixed with the diluent phase, essentially forrned from nacreous materials such as talc and mica, to form the C~llll~ailiull.
The use of a foundation comrociti- n which has a ci~ ly high conc~ .lL.aLion of nacreous material is taught in US Patent No. 3,978,207.
This foun~ti-7n, a pressed powder r --- 'I"J' I ;~' I, is ~ ~ ;, d by the presence of a nacreous material such as mica and a binder oil which provides a frosted pearl effect, that is, a lustrous look. The colour of this r~,ull~ioll is provided by the nacreous materiial.
US Patent No. 4,659,562 discloses a cosmetic make-up co~,po~;lio..
which includes, as ~ binding agent therefore, an intimate mixture of firom 5 to 95 weight percent of a mixture of finely divided silica and about 5 to 9~ weight percent of finely divided polyethylene fibres. The composition is recited to maintain its uniformity over the areas of the skin to which it is applied. That is, it is said to be 'I~ lcasc!"~,of". The comrocitinn of the '562 patent includes colourant in admixture with nacreous agents.
Nak~lula et al., Preprints of the ~Vth l.F.S.C.C. Congress, Barcelona, 1986, Vol. 1, 51-63 t 1986) describes a novel make-up Comrociti~
utilizing spherical silica and polydimethyl siloxane. This c~nmhir~tinn is recited to provide a foundation which reduces wrinkle visibility to a greater extent than make-up Guu. ~ c with which it was compared.
This reduction in wrinkle visibility is caused by optical blurring enhanced by the novel use of spherical silica and polydill,~llyl siloxane.
COSMETIC MA~E-UP COMPOSITIONS
Field of thP TnvPntinr~
The present invention relates to cosmetic make-up co., 1'~~ liO-.~ and more particularly, to pi~rnPnt.qci f~,...,.l~l;,..l make-up co- .p..~ I;onc having improved m~ n~tion e~,.,Li~ ,.. ,., arp~ ior~ ;rc, skin feel and ap~ e, together with colour .,u~ Li~_ cl~ fi..L~s.
R~ ~,....,A ofthP TnvPntinn ~ A folln~i~tiorl com~citi~ n can be applied to the face and other parts Of the body to even skin tone and texture and to hide pores, i~ f~,L-"b, fine lines and the like. A fol~n~l~tic)rl Li'~ ~7 ~ ;u~ . is also applied to ,. ~o;~ the skin, to balance the oil level of the skin and to provide protection against the adverse effects of sunlight, wind and the harsh environrnent.
Make-up cV~ o~ nc are generally available in the form of liquid or crearn su~ O~-C Pmlllcionc, gels, pressed powders or &iL,y~l-vu. oil and wax cv~..po~ll;onC
US Patent No. 3,444,291 discloses a method of filling and ~--,.-,un~ g skin cavities by applying a ~VI--pO~ Jll which includes 65 to 75 parts by weight of a microcrvstalline wax and about 25 to 35 parts of a mineral oil. The composition includes a colourant, preferably a coal tar dye, for ~ example, D &C Red No. 17, which matches the colour of the user's skin.
A ~ .adalsle, flowable and greaseless cosmetic cover-up composition is taught in US Patent ~o 4,486,405. That composition is ~,ha~ d by WO 96/039fi2 ~ P. ~ C
the presence of a first and a second alkoxylated surfactant present in sl~hst lnti ll Iy the same c~n~c~ alion.
US Patent No. 4,804~532 recites a facial cosmetic powder which utilizes crystalline silica in much lower con~c:..L.~lion than that employed in the then prior art co" ~ nc This powder, used as a blush or a facial coating, is said to be effective in hiding skin wrinkles, lines and pores.
The cUIll~JOailioll is a mixture of a colour phase and a diluent phase. The colour phase is formed by blending crystalline silica with lonr~ntc The resultant colour phase is mixed with the diluent phase, essentially forrned from nacreous materials such as talc and mica, to form the C~llll~ailiull.
The use of a foundation comrociti- n which has a ci~ ly high conc~ .lL.aLion of nacreous material is taught in US Patent No. 3,978,207.
This foun~ti-7n, a pressed powder r --- 'I"J' I ;~' I, is ~ ~ ;, d by the presence of a nacreous material such as mica and a binder oil which provides a frosted pearl effect, that is, a lustrous look. The colour of this r~,ull~ioll is provided by the nacreous materiial.
US Patent No. 4,659,562 discloses a cosmetic make-up co~,po~;lio..
which includes, as ~ binding agent therefore, an intimate mixture of firom 5 to 95 weight percent of a mixture of finely divided silica and about 5 to 9~ weight percent of finely divided polyethylene fibres. The composition is recited to maintain its uniformity over the areas of the skin to which it is applied. That is, it is said to be 'I~ lcasc!"~,of". The comrocitinn of the '562 patent includes colourant in admixture with nacreous agents.
Nak~lula et al., Preprints of the ~Vth l.F.S.C.C. Congress, Barcelona, 1986, Vol. 1, 51-63 t 1986) describes a novel make-up Comrociti~
utilizing spherical silica and polydimethyl siloxane. This c~nmhir~tinn is recited to provide a foundation which reduces wrinkle visibility to a greater extent than make-up Guu. ~ c with which it was compared.
This reduction in wrinkle visibility is caused by optical blurring enhanced by the novel use of spherical silica and polydill,~llyl siloxane.
US Patent No.5,143,722 discloses a cosmetic make-up composition comprising water-in-oil emulsions co~ ;sillg pigment coated with polysiloxane, a silicone phase~ a water phase and a polydiorganosiloxane-polyoYyalkylene copolymeric Sulr~
Metal oxide coated substrate nacreous pigrnents are known in the art and are ~~y~mplified by titanium dioxide and/or ~ UlLiUIII dioxide coated mica. Such pigments are described in US-A-3,497,515, US-A-3,418,146, US-A-3,087,828 and US-A-4,038,099. Depending on the thickness of the metal oxide coating, the pigments can exhibit hl~l r~ lce or reflection colours of blue, green, yellow, red, etc.
Foundations in the form of water-in-oil Pmlllr;- n~ are well known and provide good coverage and good skin feel, wear and ap~ G.a..ce. These have, however, not been ~ r~ fill from the vi. ~ of colour correction of the skin tone and for reducing skin redness.
It would be desirable to provide a cosmetic make-up ~ .o~ which delivers not only good coverage to the sk;in but also which serves to reduce any unevenly coloured or red skin tones. Attempts have been made in the past to correct red facial skin tones by ~ppli~ti~n of a green-coloured foundation followed by application of a conventional pigmented foun~l~tion It would be ri~sir~hhP therefore, to provide a single pigmented foundation c~ ;orl which delivers both skin colour corrective benefits and good coverage, but does not appear green on the skin.
It is acco.dill~;ly an object of the invention to provide a pi~m~n~ed make-up co...?G~;u~ in the form of a water-in-oil em~ on which exhibits good muia~ a~ion together with good coverage and skin colour corrective benefits.
Sllmm~ry of the ~nvention According to the present invention there is provided a make-up co,l.~o ,i~ion in the forrn of a water-in-oil or oil-in-water emulsion comprising:
_ _ _ _ _ ::
;' ~ 2 1 9596 ~
WO96~03962 F~, IIU~
~ , .
a) from about 1% to about 50% by weight of silicone oil selected from volatile silicones, non-volatile silicones and rnixtures thereof, b) optionally up to about 30~/0 by weight of h~
c) from about 0.1% to about 25% by weight of at least one coated or uncoated iron oxide-type pigment, and d) from about 0.1% to about 10% by weight of a TiO2-coated platelet-type illt~ .felcl.~e pigment material having a TiO? layer thickness of from about I 20mn to about 160nm or a whole number multiple thereof.
The water-in-oil PmllicionC of the present invention provide improved colour COll.~ , benefits together with good coverage, skin ~L J~.aLaL.ce and superior IIIOi ,~ Lion.
All levels and ratios are by weight of total cull~llo~ n~ lmless otherwise in iiC~tPfi Chain length and degrees of aLh,~' -m are also specified on a weight average basis.
n.~t~ilP I nPc~ tinn of thP Tnv~ntil-n The make-up c~ ;li..., accu..lillg to the present invention culll~Lises a mixture of volatile and/or non-volatile silicones, iron oxide-type pigment, T;02 platelet ty~pe illt~,.r~ ,.,ce pi~ment materiai and optionally ILI I 1 l l 1~ The c- ~ i l inn is in the forrn of a water-in-oil emulsion.
A first essential CvlllyOIl~ of the water-in-oil emulsion is â silicone oil which in preferred embodhll~ culll~lises a mixture of voiatile silicones and non-volatile silicones. The silicone oil is present in an amount of from about 1% to about 50% by weight. Suitable volatile silicone oils include cyclic and linear volatile polyorg~nogilo~-~nf~q (as used herein, "volatile" refers to ~ose materials which have a ~ vapour pressure at ambient conditions).
A description of various volatile silicones is found in Todd, et al..
"Volatile Silicone Fluids for Cocm~ticsll~ 91 Cosmetics and roilelries 27-32 (1976).
219Jr961 ~ W0 96/03962 ' - ; ~ 5,-1 10 Preferred cyclic silicones include polydimethylsiloxanes cont~ining from about 3 to about 9 silicon atoms, preferably containing from about 4 to about 5 silicon atoms. Preferred linear silicone oils include the polydimethylsiloxsnes containing from about 3 to about 9 silicon atoms.
The linear volatile silicones generally have viscosities of less than about 5 cPntictok~ps at 25~C, while the cyclic materials have viscosities of less thsTt about 10 c~ (. L ~c Examples of silicone oils useful in the present invention include: Dow Corning 344, Dow Corning 21330, Dow Coming 345, and Dow Corning 200 (" ~ ~ ~r,.. I,l.ed by the Dow Corning Corporation): Silicone 7207 snd Silicone 7158 (~ lrn- m cd by the Union Carbide Corporation). SF:202 ("- .".r.. ~"~,d by General Electric) and SWS-03314 (m Innf~rtllred by Stauffer Chemical).
Suitable non-volatile silicones preferably have an average viscosity of from about 1,000 to about 2,000,000 mm2.s~l at 25~C, more preferably from about 10,000 to about 1,800,000 mm2.s~l, even more ~1~ fi .dbl~
from about 100,000 to about 1,500,000 mm2.s~l . Lower viscosity non-volatile silicone conrliti~nin~ agents, however, csn slso be used.
Viscosity csn be measured by means of a glsss capillary ViaCOIII~t~ . as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970. Suitable non-volatile silicone fluids for use herein include polyalkyl cil/~x~nPc, polyaryl ~ Y~nPc, polyalkylaryl 5ilnY~nPc, polysiloxanes with amino functional stth5ti~ ionc, polyether siloxsne copolymers, snd mixtures thereof. The siloxanes useful in the present invention may be Pnfln~rped with sny number of moie~ies, inclll~ling for example, methyl, hydroxyl, ethylene oxide, propylene oxide, amino and csrboxyl. However, other silicone fluids having skin cnn~iitinning properties may be used. The non-volatile polyalkyl siloxane fluids that may be used include, for exsmple, polydimethylcilnx~r~Pc These siloxsnes are available, for exsmple, from the General Electric Compsny as a Viscasil (RTM) series snd from Dow Corning as the Dow Corning 200 series. Preferably, the viscosity ranges from about 10 mm2.s~l to about 100,000 mm2.s~1 at 25~C. The polyalkylsryl siloxane fluids that ~ may be used, also include, for example, pol~ ylpL~ iloxsnes.
These siloxanes sre available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid. The polyether siloxane copolymer that may be used includes, for exsmple, a polypropylene oxide modified ~h'096/03962 96 1 P II.J ,o dimethylpolysiloxane (e.g., Dow Coming DC- 1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
References disclosing suitable silicone fluids include US-A-2,826,551, Green; US-A-3,964,~00, Drakoff, issued June 22nd, 1976; US-A-4,364~837, Pader; and GB-A-849,433, Woolston. In addition, Silicone C~ o..,,ds di~L~ibu~d by Petrarch Systems Inc., 1984 provides an extensive (though not exclusive) listing of suitable silicone fluids.
Preferred non-volatile silicones for use herein include poly.liu~ ocil~ xarle-polyoxyalkylene copolymers cont~ining at least one polydiorg~n~cil~y~np segment and at least one polyoxyalkylene segment, said polydiorg~lnnq~ y~n~ segment c~n~ictin~ essentially of RbSiO(1 b)/2 siloxane units wherein b has a value of from about 0 to about 3, inclusive, there being an average value sf all~Jlu~illlat~ly 2 R radicals per silicon for all siloxane units in the copolymer, and R denotes a radical selected from methyl, ethyl, vinyl, phenyl and a divalent radical bonding said polyoxyalkylene segment to the polydiorgPnnsiloY~nP segrnent, at least about 95~/0 of all R radicals being methyl; and said polyoxyalkylene segment having an average rn- lecnl~r weight of at least about lO00 and concicting of from about 0 to about 50 mol percent polyoxypropylene units and from about 50 to about 100 mol percent polyoxyethylene units, at least one terminal portion of said polyoxyalkylene segment being bonded to said polydiorpPn~ciloy le segment, any terminal portion of said polyoxyalkylene segment not bonded to said polydiorE~Pn-silox~nP
segment being satisfied by a t~ ,";n~1l;..p radical; the weight ratio of polydiorganosiloxane segrnents to polyoxyalkylene segments in said copolymer having a value of from about 2 to about 8. Such polymers are described in US-A-4,268,499.
2 ~ 9~5 9 ~ 1 ~ WO 9ii/03962 r~ s~
More preferred for use herein are polydiorganosiloxane-polyoxyalkylene copolymers having the general forrnula:
~ E~3C--- Si --o--(Si--O)--~Si--O~y--Si--CH3 CH 3 C~ 3 C3H 6 CH 3 o -- (c2H4o1 a (C3H~O) bR
wherein x and y are selected such that the weight ratio of polydiorganosiloxane segments to polyoxalkylene segments is from about 2 to about 8, the mol ratio of a:(a+b) is from about 0.5 to about 1, and R is a chain ~- I l 1;~ lAI ;UP group, especially selected from Lyd~ug~
hydroxyl; alkyl, such as methyl, ethyl, propyl, butyl, benzyl; aryl, such as phenyl; alkoxy such as methoxy, ethoxy, propoxy, butoxy; t~,~ylv.~y, aryloxy, such as phenoxy; alkenyloxy, such as vinyloxy and allyloxy;
acyloxy, such as acetoxy, acryloxy and plvl~ onv~y and amino, such as dimethylamino.
The number of and average molecular weights of the segments in the copolymer are such that the weight ratio of pOlydivl~:ano~iloxane segments to polyoxyalkylene segments in the copolymer is preferably from about 2.5 to about 4Ø
Suitable copolymers are available ~ o~"~ ,;ally under the ~ 5 Belsil (RTM) from Wacker-Chemie GmbH, G~Crh ~ n~b. ~ ~; 1, S, Postfach D-8000 Munich 22 and Abil (RTM) from Th. Cc' ~ It Ltd,. Tego House, Victoria Road, Ruislip, MiAAI~seY HA4 OYL. P~. Li~,ulàlly preferred for use herein are Abil WE 09, Belsil (RTM) 6031, Abil (RTM) ~ B88 183 and DC3225C. A preferred silicone herein is known by its CTFA A.o~ign~tjnn as rlim~thi~-~n~ copolyol.
w0961039~2 ~ 2 ~ 9596 1 E~,",l"J'I to ~
The silicone oil phase preferably comprises from about 2% to about Z5%, more preferably from about ~/o to about 15% by weight of composition of non-volatile silicones.
Another desirable COlllpull..lt of the co,.ipo~itions herein is a hllmPc~qn~
or mixture of hllmrct~llte The h---"~ or mixhrïe of hllll~F~
herein is preferably present in an amount of from about 0.1% to about 30~~O, more preferably from about 5~/0 to about 25%, and especially from about 10% to about 20% by weight of C~ . l ;nn Suitable l .. ~ h. l are selected from glycerine and poly~4~,ylL~ ylate lubricant having a viscosity at 25~C of 300,000 to 1,100,000 cps; a specific gravity at 25~C of I to 1.2g~ml, a pH of 5.0 to 5.5; a bound water content of 33 to 58%; and, a free ~7ater content from 5 to 20%.
The h ~ thlll can be h~Cul~Jv~ ,d at least partly into the oil phase of the water-in-oil emulsion so as to form 8 ".~.ln~ e l"Illl~ -in-oil-in-water f~ a' 1ll. In these ~ ..,1~l:.". ,l~ the Oa phasc c-~ from about 0.1% to about 10%, preferably from about 0.1% to about 3% by weight of l..-,..~ ~l on a cnmr~citinn basis. Suitably, the l,.~...~- l...,l is introduced into the o~il phase in the fonn of a mixture with or h~ul~v~ted within a particulate lipophilic or hy~Lv~hv[~ c carrier material, for example a cross-lif~lced lly~Lvpllobic acrylate or methacrylate copolyrner as described in detail hereaf~er.
Suitable polygly~ y~ LLa~ylate lu~ are marketed by &uardian Chemical Corporation under the trademark "Lubrajel". The "Lubrajels"
identified as "Lubrajel DV", "Lubrajel hlS", and "Lubrajel CG" are preferred in the present invention. The gelling agents sold under these tlad~lllalL~ contain about 1% propylene glycol.
Other suitable hnm~rt~nte include sorbitol, p~nth~n-~1c, propylene glycol, butylene glycol, hexylene glycol, alkoxylated glucose d l;V~ s, such as Glucam (RTM) E-20, hexanetriol, glucose ethers, sodiurn hyaluronate, and mhctures thereof. Urea is also suitably added as a h..l~c~ in the internal aqueous phase.
The panthenol moisturiser can be selected from D-panthenol (ER]-2,4-dihydroxy-N-[3-hydluA,y~ ,yl)]-3,3-dimethylbu~nide), DL-p~nthrn~
,, _,, _ . _ _, _ , , , , , , , , , _ ~ W0 96/03962 calcium p~ntoth~n~te, royal jelly, p~nth~tin~ pantotheine, panthenyl ethyl ether, pangamic acid, pyridoxin, pantoyl lactose and Vitamin B
complex.
In preferred embodiments, the hl~m~ct~nt is selected from glycerine and sodium hyaluronate, and mixtures thereo~ Chemi(~lly, glycerine is 1,2,3-1,.u~ . hiol and is a product of CC711~ ;. 'When present, sodium hyaluronate is preferably illCUl~Ulai~,d at a level of from about 0.05% to about 2% by weight. The mixtures are especially valua'ble herein from the viewpoint of providing enhanced " ",;~, . "; ~1 ;on.
Another essential ~o~.,p,~ herein is at least one iron oxide-type pigment. The iron oxide-type pigment used herein can be either coated or lmro ItPA The pigments can be treated with cc.,..l.o~ such as amino acids, silicones, lecithin and ester oils. The more preferred pigments are the silicone (polysiloxane) treated pi~rnPntC
The total cù--~ LIdhon of the iron oxide-type pigment in the c- ~ ~ i ~v~ll ;o~
is from about 0.1 to about 25% by weight and is preferably from about I
to about 15% by weight of the total c~ .l.o~ The exact COIlCt:llLla~iOil of pigments in the co.. ~1~~~ l ;o.- is A~ to some extent upon the specific mixture of pigments selected for use in a foundation make-up or blusher to achieve the desired shades. The preferred compositions contain from about 2% tO about 20% by weight of titanium dioxide and most preferably from about 5% to about 10% by weight of titanium dioxide.
Another essential cu,l,~un..lt of the cosmetic cc,lll~vailions of tne invention is a TiO2-coated platelet type illt~.lf~l. .l~,e pigment material.
Preferably, the illt~ .f~L~,I.,e pigment material Cuul~ platelet type mica which is coated with TiO2. The colour of the reflected light varies A-~pPnAinp on the thickness of the layer. The i...~,lf~ ll,ncc pigment material used in the present invention c~ at least a proportion of pigment material having a TiO2 layer thickness of from aoout 120nm to about 160nm or a whole number multiple thereof such that the pigment itself has an overall green a~ ance when applied to skin as a result of light reflection from the pigment platelets. Preferred i.it~ .r~ .~ nce pigment materials for use in the comroiitit)n of the invention are those 9 ~ 9 ~
WO 96~03~6~
supplied by Merck under the trade name Timiron, especially Timiron Super Green.
The TiO2-coated platelet type h~ f~ l.ce pigment material is used herein at a level of from about 0.1% to about 10%, preferably from about 0.1% to about 5~/O, more preferably from about 0.59/O to 3~/O by weight of ~ u.l.p~,~iLion.
Other suitable pigments for use herein can be inorganic andlor organic.
Also included with-in the term pigment are rnaterials having a low colour or lustre such as matte finishing agents, and also light 5c~t~in~ agents.
Examples of other suitable pigments are acylgl, ~~ iron oxides, U~ ;r'f blue, D~C dyes, carmine, and mixtures thereo~ Depending upon the type of rn~ke-up cv~ l/v~;l ;on, whether fs~m~ ion or blusher, a mixture of pigrnents will normally be used.
The Çu~ c.,...~ u.~ can also include from about 0.1% to about 10% of at least one matte finishing agent. The function ofthe matte finishing agent is to hide skin defects and reduce shine. Such co;"..~ ,ally a~c p~ inorganic agents, i.e., those included in the CTFA Cosmetic rngredient Dictionary, Third Ed., as spherical silica, hydrated silica, silicone-treated silica beads, mica, talc, polyethylene, titanium dioxide, b~ntrmit~ hectonte, kaolin, chalk, ~ lu~ euu~ earth, attapulgite and the like may be utilized. Of ~ li. ul.u n~filln~c~ as a matte finishing agent is low lustre pigment such as titanated mica (mica coated with titanium dioxide) coated with barium sulfate. Of the inorganic r~ useful as a matte finishing a~ent low lustre pigment, talc, polyethylene, hydrated silica, kaolin, titanium dioxide and mixtures thereof are pallicukuly preferred. Materials suitable for use herein as light-s~ . i"p agents can be generally described as spherical shaped inorganic materials having a particle size of up to about 100 microns, preferably from about 5 to about 50 microns, for example spherical silica particles. Highly preferred from the viewpoint of oil absorption and shine reduction, especially in ~ cg~t~ininp products, are spherical silica particles having a specific surface area (N2, BET) of at least 150 m2/g (ASTM-D3663-9 1 ) and a pore volume of at least 0.5 ml/g (ASTM-D4222-91~.
~ WO 9C103962 , ~ 2 ~ 9 ~ 9 6 t F~
The bal nce of the composition of the present invention colllp.;se .
deionized water. The composition preferably comprises from about 15%
to about 95%, more preferably from about 20% to about 80% by weight of the oil phase, and from about 5~/0 to about 85%, more preferably from about 20% to about 80% by weight of the water phase.
The make-up compositions of the present invention can also comprise a particulate cross-limced hyd.o~llob;c acrylate or ~ l.a~ .~/late copolymer.
This copolymer is ~Jal~ ~ly valuable for reducing shine and controlling oil while helping to provide effecdve mni~hn i7~ri--~n benefits.
The cross-linked hy.Lul.hobic polymer is preferably in the form of a copolymer lattice with at least one active ingredient dispersed uniformly throughout and elllla~cd within the copolymer lattice. All~.lla.h,~ ly, the hy~Lupl.ob:c polymer can talce the form of a porous particle having a surface area (N2-BET) in the range from about 50 to 500, ~Icr~ lably 100 to 300m2/g and having the active h.~;., l;~..l absorbed therein.
The cross-linked hyLù~,hob;c polymer when used herein is in an amount of from about 0.1% to about 10%, I..ef~,.d'~l~ from about 0.3-3% by weight and is IJI~ir I !y il.cull w..t.,1 in the exte nal silicone-c~ .;..;..g oil phase. Tne active i~ ll can be one or more or a mixture of skin compatible oils, skin compatible 1..~ ;, emollients, moisturizing agents and sunscreens. The polymer material is in the form of a powder, the powder being a comhin~d system of particles. The system of powder particles forms a lattice which includes unit particles of less than about one micron in average diameter, agglomerates of fused unit particles of sized in the range of about 20 to 100 microns in average diameter and ag~,,t, s of clusters of fused agglomerates of sizes in the range of about 200 to 1,200 microns in average diameter.
The powder material of the present invention which can be employed as the carrier for the active ill~ l can be broadly ~le~r~iked as a cross-linked "post absorbed" hydrophobic polymer lattice. The powder preferably has entrapped and dispersed therein, an active which may be in the form of a solid, liquid or gas. The lattice is in particulate form and conctit~tec free flowing discrete solid particles when loaded with the activematerial. Thelatticemaycontaina~ e.~ -..in~dquantityofthe active material. The polymer has the structural formula:
, ~tO 96/03g62 ~ ' ' '. t ~ 2 1 9~96 ~ r~ . tO
CH3 ¦ C~3 C=O C--O
R' R' ' C=O
CM~ C
where the ratio of x to y is 80:20, R' is -CH2CH2- and R" is -(CH2)1 ICH3.
The hydrophobic polymer is a highly c}osslinked polymer, more particularly a highly cross-linked polyrnethacrylate copolymer. The material is m~mlf~rt~lred by the I)ow Corning C.,.~o,~l~iu,., Midland.
Michigan, IJSA, and sold under the trademark POL~RAP (RTM) . It is an ultralight free-flowing white powder and the particles are capable of a~50~ b ;l~g high levels of lil-sphili~ liquids and some hydrophilic liquids while at the satne time l..~ t~ a free-flowing powder character. The powder structure consists of a lattice of unit particles less than one micron that are fused into agglomerates of 20 to 100 microns and the agglomerates are loosely clustered into macro-particles or ag~ es of about 200 to about 1200 micron size. The polymer powder is capable of cnn~ininp as much as four times its weight of fluids, emlllcionc dispersions or melted solids.
~ W0!)6~03962 ' ' ''~ 21 9596 ¦ r~.,.J.,,s :c Adsorption of actives onto the polymer powder can be accomplished using a stainless steel mixing bowl and a spoon, wherein the active is added to the powder and the spoon is used to gently fold the active into the polymer powder. Low viscosity fluids may be adsorbed by addition of the fluids to a sealable vessel cont~ining the polymer and then tumbling the materials until a co .~ . L~,y is achieved. More elaborate blending eqnipmPnt such as ribbon or twin cone blenders can also be employed. The preferred active in~ for use herein is glycerine.
Preferably, the weight ratio of 1,.1...~ carrier is from about 1:4 to about 3:1.
Also suitable as a highly cross-linked polymethacrylate copolymer is Micl u~,oll~Ses 5647. This takes the form of generally spherical particles of cross-linked h~ u~llOb C polymer having a pore size of from about 0.01 to about 0.05~m and a surface area of 200-300m2/g. Again, it is preferably loaded with 1~ in the levels d~srrihet above.
The cv5llpo~ ions of the invention can also contain a hydrophilic gelling agent at a level ~Icf~..dl)ly from about 0.01% to about 10%, more preferably from about 0.02% to about 2%, and especially from about 0.02% to about 0.5%. The gelling agent preferably has a viscosity (1%
aqueous solution, 20~C, Brookfield RVT) of at least about 4000 mPas, more preferably at least about 10,000 mPa.s and especially at least 50,000 mPa.s.
Suitable hydrophilic gelling agents can generally be described as water-soluble or colloidally water-soluble polymers, and include cellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose, h~d.u~,u~ylmethyl cellulose), polyvinylpyrrolidone, polyvinylalcohol, polyqu~t.~mil~m-10, guar gum, hy.hu~ u~,yl guar gum and xanth~n gum.
Among suitable hydrophilic gelling agents are acrylic acid/ethyl acrylate copolymers and the carboxyvinyl polymers sold by the B.F. Goodrich Company under the trade mark of Carbopol resins. These resins consist essentially of a colloidally water-soluble polyalkenyl polyether crosslinked polymer of acrylic acid cros~link~d with from 0.75% to 2.00% of a cro~linkin~ agent such as for example polyallyl sucrose or W0 96/03962 ~ 2 ~ 9 5 ~ 6 1 I ~
polyallyl pentaer~thritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980, Carbopol 951 and Carbopol 981. Carbopol 934 is a water-soluble polymer of acrylic acid crossliniced with about 1%
of a polyallyl ether of sucrose having an averagc of about 5.8 allyl groups for each sucrose molecule. Also suitable for use herein are hydrophobically-modified cross-linked polyme~, of acrylic acid having ~mphir~thic tJIu~7,,L~,5 available under the Trade Name Carbopol 1382, Carbopol 1342 and Pemulen TR-I ~C IFA DPci~tit-n AcrylatesllO-30 Alkyl Acrylate Crosspolymer~. A comhin~tinn of the polyaikenyl polyethercross-linkedacrylicacidpolymerandt'nehy~L-r'l L: ~Iy modified cross-linked acrylic acid polymer is also suitable for use herein.
The gelling agents herein are particularly valuable for providing excellent stability ~,haL~ .L~;li ,Lics over both normal and elevated temperatures.
Neutr~li7in~ agents suitable for use in n. ,.~ acidic group ~o-.
hydrophilic gelling agents herein include sodium 4~,~dlu~i~c~ p,,.t~
hydroxide~ ~Tnmr~nillm hydroxide" ~ r~ .ol_...;..- and t~jeth7lnr~ nin~
T~e make-up comrocitit~n~ herein ca n a~ it~ lly conprise an emollient. Fmo~ .ntc suitable for the compositions of tne present invention include na~tural and synthetic oils selected ~m mineral, vegetable, and animal oils, fats and waxes, fatty acid csters, fatty alcohols, alkylene glycol and polyalkylene glycol ethers and esters, fatty acids and mixtures thereof.
Suitable ~7~ tte for use herein include, for example, optionally hydroxy-s-ln.,llL s~i Cg-Cso ~ n ~d fatty acids and esters thereof, C l-C24 esters of C~-C30 saturated fatty acids such as isopropyl my;istate, cetyl palmitate and octyldode. ~hl,rl;a~dLc IWickenol 142), beeswax, saturated and un~tln at~d fatty alcohûls such as behenyl alcohol and cetyl alcohol, hy(llu- ~kons such as mineral oils, p~.~luln~
and squalane, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26 1976), lanolin and lanolin derivatives, such as lanolin alcohol ethoxylated, hyd~u~ Led and ac,.yli l~d lanolins7 cholesterol and derivatives thereof,~ animal and vegetable triglycerides such as almond oil, peanut oil, whoat germ oil, linseed oil, jojoba oil, oil of apricot pits, , . . . . . .
, T ,, ~ j V i~ ~ 2 1 ~ 5 ~ 6 1 ~ W096/03962 ' '' : :', ._I/IJ~_, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grapeseed oil, and sunflower seed oil and C l C24 esters of dimer and trimer acids such as diisopropyl dimerate, diisostearylmalate, diisostearyldimerate and lliiSua~cài.~'lliilllCLdl~
Preferred emollients are selected from cetearyl ieon~m~n~t.~, isopropyl psllmit~t-o, isopropyl iso~t~ , cetyl ocr~no~tP~ cetyl acetate, trioctyl citrate, PEG isoceteth-3 acetate, dioctyl maleate, propylene glycol dicaprylate/~lir~pr~t~, caprylic/ capric triglyceride, mineral oil, PPG-20 methylglucose ether, and lanolin alcohol, and mixtures thereof. These emollients may be used inrl~p~n-lPntly or in mixtures and may be present in the cul.lpo~ilion of the present invention in an amount from about 1%
to about 30% by weight, and preferably are present in an amount from about 5D/o to about l 5% by weight of the total c~
The c~ po~;l ;.~-. may also contain 9,~ t~ materials such as, for example, Çlag,iallces~ fillers such as nylon, sun-screens, p.~a~dti~es, proteins, antioxidants, chelating agents and water-in-oil Pnn~ ifiprs as u~
Another optional c~ pùn .1 of the make-up composition is one or more ultraviolet absorbing agents. Ultraviolet absorbing agents, often described as ~uu~ e~ g agents, can be present in a c~n~ l ;on in the range of between about 1% and about 12% by weight, based on the total weight of co ~ OC l ;~ ~ Preferably, the W abso- I,;..g agents constitute between about 2% and 8% by weight. More preferably, the W
absu.b;l.g agents can be present in the cV~ v~ n in a cùllc~ alion range of between about 4~/0 and about 6% by weight. Of the ultraviolet absorbing agents suitable for use herein, t- .,>,~ph~ -3, octyl dimethyl PABA ~Padimate O) and mixtures thereof are p~li~ ulally preferred.
Ultrafine TiO2 is also suitable for use herein.
A chelating agent can also be hlcul~vlat~ .i in the make-up composition.
A chelating agent is preferably present in the cornposition in a concentration in the range of between about 0.02% to about 0.10% by weight, based on the total weight ofthe co...l.-,~;lion. Preferably, the ~ s W096/03962 ~ 2 ~ 7u t _ ,,~ c chelating agent is present in a CU1l~ t llilo~iOQ in the range of between about 0.03% and about 0.07~/O by weight, based on the total weight of the composition. Among the chelating agents that may be included in the composition is trisodium EDTA.
Another optional but preferred cu.ll~o~ of the f~t~lnr7~tinn cc,~ o~;Liu-isoneormorepreservatives. The~n.~,.,. rdli~,C'~ '; tninthe foundation c~tmpn~hion, based on the total weight of that co.,.~ ;on~ is in the range of bet~veen about 0.2% and about 0.8% by we;ght, preferably between about 0.4% and about 0.6% by weight. Suitable preservatives for use herein include f1;~7 ~ yl urea, methyl paraben and ethyl paraben, and mixtures thereo~
Another optional but preferred co.ll~o~ of the f~ u l~a~iO~ c ~ ; tn is a sebum spreading agent. The sebum spreader is present at a level of from about 0.0 l% ~û about 5~/O by weight of c-,., .l .. . ~ . A preferrod sebum ~ o1hlg agent is sodium Cg-C16 isoalkyL..l~,c~ Jl~
sulfonate (Biopol(Rl~I) OE).
A lower (C l-C6) alcohol may also be present in the fol~n~ ~finrt of the present invention at a level of from about 0.5~/O to about 10% by weight of culll~ ition. Suitable lower alcohols for use herein include ethanol, hexylene glycol, bu~lene glycol, propanol and propylene glycol, preferably ethanol.
The make-up comrocitionC of the present invention can be in the form offou.l~l a ;u.,~ blushers, c~ compâct powders, and the like, preferably as follnfi~tionc and blushers.
The following Table is provided to illustrate cnmr~Citi~nq of the make-up of the present invention:
Example I Il III IV V Vl VII VIII
~YI Wt Wt Wt Wt Wt Wt Wt o~O o~O ~/0 ~/0 ~/~ YO ~/0 ~/0 A.
Cetyloctanoate 2.00 o.o o.o 2.0 0.0 0.0 0.0 0.0 Cyl 1...,.. ,1.: ....~ &.57~ 12.Z5 12.25 15.0 12.0 g.574 8.57 15.58 WOg6/03962 ~ q596 1 r~ ,s~ ~o Cy~ ml th;~ n~ /
~lim~th~ n~l copolyol (90:10) 17.16 15 0 20.0 5 0 8 0 13 017 16 12.5 Plul.yl,ualaL~Il 0 25 0.25 0.25 0 250.25 0.250.25 0 25 laureth-7 0.5 O S 0.0 0 5 0.0 0.5 0.0 0.5 Dioctyl maleate 0 0 0.0 0.0 0.0 10 0 0.0 0.0 0.0 Di.. ~ u.l~ 0 0 0 0 0 0 3 0 5.0 10 0 0.0 0 0 B ~ 3 0 0 0.0 0.0 0.0 0.0 2.0 0.0 0.0 Propylene glycol 0.5 0.5 0.0 0.0 0.0 0.0 0.0 0.0 Dicaprylate/
Dicaprate 0.0 0.0 0.0 5.0 0.0 10.0 0.0 0 0 Titanium~ Dioxide 8.25 6.0 1.5 6.0 8.0 200 9.0 70 Titanium Dioxide treated (Aluminium hydrate, stearic acid) 0.25 0.5 3.0 0.250.25 0.0 0.25 0.25 Titanated Micas 0.1 0.1 0.1 0.25 1 0 0 0 0.1 0 1 Tâlc 3.387 4.5 6.0 0 7 0.7 0.7 3 387 4.0 Nylon 0 0 0-0 ~-~ ~-~ 0 5 ~ ~ ~ ~ ~ ~Timiron Super 2 0 2.0 3 0 2 0 0.1 2 0 0.5 2.0 Green WO 96103962 ' ~ ~ .
Example I 11 111 IV V Vl VII Vlll ~t Wt Wt Wt Wt Wt Wt Wt .~o % o/o o~o o~O 0~o 0~o O~
C.
C,~. 1.. 11,:. ,"" I
h.......
copolyol (90:10)1.858 1.5 1.85 5.0 1.0 1.0 1.858 1.0 Acrylates Copolyrner Q.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 Acrylates Copolymer ~loaded with glycerine) 1.0 0.0 6.0 1.0 0.0 1.0 1.0 0.0 Yellow Iron Oxide 1.2 1.2 0.6 0.4 1.2 1.2 1.2 1.2 Red Iron Oxide 0.49 0.6 0.6 0.490.49 0.2 0.6 0.42 BlacklronOxide 0.16 0.1 0.24 0.1 0.1 0.240.24 0.22 Ultramarine Bluea.o o.oo o.oo o.l o.o o.o o.o o.o Cy~ h.--. 0,0 0,0 0.0 0.0 0.68 0.0 0.0 0.0 Silica (spheron P1500) 3.0 6.0 -- 0.1 -- 0.0 Silica besds (Sphe~n L1500) 0.0 0.0 1.0 0.1 0.5 0.5 Synthetic Wax 0.1 0.5 O.S 0.1 ~ 0.1 Arachidyl behenate 0.3 -- 0.3 0.0 0.3 0.3 0.3 Stearic Acid 0.0 -- ~ -- -- -- 2.5 0.0 Palmitic Acid 0.0 -- - - 2.5 -- 0.0 096/039G2 , 2~95961 r~".,~
Example I 11 111 IV V Vl Vll Vlll Wt Wt Wt Wt ~h't Wt Wt Wt o~ o/O o~o o/o o/o ~/0 /0 /0 Trihydroxy-stearul 0.3 0.3 1.5 1.5 - 0.3 C~ 1.0 4.0 -- -- 4.0 4.0 4.0 1.0 Beeswax 1.5 1.2 -- -- 1.3 -- - 0.0 A bil ~Vl~ 09 -- 3.0 - -- 0.0 Palm Oil -- -- - 4 o.o Al Mg hydroxy stearate/
(20:80) 0.5 1.5 1.8 1.5 10.0 3.0 3.0 0.0 Ethylene btassylate 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 B H T 0.05 0.05 0 05 0 05 0 05 0 05 0 05 0 05 H.
Deiorlized water -- - --~- - -100- - ---- -~-- --~--to Methyl paraben 0.12 0.15 0.15 0.12 0.12 0.12 0.15 0.12 Propylene glycol 8.0 8.0 0.0 0.0 1.75 8.00 0.0 0.0 Sodiuro c~loride 2.0 1.4 1.4 0.5 2.0 2.0 2.5 2.0 Sodium dil.~' 0.3 0.3 0.3 0.8 0.8 0.3 0.8 03 Glyceti~e 0.0 15.0 10.0 5.0 6.5 3.0 3.0 10.0 Trisodium EDTA 0.0 0.0 0.0 0.0 0.0 0.0 0.01 0.0 Tr;~ 0.0 0.0 0.0 0.0 0.0 0.0 0.75 0.0 Allaraoin 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 Biopol OE -- 0.5 -- 0.5 0.0 ELh2m ol - 6 -- - - 2 -- 0.0 ~t q596 ~
... ,......................................... _ wo 96/03962 Example I 11 III IV V Vl Vll VIIT
~It \,~/t Wt Wt Wt Wt Wt Wt ~/ 0/o o/O o~O o~o % /o /o Panthenol ~ 2 -- -- 2 -- 0.0 h~L.,~
cellulose 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 sunscreen 0.0 0.0 0.0 0.2 0.2 0.0 0.0 0.0 Sodiutn L~ ' . 0.0 0.05 0.08 0. l 0.0 0.0 0.2 0.0 Deionized Water 0.0 0.0 0.0 0.0 10.0 -- -- 0.0 T~ ~ -Aluminium Silicate ~ 0.Z -- -- 0.0 Propylene Glycol 0.0 0.0 0.0 2.0 0.0 0.0 0.0 0.0 Xanthan Gum 0.0 0.0 0.0 0.08 0.0 0.0 0.0 0.0 Essential Oils 0.0 -- -- 0.20 -- -- -- 0.0 Perfilme Oil 0.0 0.25 -- 0.20 -- -- 0.0 Vitamin A Q05 -- -- ~~ ~~ ~~ ~- ~ ~
Palrnitate 0.0 0.05 -- -- -- - -- ~ ~
Aloe Vers Gel 0.0 0.0 3.0 -- -- -- -- 0.0 Extract 0.0 0.0 0.1 ~ 0.0 The various CO~ O~ ' listed in the Table have been se~e1 into groups, the conctinlPntc of each group being mixed together before being added to members of the remaining groups in acc- ~-l~nce ~ith the IJlu~,edu~ set forth below.
~ W096/03962 ~ 2 1 9596 1 ~"~
In the first step, the mixture of components of phase A is stirred for approximately 5 minutes with sheer mixing until homogeneous. With high speed sheer mixing, the materials of phase B are added gradually to A and the batch is mixed for 35 minutes until dispersed.
The colll~o~ of phase C and then phase D are slowly added to the mixture of phases A and B with high shear mixing until ~ pPr5e~ Silica is added at this point and dispersed through the mixture.
The culllpon~ of phase E are added into the resulting batch which is then heated to 84~C and mixed until dispersed. The vessel is cooled to 45~C and the premixed phase F is added. The batch is mixed until homog~n~ou~ The mixture is cooled to 30~C and phase G is added.
A premix of phase H is made by mixing all the c-., .,1,. 1l~l .,1~ until c---p'~ 'y dissolved. At 30~C the premix of phase H is added sparingly to the batch mixture with high shear, ensuring that there is no excess water on the surface. The mi7cture is then mixed for 15 minutes. Finally phases I, J, K, and L are added.
The resulting make-up co"~ ;(ioll is ready for packing.
The make-up c~ onc of the Examples exhibit improved moisturisation, application cl~ ics, skin feel and al"~ed.d..ce, together with colour corrective ~Ldl a~,t~ Lics.
Metal oxide coated substrate nacreous pigrnents are known in the art and are ~~y~mplified by titanium dioxide and/or ~ UlLiUIII dioxide coated mica. Such pigments are described in US-A-3,497,515, US-A-3,418,146, US-A-3,087,828 and US-A-4,038,099. Depending on the thickness of the metal oxide coating, the pigments can exhibit hl~l r~ lce or reflection colours of blue, green, yellow, red, etc.
Foundations in the form of water-in-oil Pmlllr;- n~ are well known and provide good coverage and good skin feel, wear and ap~ G.a..ce. These have, however, not been ~ r~ fill from the vi. ~ of colour correction of the skin tone and for reducing skin redness.
It would be desirable to provide a cosmetic make-up ~ .o~ which delivers not only good coverage to the sk;in but also which serves to reduce any unevenly coloured or red skin tones. Attempts have been made in the past to correct red facial skin tones by ~ppli~ti~n of a green-coloured foundation followed by application of a conventional pigmented foun~l~tion It would be ri~sir~hhP therefore, to provide a single pigmented foundation c~ ;orl which delivers both skin colour corrective benefits and good coverage, but does not appear green on the skin.
It is acco.dill~;ly an object of the invention to provide a pi~m~n~ed make-up co...?G~;u~ in the form of a water-in-oil em~ on which exhibits good muia~ a~ion together with good coverage and skin colour corrective benefits.
Sllmm~ry of the ~nvention According to the present invention there is provided a make-up co,l.~o ,i~ion in the forrn of a water-in-oil or oil-in-water emulsion comprising:
_ _ _ _ _ ::
;' ~ 2 1 9596 ~
WO96~03962 F~, IIU~
~ , .
a) from about 1% to about 50% by weight of silicone oil selected from volatile silicones, non-volatile silicones and rnixtures thereof, b) optionally up to about 30~/0 by weight of h~
c) from about 0.1% to about 25% by weight of at least one coated or uncoated iron oxide-type pigment, and d) from about 0.1% to about 10% by weight of a TiO2-coated platelet-type illt~ .felcl.~e pigment material having a TiO? layer thickness of from about I 20mn to about 160nm or a whole number multiple thereof.
The water-in-oil PmllicionC of the present invention provide improved colour COll.~ , benefits together with good coverage, skin ~L J~.aLaL.ce and superior IIIOi ,~ Lion.
All levels and ratios are by weight of total cull~llo~ n~ lmless otherwise in iiC~tPfi Chain length and degrees of aLh,~' -m are also specified on a weight average basis.
n.~t~ilP I nPc~ tinn of thP Tnv~ntil-n The make-up c~ ;li..., accu..lillg to the present invention culll~Lises a mixture of volatile and/or non-volatile silicones, iron oxide-type pigment, T;02 platelet ty~pe illt~,.r~ ,.,ce pi~ment materiai and optionally ILI I 1 l l 1~ The c- ~ i l inn is in the forrn of a water-in-oil emulsion.
A first essential CvlllyOIl~ of the water-in-oil emulsion is â silicone oil which in preferred embodhll~ culll~lises a mixture of voiatile silicones and non-volatile silicones. The silicone oil is present in an amount of from about 1% to about 50% by weight. Suitable volatile silicone oils include cyclic and linear volatile polyorg~nogilo~-~nf~q (as used herein, "volatile" refers to ~ose materials which have a ~ vapour pressure at ambient conditions).
A description of various volatile silicones is found in Todd, et al..
"Volatile Silicone Fluids for Cocm~ticsll~ 91 Cosmetics and roilelries 27-32 (1976).
219Jr961 ~ W0 96/03962 ' - ; ~ 5,-1 10 Preferred cyclic silicones include polydimethylsiloxanes cont~ining from about 3 to about 9 silicon atoms, preferably containing from about 4 to about 5 silicon atoms. Preferred linear silicone oils include the polydimethylsiloxsnes containing from about 3 to about 9 silicon atoms.
The linear volatile silicones generally have viscosities of less than about 5 cPntictok~ps at 25~C, while the cyclic materials have viscosities of less thsTt about 10 c~ (. L ~c Examples of silicone oils useful in the present invention include: Dow Corning 344, Dow Corning 21330, Dow Coming 345, and Dow Corning 200 (" ~ ~ ~r,.. I,l.ed by the Dow Corning Corporation): Silicone 7207 snd Silicone 7158 (~ lrn- m cd by the Union Carbide Corporation). SF:202 ("- .".r.. ~"~,d by General Electric) and SWS-03314 (m Innf~rtllred by Stauffer Chemical).
Suitable non-volatile silicones preferably have an average viscosity of from about 1,000 to about 2,000,000 mm2.s~l at 25~C, more preferably from about 10,000 to about 1,800,000 mm2.s~l, even more ~1~ fi .dbl~
from about 100,000 to about 1,500,000 mm2.s~l . Lower viscosity non-volatile silicone conrliti~nin~ agents, however, csn slso be used.
Viscosity csn be measured by means of a glsss capillary ViaCOIII~t~ . as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970. Suitable non-volatile silicone fluids for use herein include polyalkyl cil/~x~nPc, polyaryl ~ Y~nPc, polyalkylaryl 5ilnY~nPc, polysiloxanes with amino functional stth5ti~ ionc, polyether siloxsne copolymers, snd mixtures thereof. The siloxanes useful in the present invention may be Pnfln~rped with sny number of moie~ies, inclll~ling for example, methyl, hydroxyl, ethylene oxide, propylene oxide, amino and csrboxyl. However, other silicone fluids having skin cnn~iitinning properties may be used. The non-volatile polyalkyl siloxane fluids that may be used include, for exsmple, polydimethylcilnx~r~Pc These siloxsnes are available, for exsmple, from the General Electric Compsny as a Viscasil (RTM) series snd from Dow Corning as the Dow Corning 200 series. Preferably, the viscosity ranges from about 10 mm2.s~l to about 100,000 mm2.s~1 at 25~C. The polyalkylsryl siloxane fluids that ~ may be used, also include, for example, pol~ ylpL~ iloxsnes.
These siloxanes sre available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid. The polyether siloxane copolymer that may be used includes, for exsmple, a polypropylene oxide modified ~h'096/03962 96 1 P II.J ,o dimethylpolysiloxane (e.g., Dow Coming DC- 1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
References disclosing suitable silicone fluids include US-A-2,826,551, Green; US-A-3,964,~00, Drakoff, issued June 22nd, 1976; US-A-4,364~837, Pader; and GB-A-849,433, Woolston. In addition, Silicone C~ o..,,ds di~L~ibu~d by Petrarch Systems Inc., 1984 provides an extensive (though not exclusive) listing of suitable silicone fluids.
Preferred non-volatile silicones for use herein include poly.liu~ ocil~ xarle-polyoxyalkylene copolymers cont~ining at least one polydiorg~n~cil~y~np segment and at least one polyoxyalkylene segment, said polydiorg~lnnq~ y~n~ segment c~n~ictin~ essentially of RbSiO(1 b)/2 siloxane units wherein b has a value of from about 0 to about 3, inclusive, there being an average value sf all~Jlu~illlat~ly 2 R radicals per silicon for all siloxane units in the copolymer, and R denotes a radical selected from methyl, ethyl, vinyl, phenyl and a divalent radical bonding said polyoxyalkylene segment to the polydiorgPnnsiloY~nP segrnent, at least about 95~/0 of all R radicals being methyl; and said polyoxyalkylene segment having an average rn- lecnl~r weight of at least about lO00 and concicting of from about 0 to about 50 mol percent polyoxypropylene units and from about 50 to about 100 mol percent polyoxyethylene units, at least one terminal portion of said polyoxyalkylene segment being bonded to said polydiorpPn~ciloy le segment, any terminal portion of said polyoxyalkylene segment not bonded to said polydiorE~Pn-silox~nP
segment being satisfied by a t~ ,";n~1l;..p radical; the weight ratio of polydiorganosiloxane segrnents to polyoxyalkylene segments in said copolymer having a value of from about 2 to about 8. Such polymers are described in US-A-4,268,499.
2 ~ 9~5 9 ~ 1 ~ WO 9ii/03962 r~ s~
More preferred for use herein are polydiorganosiloxane-polyoxyalkylene copolymers having the general forrnula:
~ E~3C--- Si --o--(Si--O)--~Si--O~y--Si--CH3 CH 3 C~ 3 C3H 6 CH 3 o -- (c2H4o1 a (C3H~O) bR
wherein x and y are selected such that the weight ratio of polydiorganosiloxane segments to polyoxalkylene segments is from about 2 to about 8, the mol ratio of a:(a+b) is from about 0.5 to about 1, and R is a chain ~- I l 1;~ lAI ;UP group, especially selected from Lyd~ug~
hydroxyl; alkyl, such as methyl, ethyl, propyl, butyl, benzyl; aryl, such as phenyl; alkoxy such as methoxy, ethoxy, propoxy, butoxy; t~,~ylv.~y, aryloxy, such as phenoxy; alkenyloxy, such as vinyloxy and allyloxy;
acyloxy, such as acetoxy, acryloxy and plvl~ onv~y and amino, such as dimethylamino.
The number of and average molecular weights of the segments in the copolymer are such that the weight ratio of pOlydivl~:ano~iloxane segments to polyoxyalkylene segments in the copolymer is preferably from about 2.5 to about 4Ø
Suitable copolymers are available ~ o~"~ ,;ally under the ~ 5 Belsil (RTM) from Wacker-Chemie GmbH, G~Crh ~ n~b. ~ ~; 1, S, Postfach D-8000 Munich 22 and Abil (RTM) from Th. Cc' ~ It Ltd,. Tego House, Victoria Road, Ruislip, MiAAI~seY HA4 OYL. P~. Li~,ulàlly preferred for use herein are Abil WE 09, Belsil (RTM) 6031, Abil (RTM) ~ B88 183 and DC3225C. A preferred silicone herein is known by its CTFA A.o~ign~tjnn as rlim~thi~-~n~ copolyol.
w0961039~2 ~ 2 ~ 9596 1 E~,",l"J'I to ~
The silicone oil phase preferably comprises from about 2% to about Z5%, more preferably from about ~/o to about 15% by weight of composition of non-volatile silicones.
Another desirable COlllpull..lt of the co,.ipo~itions herein is a hllmPc~qn~
or mixture of hllmrct~llte The h---"~ or mixhrïe of hllll~F~
herein is preferably present in an amount of from about 0.1% to about 30~~O, more preferably from about 5~/0 to about 25%, and especially from about 10% to about 20% by weight of C~ . l ;nn Suitable l .. ~ h. l are selected from glycerine and poly~4~,ylL~ ylate lubricant having a viscosity at 25~C of 300,000 to 1,100,000 cps; a specific gravity at 25~C of I to 1.2g~ml, a pH of 5.0 to 5.5; a bound water content of 33 to 58%; and, a free ~7ater content from 5 to 20%.
The h ~ thlll can be h~Cul~Jv~ ,d at least partly into the oil phase of the water-in-oil emulsion so as to form 8 ".~.ln~ e l"Illl~ -in-oil-in-water f~ a' 1ll. In these ~ ..,1~l:.". ,l~ the Oa phasc c-~ from about 0.1% to about 10%, preferably from about 0.1% to about 3% by weight of l..-,..~ ~l on a cnmr~citinn basis. Suitably, the l,.~...~- l...,l is introduced into the o~il phase in the fonn of a mixture with or h~ul~v~ted within a particulate lipophilic or hy~Lv~hv[~ c carrier material, for example a cross-lif~lced lly~Lvpllobic acrylate or methacrylate copolyrner as described in detail hereaf~er.
Suitable polygly~ y~ LLa~ylate lu~ are marketed by &uardian Chemical Corporation under the trademark "Lubrajel". The "Lubrajels"
identified as "Lubrajel DV", "Lubrajel hlS", and "Lubrajel CG" are preferred in the present invention. The gelling agents sold under these tlad~lllalL~ contain about 1% propylene glycol.
Other suitable hnm~rt~nte include sorbitol, p~nth~n-~1c, propylene glycol, butylene glycol, hexylene glycol, alkoxylated glucose d l;V~ s, such as Glucam (RTM) E-20, hexanetriol, glucose ethers, sodiurn hyaluronate, and mhctures thereof. Urea is also suitably added as a h..l~c~ in the internal aqueous phase.
The panthenol moisturiser can be selected from D-panthenol (ER]-2,4-dihydroxy-N-[3-hydluA,y~ ,yl)]-3,3-dimethylbu~nide), DL-p~nthrn~
,, _,, _ . _ _, _ , , , , , , , , , _ ~ W0 96/03962 calcium p~ntoth~n~te, royal jelly, p~nth~tin~ pantotheine, panthenyl ethyl ether, pangamic acid, pyridoxin, pantoyl lactose and Vitamin B
complex.
In preferred embodiments, the hl~m~ct~nt is selected from glycerine and sodium hyaluronate, and mixtures thereo~ Chemi(~lly, glycerine is 1,2,3-1,.u~ . hiol and is a product of CC711~ ;. 'When present, sodium hyaluronate is preferably illCUl~Ulai~,d at a level of from about 0.05% to about 2% by weight. The mixtures are especially valua'ble herein from the viewpoint of providing enhanced " ",;~, . "; ~1 ;on.
Another essential ~o~.,p,~ herein is at least one iron oxide-type pigment. The iron oxide-type pigment used herein can be either coated or lmro ItPA The pigments can be treated with cc.,..l.o~ such as amino acids, silicones, lecithin and ester oils. The more preferred pigments are the silicone (polysiloxane) treated pi~rnPntC
The total cù--~ LIdhon of the iron oxide-type pigment in the c- ~ ~ i ~v~ll ;o~
is from about 0.1 to about 25% by weight and is preferably from about I
to about 15% by weight of the total c~ .l.o~ The exact COIlCt:llLla~iOil of pigments in the co.. ~1~~~ l ;o.- is A~ to some extent upon the specific mixture of pigments selected for use in a foundation make-up or blusher to achieve the desired shades. The preferred compositions contain from about 2% tO about 20% by weight of titanium dioxide and most preferably from about 5% to about 10% by weight of titanium dioxide.
Another essential cu,l,~un..lt of the cosmetic cc,lll~vailions of tne invention is a TiO2-coated platelet type illt~.lf~l. .l~,e pigment material.
Preferably, the illt~ .f~L~,I.,e pigment material Cuul~ platelet type mica which is coated with TiO2. The colour of the reflected light varies A-~pPnAinp on the thickness of the layer. The i...~,lf~ ll,ncc pigment material used in the present invention c~ at least a proportion of pigment material having a TiO2 layer thickness of from aoout 120nm to about 160nm or a whole number multiple thereof such that the pigment itself has an overall green a~ ance when applied to skin as a result of light reflection from the pigment platelets. Preferred i.it~ .r~ .~ nce pigment materials for use in the comroiitit)n of the invention are those 9 ~ 9 ~
WO 96~03~6~
supplied by Merck under the trade name Timiron, especially Timiron Super Green.
The TiO2-coated platelet type h~ f~ l.ce pigment material is used herein at a level of from about 0.1% to about 10%, preferably from about 0.1% to about 5~/O, more preferably from about 0.59/O to 3~/O by weight of ~ u.l.p~,~iLion.
Other suitable pigments for use herein can be inorganic andlor organic.
Also included with-in the term pigment are rnaterials having a low colour or lustre such as matte finishing agents, and also light 5c~t~in~ agents.
Examples of other suitable pigments are acylgl, ~~ iron oxides, U~ ;r'f blue, D~C dyes, carmine, and mixtures thereo~ Depending upon the type of rn~ke-up cv~ l/v~;l ;on, whether fs~m~ ion or blusher, a mixture of pigrnents will normally be used.
The Çu~ c.,...~ u.~ can also include from about 0.1% to about 10% of at least one matte finishing agent. The function ofthe matte finishing agent is to hide skin defects and reduce shine. Such co;"..~ ,ally a~c p~ inorganic agents, i.e., those included in the CTFA Cosmetic rngredient Dictionary, Third Ed., as spherical silica, hydrated silica, silicone-treated silica beads, mica, talc, polyethylene, titanium dioxide, b~ntrmit~ hectonte, kaolin, chalk, ~ lu~ euu~ earth, attapulgite and the like may be utilized. Of ~ li. ul.u n~filln~c~ as a matte finishing agent is low lustre pigment such as titanated mica (mica coated with titanium dioxide) coated with barium sulfate. Of the inorganic r~ useful as a matte finishing a~ent low lustre pigment, talc, polyethylene, hydrated silica, kaolin, titanium dioxide and mixtures thereof are pallicukuly preferred. Materials suitable for use herein as light-s~ . i"p agents can be generally described as spherical shaped inorganic materials having a particle size of up to about 100 microns, preferably from about 5 to about 50 microns, for example spherical silica particles. Highly preferred from the viewpoint of oil absorption and shine reduction, especially in ~ cg~t~ininp products, are spherical silica particles having a specific surface area (N2, BET) of at least 150 m2/g (ASTM-D3663-9 1 ) and a pore volume of at least 0.5 ml/g (ASTM-D4222-91~.
~ WO 9C103962 , ~ 2 ~ 9 ~ 9 6 t F~
The bal nce of the composition of the present invention colllp.;se .
deionized water. The composition preferably comprises from about 15%
to about 95%, more preferably from about 20% to about 80% by weight of the oil phase, and from about 5~/0 to about 85%, more preferably from about 20% to about 80% by weight of the water phase.
The make-up compositions of the present invention can also comprise a particulate cross-limced hyd.o~llob;c acrylate or ~ l.a~ .~/late copolymer.
This copolymer is ~Jal~ ~ly valuable for reducing shine and controlling oil while helping to provide effecdve mni~hn i7~ri--~n benefits.
The cross-linked hy.Lul.hobic polymer is preferably in the form of a copolymer lattice with at least one active ingredient dispersed uniformly throughout and elllla~cd within the copolymer lattice. All~.lla.h,~ ly, the hy~Lupl.ob:c polymer can talce the form of a porous particle having a surface area (N2-BET) in the range from about 50 to 500, ~Icr~ lably 100 to 300m2/g and having the active h.~;., l;~..l absorbed therein.
The cross-linked hyLù~,hob;c polymer when used herein is in an amount of from about 0.1% to about 10%, I..ef~,.d'~l~ from about 0.3-3% by weight and is IJI~ir I !y il.cull w..t.,1 in the exte nal silicone-c~ .;..;..g oil phase. Tne active i~ ll can be one or more or a mixture of skin compatible oils, skin compatible 1..~ ;, emollients, moisturizing agents and sunscreens. The polymer material is in the form of a powder, the powder being a comhin~d system of particles. The system of powder particles forms a lattice which includes unit particles of less than about one micron in average diameter, agglomerates of fused unit particles of sized in the range of about 20 to 100 microns in average diameter and ag~,,t, s of clusters of fused agglomerates of sizes in the range of about 200 to 1,200 microns in average diameter.
The powder material of the present invention which can be employed as the carrier for the active ill~ l can be broadly ~le~r~iked as a cross-linked "post absorbed" hydrophobic polymer lattice. The powder preferably has entrapped and dispersed therein, an active which may be in the form of a solid, liquid or gas. The lattice is in particulate form and conctit~tec free flowing discrete solid particles when loaded with the activematerial. Thelatticemaycontaina~ e.~ -..in~dquantityofthe active material. The polymer has the structural formula:
, ~tO 96/03g62 ~ ' ' '. t ~ 2 1 9~96 ~ r~ . tO
CH3 ¦ C~3 C=O C--O
R' R' ' C=O
CM~ C
where the ratio of x to y is 80:20, R' is -CH2CH2- and R" is -(CH2)1 ICH3.
The hydrophobic polymer is a highly c}osslinked polymer, more particularly a highly cross-linked polyrnethacrylate copolymer. The material is m~mlf~rt~lred by the I)ow Corning C.,.~o,~l~iu,., Midland.
Michigan, IJSA, and sold under the trademark POL~RAP (RTM) . It is an ultralight free-flowing white powder and the particles are capable of a~50~ b ;l~g high levels of lil-sphili~ liquids and some hydrophilic liquids while at the satne time l..~ t~ a free-flowing powder character. The powder structure consists of a lattice of unit particles less than one micron that are fused into agglomerates of 20 to 100 microns and the agglomerates are loosely clustered into macro-particles or ag~ es of about 200 to about 1200 micron size. The polymer powder is capable of cnn~ininp as much as four times its weight of fluids, emlllcionc dispersions or melted solids.
~ W0!)6~03962 ' ' ''~ 21 9596 ¦ r~.,.J.,,s :c Adsorption of actives onto the polymer powder can be accomplished using a stainless steel mixing bowl and a spoon, wherein the active is added to the powder and the spoon is used to gently fold the active into the polymer powder. Low viscosity fluids may be adsorbed by addition of the fluids to a sealable vessel cont~ining the polymer and then tumbling the materials until a co .~ . L~,y is achieved. More elaborate blending eqnipmPnt such as ribbon or twin cone blenders can also be employed. The preferred active in~ for use herein is glycerine.
Preferably, the weight ratio of 1,.1...~ carrier is from about 1:4 to about 3:1.
Also suitable as a highly cross-linked polymethacrylate copolymer is Micl u~,oll~Ses 5647. This takes the form of generally spherical particles of cross-linked h~ u~llOb C polymer having a pore size of from about 0.01 to about 0.05~m and a surface area of 200-300m2/g. Again, it is preferably loaded with 1~ in the levels d~srrihet above.
The cv5llpo~ ions of the invention can also contain a hydrophilic gelling agent at a level ~Icf~..dl)ly from about 0.01% to about 10%, more preferably from about 0.02% to about 2%, and especially from about 0.02% to about 0.5%. The gelling agent preferably has a viscosity (1%
aqueous solution, 20~C, Brookfield RVT) of at least about 4000 mPas, more preferably at least about 10,000 mPa.s and especially at least 50,000 mPa.s.
Suitable hydrophilic gelling agents can generally be described as water-soluble or colloidally water-soluble polymers, and include cellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose, h~d.u~,u~ylmethyl cellulose), polyvinylpyrrolidone, polyvinylalcohol, polyqu~t.~mil~m-10, guar gum, hy.hu~ u~,yl guar gum and xanth~n gum.
Among suitable hydrophilic gelling agents are acrylic acid/ethyl acrylate copolymers and the carboxyvinyl polymers sold by the B.F. Goodrich Company under the trade mark of Carbopol resins. These resins consist essentially of a colloidally water-soluble polyalkenyl polyether crosslinked polymer of acrylic acid cros~link~d with from 0.75% to 2.00% of a cro~linkin~ agent such as for example polyallyl sucrose or W0 96/03962 ~ 2 ~ 9 5 ~ 6 1 I ~
polyallyl pentaer~thritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980, Carbopol 951 and Carbopol 981. Carbopol 934 is a water-soluble polymer of acrylic acid crossliniced with about 1%
of a polyallyl ether of sucrose having an averagc of about 5.8 allyl groups for each sucrose molecule. Also suitable for use herein are hydrophobically-modified cross-linked polyme~, of acrylic acid having ~mphir~thic tJIu~7,,L~,5 available under the Trade Name Carbopol 1382, Carbopol 1342 and Pemulen TR-I ~C IFA DPci~tit-n AcrylatesllO-30 Alkyl Acrylate Crosspolymer~. A comhin~tinn of the polyaikenyl polyethercross-linkedacrylicacidpolymerandt'nehy~L-r'l L: ~Iy modified cross-linked acrylic acid polymer is also suitable for use herein.
The gelling agents herein are particularly valuable for providing excellent stability ~,haL~ .L~;li ,Lics over both normal and elevated temperatures.
Neutr~li7in~ agents suitable for use in n. ,.~ acidic group ~o-.
hydrophilic gelling agents herein include sodium 4~,~dlu~i~c~ p,,.t~
hydroxide~ ~Tnmr~nillm hydroxide" ~ r~ .ol_...;..- and t~jeth7lnr~ nin~
T~e make-up comrocitit~n~ herein ca n a~ it~ lly conprise an emollient. Fmo~ .ntc suitable for the compositions of tne present invention include na~tural and synthetic oils selected ~m mineral, vegetable, and animal oils, fats and waxes, fatty acid csters, fatty alcohols, alkylene glycol and polyalkylene glycol ethers and esters, fatty acids and mixtures thereof.
Suitable ~7~ tte for use herein include, for example, optionally hydroxy-s-ln.,llL s~i Cg-Cso ~ n ~d fatty acids and esters thereof, C l-C24 esters of C~-C30 saturated fatty acids such as isopropyl my;istate, cetyl palmitate and octyldode. ~hl,rl;a~dLc IWickenol 142), beeswax, saturated and un~tln at~d fatty alcohûls such as behenyl alcohol and cetyl alcohol, hy(llu- ~kons such as mineral oils, p~.~luln~
and squalane, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26 1976), lanolin and lanolin derivatives, such as lanolin alcohol ethoxylated, hyd~u~ Led and ac,.yli l~d lanolins7 cholesterol and derivatives thereof,~ animal and vegetable triglycerides such as almond oil, peanut oil, whoat germ oil, linseed oil, jojoba oil, oil of apricot pits, , . . . . . .
, T ,, ~ j V i~ ~ 2 1 ~ 5 ~ 6 1 ~ W096/03962 ' '' : :', ._I/IJ~_, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grapeseed oil, and sunflower seed oil and C l C24 esters of dimer and trimer acids such as diisopropyl dimerate, diisostearylmalate, diisostearyldimerate and lliiSua~cài.~'lliilllCLdl~
Preferred emollients are selected from cetearyl ieon~m~n~t.~, isopropyl psllmit~t-o, isopropyl iso~t~ , cetyl ocr~no~tP~ cetyl acetate, trioctyl citrate, PEG isoceteth-3 acetate, dioctyl maleate, propylene glycol dicaprylate/~lir~pr~t~, caprylic/ capric triglyceride, mineral oil, PPG-20 methylglucose ether, and lanolin alcohol, and mixtures thereof. These emollients may be used inrl~p~n-lPntly or in mixtures and may be present in the cul.lpo~ilion of the present invention in an amount from about 1%
to about 30% by weight, and preferably are present in an amount from about 5D/o to about l 5% by weight of the total c~
The c~ po~;l ;.~-. may also contain 9,~ t~ materials such as, for example, Çlag,iallces~ fillers such as nylon, sun-screens, p.~a~dti~es, proteins, antioxidants, chelating agents and water-in-oil Pnn~ ifiprs as u~
Another optional c~ pùn .1 of the make-up composition is one or more ultraviolet absorbing agents. Ultraviolet absorbing agents, often described as ~uu~ e~ g agents, can be present in a c~n~ l ;on in the range of between about 1% and about 12% by weight, based on the total weight of co ~ OC l ;~ ~ Preferably, the W abso- I,;..g agents constitute between about 2% and 8% by weight. More preferably, the W
absu.b;l.g agents can be present in the cV~ v~ n in a cùllc~ alion range of between about 4~/0 and about 6% by weight. Of the ultraviolet absorbing agents suitable for use herein, t- .,>,~ph~ -3, octyl dimethyl PABA ~Padimate O) and mixtures thereof are p~li~ ulally preferred.
Ultrafine TiO2 is also suitable for use herein.
A chelating agent can also be hlcul~vlat~ .i in the make-up composition.
A chelating agent is preferably present in the cornposition in a concentration in the range of between about 0.02% to about 0.10% by weight, based on the total weight ofthe co...l.-,~;lion. Preferably, the ~ s W096/03962 ~ 2 ~ 7u t _ ,,~ c chelating agent is present in a CU1l~ t llilo~iOQ in the range of between about 0.03% and about 0.07~/O by weight, based on the total weight of the composition. Among the chelating agents that may be included in the composition is trisodium EDTA.
Another optional but preferred cu.ll~o~ of the f~t~lnr7~tinn cc,~ o~;Liu-isoneormorepreservatives. The~n.~,.,. rdli~,C'~ '; tninthe foundation c~tmpn~hion, based on the total weight of that co.,.~ ;on~ is in the range of bet~veen about 0.2% and about 0.8% by we;ght, preferably between about 0.4% and about 0.6% by weight. Suitable preservatives for use herein include f1;~7 ~ yl urea, methyl paraben and ethyl paraben, and mixtures thereo~
Another optional but preferred co.ll~o~ of the f~ u l~a~iO~ c ~ ; tn is a sebum spreading agent. The sebum spreader is present at a level of from about 0.0 l% ~û about 5~/O by weight of c-,., .l .. . ~ . A preferrod sebum ~ o1hlg agent is sodium Cg-C16 isoalkyL..l~,c~ Jl~
sulfonate (Biopol(Rl~I) OE).
A lower (C l-C6) alcohol may also be present in the fol~n~ ~finrt of the present invention at a level of from about 0.5~/O to about 10% by weight of culll~ ition. Suitable lower alcohols for use herein include ethanol, hexylene glycol, bu~lene glycol, propanol and propylene glycol, preferably ethanol.
The make-up comrocitionC of the present invention can be in the form offou.l~l a ;u.,~ blushers, c~ compâct powders, and the like, preferably as follnfi~tionc and blushers.
The following Table is provided to illustrate cnmr~Citi~nq of the make-up of the present invention:
Example I Il III IV V Vl VII VIII
~YI Wt Wt Wt Wt Wt Wt Wt o~O o~O ~/0 ~/0 ~/~ YO ~/0 ~/0 A.
Cetyloctanoate 2.00 o.o o.o 2.0 0.0 0.0 0.0 0.0 Cyl 1...,.. ,1.: ....~ &.57~ 12.Z5 12.25 15.0 12.0 g.574 8.57 15.58 WOg6/03962 ~ q596 1 r~ ,s~ ~o Cy~ ml th;~ n~ /
~lim~th~ n~l copolyol (90:10) 17.16 15 0 20.0 5 0 8 0 13 017 16 12.5 Plul.yl,ualaL~Il 0 25 0.25 0.25 0 250.25 0.250.25 0 25 laureth-7 0.5 O S 0.0 0 5 0.0 0.5 0.0 0.5 Dioctyl maleate 0 0 0.0 0.0 0.0 10 0 0.0 0.0 0.0 Di.. ~ u.l~ 0 0 0 0 0 0 3 0 5.0 10 0 0.0 0 0 B ~ 3 0 0 0.0 0.0 0.0 0.0 2.0 0.0 0.0 Propylene glycol 0.5 0.5 0.0 0.0 0.0 0.0 0.0 0.0 Dicaprylate/
Dicaprate 0.0 0.0 0.0 5.0 0.0 10.0 0.0 0 0 Titanium~ Dioxide 8.25 6.0 1.5 6.0 8.0 200 9.0 70 Titanium Dioxide treated (Aluminium hydrate, stearic acid) 0.25 0.5 3.0 0.250.25 0.0 0.25 0.25 Titanated Micas 0.1 0.1 0.1 0.25 1 0 0 0 0.1 0 1 Tâlc 3.387 4.5 6.0 0 7 0.7 0.7 3 387 4.0 Nylon 0 0 0-0 ~-~ ~-~ 0 5 ~ ~ ~ ~ ~ ~Timiron Super 2 0 2.0 3 0 2 0 0.1 2 0 0.5 2.0 Green WO 96103962 ' ~ ~ .
Example I 11 111 IV V Vl VII Vlll ~t Wt Wt Wt Wt Wt Wt Wt .~o % o/o o~o o~O 0~o 0~o O~
C.
C,~. 1.. 11,:. ,"" I
h.......
copolyol (90:10)1.858 1.5 1.85 5.0 1.0 1.0 1.858 1.0 Acrylates Copolyrner Q.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 Acrylates Copolymer ~loaded with glycerine) 1.0 0.0 6.0 1.0 0.0 1.0 1.0 0.0 Yellow Iron Oxide 1.2 1.2 0.6 0.4 1.2 1.2 1.2 1.2 Red Iron Oxide 0.49 0.6 0.6 0.490.49 0.2 0.6 0.42 BlacklronOxide 0.16 0.1 0.24 0.1 0.1 0.240.24 0.22 Ultramarine Bluea.o o.oo o.oo o.l o.o o.o o.o o.o Cy~ h.--. 0,0 0,0 0.0 0.0 0.68 0.0 0.0 0.0 Silica (spheron P1500) 3.0 6.0 -- 0.1 -- 0.0 Silica besds (Sphe~n L1500) 0.0 0.0 1.0 0.1 0.5 0.5 Synthetic Wax 0.1 0.5 O.S 0.1 ~ 0.1 Arachidyl behenate 0.3 -- 0.3 0.0 0.3 0.3 0.3 Stearic Acid 0.0 -- ~ -- -- -- 2.5 0.0 Palmitic Acid 0.0 -- - - 2.5 -- 0.0 096/039G2 , 2~95961 r~".,~
Example I 11 111 IV V Vl Vll Vlll Wt Wt Wt Wt ~h't Wt Wt Wt o~ o/O o~o o/o o/o ~/0 /0 /0 Trihydroxy-stearul 0.3 0.3 1.5 1.5 - 0.3 C~ 1.0 4.0 -- -- 4.0 4.0 4.0 1.0 Beeswax 1.5 1.2 -- -- 1.3 -- - 0.0 A bil ~Vl~ 09 -- 3.0 - -- 0.0 Palm Oil -- -- - 4 o.o Al Mg hydroxy stearate/
(20:80) 0.5 1.5 1.8 1.5 10.0 3.0 3.0 0.0 Ethylene btassylate 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 B H T 0.05 0.05 0 05 0 05 0 05 0 05 0 05 0 05 H.
Deiorlized water -- - --~- - -100- - ---- -~-- --~--to Methyl paraben 0.12 0.15 0.15 0.12 0.12 0.12 0.15 0.12 Propylene glycol 8.0 8.0 0.0 0.0 1.75 8.00 0.0 0.0 Sodiuro c~loride 2.0 1.4 1.4 0.5 2.0 2.0 2.5 2.0 Sodium dil.~' 0.3 0.3 0.3 0.8 0.8 0.3 0.8 03 Glyceti~e 0.0 15.0 10.0 5.0 6.5 3.0 3.0 10.0 Trisodium EDTA 0.0 0.0 0.0 0.0 0.0 0.0 0.01 0.0 Tr;~ 0.0 0.0 0.0 0.0 0.0 0.0 0.75 0.0 Allaraoin 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 Biopol OE -- 0.5 -- 0.5 0.0 ELh2m ol - 6 -- - - 2 -- 0.0 ~t q596 ~
... ,......................................... _ wo 96/03962 Example I 11 III IV V Vl Vll VIIT
~It \,~/t Wt Wt Wt Wt Wt Wt ~/ 0/o o/O o~O o~o % /o /o Panthenol ~ 2 -- -- 2 -- 0.0 h~L.,~
cellulose 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 sunscreen 0.0 0.0 0.0 0.2 0.2 0.0 0.0 0.0 Sodiutn L~ ' . 0.0 0.05 0.08 0. l 0.0 0.0 0.2 0.0 Deionized Water 0.0 0.0 0.0 0.0 10.0 -- -- 0.0 T~ ~ -Aluminium Silicate ~ 0.Z -- -- 0.0 Propylene Glycol 0.0 0.0 0.0 2.0 0.0 0.0 0.0 0.0 Xanthan Gum 0.0 0.0 0.0 0.08 0.0 0.0 0.0 0.0 Essential Oils 0.0 -- -- 0.20 -- -- -- 0.0 Perfilme Oil 0.0 0.25 -- 0.20 -- -- 0.0 Vitamin A Q05 -- -- ~~ ~~ ~~ ~- ~ ~
Palrnitate 0.0 0.05 -- -- -- - -- ~ ~
Aloe Vers Gel 0.0 0.0 3.0 -- -- -- -- 0.0 Extract 0.0 0.0 0.1 ~ 0.0 The various CO~ O~ ' listed in the Table have been se~e1 into groups, the conctinlPntc of each group being mixed together before being added to members of the remaining groups in acc- ~-l~nce ~ith the IJlu~,edu~ set forth below.
~ W096/03962 ~ 2 1 9596 1 ~"~
In the first step, the mixture of components of phase A is stirred for approximately 5 minutes with sheer mixing until homogeneous. With high speed sheer mixing, the materials of phase B are added gradually to A and the batch is mixed for 35 minutes until dispersed.
The colll~o~ of phase C and then phase D are slowly added to the mixture of phases A and B with high shear mixing until ~ pPr5e~ Silica is added at this point and dispersed through the mixture.
The culllpon~ of phase E are added into the resulting batch which is then heated to 84~C and mixed until dispersed. The vessel is cooled to 45~C and the premixed phase F is added. The batch is mixed until homog~n~ou~ The mixture is cooled to 30~C and phase G is added.
A premix of phase H is made by mixing all the c-., .,1,. 1l~l .,1~ until c---p'~ 'y dissolved. At 30~C the premix of phase H is added sparingly to the batch mixture with high shear, ensuring that there is no excess water on the surface. The mi7cture is then mixed for 15 minutes. Finally phases I, J, K, and L are added.
The resulting make-up co"~ ;(ioll is ready for packing.
The make-up c~ onc of the Examples exhibit improved moisturisation, application cl~ ics, skin feel and al"~ed.d..ce, together with colour corrective ~Ldl a~,t~ Lics.
Claims (25)
1. A make-up composition in the form of a water-in-oil or oil-in-water emulsion comprising:
a) from about 1% to about 50% by weight of silicone oil selected from volatile silicones, non-volatile silicones and mixtures thereof, b) optionally up to about 30% by weight of humectant, c) from about 0.1% to about 25% by weight of at least one coated or uncoated iron oxide-type pigment, and d) from about 0.1% to about 10% by weight of a TiO2-coated platelet-type interference pigment material having a TiO2 layer thickness of from about 120nm to about 160nm or a whole number multiple thereof.
a) from about 1% to about 50% by weight of silicone oil selected from volatile silicones, non-volatile silicones and mixtures thereof, b) optionally up to about 30% by weight of humectant, c) from about 0.1% to about 25% by weight of at least one coated or uncoated iron oxide-type pigment, and d) from about 0.1% to about 10% by weight of a TiO2-coated platelet-type interference pigment material having a TiO2 layer thickness of from about 120nm to about 160nm or a whole number multiple thereof.
2. A make-up composition according to Claim 1 wherein the platelet-type interference pigment material is mica.
3. A make-up composition according to Claim 1 or 2 comprising from about 0.1% to about 30% by weight of humectant.
4. A make-up composition according to any of Claims 1 or 3 wherein the volatile silicone oil is selected from cyclic polyorganosiloxanes having viscosities of less than about 10 centistokes and linear polyorganosiloxanes having viscosities of less than about 5 centistokes at 25°C, and mixtures thereof.
5. A make-up composition according to Claim 4 wherein the volatile silicone oil is selected from cyclic polydimethylsiloxanes containing from about 3 to about 9 silicon atoms, preferably containing from about 4 to about 5 silicon atoms and linear polydimethylsiloxanes containing from about 3 to about 9 silicon atoms.
6. A make-up composition according to any of Claims 1 to 5 wherein the non-volatile silicone oil comprises a polydiorganosiloxane-polyoxyalkylene copolymer containing at least one polydiorganosiloxane segment and at least one polyoxyalkylene segment.
7. A make-up composition according to Claim 6 wherein the polydiorganosiloxane-polyoxyalkylene copolymer is dimethicone copolyol.
8. A make-up composition according to Claim 3 wherein the humectant is selected from glycerine and polyglycerylmethacrylate lubricants having a viscosity of from about 300,000-1,100,000cps at 25°C, and mixtures thereof.
9. A make-up composition according to Claim 8 wherein the humectant is glycerine.
10. A make-up composition according to any of Claims 1 to 9 wherein the silicone oil comprises from about 2% to about 25%, preferably from about 5% to about 15% by weight of composition of non-volatile silicones.
11. A make-up composition according to any of Claims 1 to 10 wherein the iron oxide - type pigment is silicone treated.
12. A make-up composition according to any of Claims 1 to 11 comprising from about 5% to about 25% by weight of composition of humectant.
13. A make-up composition according to any of Claims 1 to 12 additionally comprising from about 0.1% to about 10% by weight of a cross-linked hydrophobic acrylate or methacrylate copolymer.
14. A make-up composition according to Claim 13 wherein the cross-linked hydrophobic copolymer is in the form of a lattice and wherein at least one active ingredient is dispersed uniformly throughout and entrapped within the copolymer lattice, the active ingredient being selected from skin compatible oils, skin compatible humectants, emollients, moisturizing agents and sunscreens.
15. A make-up composition according to Claim 14 wherein the active ingredient is selected from humectants, preferably glycerine.
16. A make-up composition according to any of Claims 1 to 15 additionally comprising from about 0.1% to about 10% by weight of a matte finishing agent selected from silica, hydrated silica, mica, talc, polyethylene, titanium dioxide, bentonite, hectorite, kaolin, chalk, diatomaceous earth and attapulgite, and mixtures thereof.
17. A make-up composition according to Claim 16 wherein the matte finishing agent is selected from spherical silica or hydrated silica.
18. A make-up composition according to any of Claims 1 to 17 additionally comprising from about 1% to about 15% by weight of an emollient which is a natural or synthetic oil selected from mineral, vegetable and animal oils, fats and waxes, fatty acid esters, fatty alcohols, alkylene glycol and polyalkylene glycol ethers and esters, fatty acids and mixtures thereof.
19. A make-up composition according to Claim 18 wherein the emollient is selected from isopropyl palmitate, isopropyl isostearate, dioctyl maleate, propylene glycol dicaprylate/propylene glycol dicaprate, caprylic triglyceride/capric triglyceride, squalane, mineral oil, cetearylisononoate and lanolin alcohol, and mixtures thereof.
20. A make-up composition according to any of Claims 1 to 19 wherein the oil phase comprises from about 0.1% to about 10%, preferably from about 0.1% to about 3% by weight of humectant on a composition basis.
21. A make-up composition according to any of Claims 1 to 20 comprising from about 15% to about 95%, preferably from about 20% to about 60% by weight of the oil phase, and from about 5% to about 35%, preferably from about 40% to about 80% by weight of the water phase.
22. A make-up composition according to any of Claims 1 to 21 additionally comprising one or more ultraviolet absorbing agents.
23. A make-up composition according to any of Claims 1 to 22 wherein the humectant is selected from glycerin and sodium hyaluronate, and mixtures thereof.
24. A make-up composition according to any of Claims 1 to 23 additionally comprising a C1-C6 alcohol, preferably ethanol.
25. A make-up composition according to any of Claims 1 to 24 in the form of a water-in-oil emulsion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9415451A GB9415451D0 (en) | 1994-07-30 | 1994-07-30 | Cosmetic make-up compositions |
| GB9415451.5 | 1994-07-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2195961A1 true CA2195961A1 (en) | 1996-02-15 |
Family
ID=10759182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002195961A Abandoned CA2195961A1 (en) | 1994-07-30 | 1995-06-30 | Cosmetic make-up compositions |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0774950A4 (en) |
| JP (1) | JPH10503515A (en) |
| KR (1) | KR970704412A (en) |
| AU (1) | AU2915695A (en) |
| CA (1) | CA2195961A1 (en) |
| CZ (1) | CZ23997A3 (en) |
| GB (1) | GB9415451D0 (en) |
| MX (1) | MX9700793A (en) |
| WO (1) | WO1996003962A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0701810B1 (en) * | 1994-09-14 | 2004-11-17 | Shiseido Company Limited | Skin-colour adjusting method, and coloured titanium oxide coated mica used therefor |
| US5849275A (en) * | 1995-06-26 | 1998-12-15 | Revlon Consumer Products Corporation | Glossy transfer resistant cosmetic compositions |
| US5855877A (en) * | 1996-09-06 | 1999-01-05 | Colgate-Palmolive Company | Non-aqueous antiperspirant composition |
| US6117435A (en) * | 1998-06-24 | 2000-09-12 | Color Access, Inc. | Natural look cosmetic compositions |
| FR2791886B1 (en) | 1999-04-07 | 2001-06-01 | Caster | HOMOGENEOUS LIQUID PERFUMING COMPOSITION BASED ON VOLATILE SILICONES |
| US20030157041A1 (en) * | 2000-01-13 | 2003-08-21 | Dreher John D. | Optical makeup compositon |
| EP1532211A1 (en) | 2002-08-30 | 2005-05-25 | Ciba SC Holding AG | Coulored gloss pigments having at least one coating of siox, with x=0.03 to 0.95 for use in cosmetic and personal care formulations |
| 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 |
| US7939489B2 (en) | 2002-12-23 | 2011-05-10 | Avon Products, Inc. | Oil absorbent topical compositions and methods for using same |
| DE10357046A1 (en) † | 2003-12-04 | 2005-06-30 | Beiersdorf Ag | Cosmetic or dermatological preparations containing a combination of green dye and anti-inflammatory agent |
| US7780955B2 (en) | 2004-11-12 | 2010-08-24 | L'oreal | Cosmetic composition with a lightening effect |
| WO2009068462A1 (en) * | 2007-11-27 | 2009-06-04 | Basf Se | Use of zero-order diffractive pigments |
| US9168209B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9320687B2 (en) | 2013-03-13 | 2016-04-26 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9168393B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| US9168394B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
| WO2016061109A1 (en) * | 2014-10-14 | 2016-04-21 | Elc Management Llc | Oil-controlling cosmetic powder |
| WO2021065123A1 (en) * | 2019-10-04 | 2021-04-08 | 株式会社 資生堂 | Solid oil-in-water type emulsified cosmetic |
| CA3189438A1 (en) | 2020-07-21 | 2022-01-27 | Chembeau LLC | Diester cosmetic formulations and uses thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6156113A (en) * | 1984-08-27 | 1986-03-20 | Shiseido Co Ltd | Water-in-oil type emulsified cosmetic |
| US5143722B1 (en) * | 1986-12-19 | 1999-08-24 | Revlon Consumer Prod Corp | Cosmetic makeup compositions comprising water-in-oil emulsions containing pigment |
| US5066485A (en) * | 1987-02-06 | 1991-11-19 | Revlon, Inc. | Cosmetic compositions comprising oil-in-water emulsion containing pigment |
| JP3026582B2 (en) * | 1990-05-24 | 2000-03-27 | メルク・ジャパン株式会社 | Blue-green pigment and method for producing the same |
| TR27424A (en) * | 1993-01-11 | 1995-04-21 | Procter & Gamble | Cosmetic compositions containing surface-treated pigments. |
| JPH07309715A (en) * | 1994-05-17 | 1995-11-28 | Pola Chem Ind Inc | Makeup cosmetic |
-
1994
- 1994-07-30 GB GB9415451A patent/GB9415451D0/en active Pending
-
1995
- 1995-06-30 EP EP95924770A patent/EP0774950A4/en not_active Withdrawn
- 1995-06-30 KR KR1019970700608A patent/KR970704412A/en not_active Application Discontinuation
- 1995-06-30 WO PCT/US1995/008340 patent/WO1996003962A1/en not_active Application Discontinuation
- 1995-06-30 CA CA002195961A patent/CA2195961A1/en not_active Abandoned
- 1995-06-30 JP JP8506496A patent/JPH10503515A/en active Pending
- 1995-06-30 AU AU29156/95A patent/AU2915695A/en not_active Abandoned
- 1995-06-30 CZ CZ97239A patent/CZ23997A3/en unknown
- 1995-06-30 MX MX9700793A patent/MX9700793A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU2915695A (en) | 1996-03-04 |
| MX9700793A (en) | 1997-05-31 |
| JPH10503515A (en) | 1998-03-31 |
| CZ23997A3 (en) | 1997-07-16 |
| EP0774950A4 (en) | 1998-12-23 |
| KR970704412A (en) | 1997-09-06 |
| EP0774950A1 (en) | 1997-05-28 |
| WO1996003962A1 (en) | 1996-02-15 |
| GB9415451D0 (en) | 1994-09-21 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |