CN105848626A - Transparent composition containing oil and microcapsules - Google Patents

Transparent composition containing oil and microcapsules Download PDF

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Publication number
CN105848626A
CN105848626A CN201480070567.4A CN201480070567A CN105848626A CN 105848626 A CN105848626 A CN 105848626A CN 201480070567 A CN201480070567 A CN 201480070567A CN 105848626 A CN105848626 A CN 105848626A
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weight
compositions
microcapsule
acid
oil
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A-L.伯纳德
池田侑市
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LOreal SA
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LOreal SA
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11Encapsulated compositions
    • 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
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • 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
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • 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
    • A61K8/34Alcohols
    • 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
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • 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
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26Optical properties
    • A61K2800/262Transparent; Translucent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42Colour properties
    • A61K2800/43Pigments; Dyes

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)

Abstract

A transparent composition in the form of a nano- or micro-emulsion containing a microcapsule containing releasable colorant(s). The composition contains at least one fatty phase, at least one nonionic surfactant, at least one microcapsule containing releasable colorant(s), and water. This composition provides a high cosmeticity such as emolliency and high slipperiness while giving consumers a color change sensation upon shear.

Description

Comprise the transparent composition of oil and microcapsule
Technical field
The present invention relates to comprise the compositions of oil and microcapsule.More particularly, it relates to microemulsion or nanometer The compositions of emulsion form, it microcapsule including comprising releasable coloring agent.
Background technology
Cosmetic composition is normally used for giving the color of skin beauty, and it is the most rubescent to hide skin defect And/or speckle (redness).Have been developed for many formula up to now.Additionally, response external is stimulated as sheared Power and provide the interest of the cosmetic product that color changes day by day to strengthen.
Generally, realize this purpose by comprising the coloring agent of micro encapsulation in the composition, wherein using After on skin, compositions provides color change.More particularly, color is provided by the microcapsule containing coloring agent Change, described microcapsule is discharging the coloring agent of embedding after rupturing in compositions by applying mechanical force, from And change its color.Mechanism by topical composition drawout and promotes that it penetrates into skin such as friction.Group The change immediately of compound color provides visual aesthetic.
Already known in this area pigment is introduced in cosmetic composition, particularly comprise a large amount of water for skin Skin nursing or the compositions for cosmetic skin.Expect that these compositionss have salubrious (fresh) sense organ after application Effect and the imparting suitable color and luster of skin (color shade).Additionally, the ability that they comprise a large amount of active component obtains Must highly praise.
This salubrious sense organ and optical effect such as in " quickly breaking (quick break) type " formula, in face It is needs in portion's essence (face serum), in eye essence (eye serum) and in foundation cream.
But, introduce a large amount of pigment and can damage salubrious effect: pigment tends to absorb water, causes compositions faster Kill, hence in so that compositions is more difficult to be applied in equably on skin fastly.
Thus, after being administered to skin, the color of this compositions is not reaching to desired requirement about homogeneity. Additionally, once compositions has formed dry film on skin, in practice it is not always possible to remedy this problem.
In order to provide transparent cosmetics, the most use techniques below.This is cosmetics or Dermatology neck Known practice in territory: use oil-in-water (O/W) emulsion.These emulsions (its by be dispersed in aqueous phase oil phase (or Oleophylic phase) composition) there is outer water phase.Therefore, described product more makes owing to salubrious sense that they provide uses People is joyful.But, in the presence of big gauging, they lack stability relatively.For some are applied, favourable It is that there is big gauging, because oil provides skin with comfortable, nourishes it, and when these oil have makeup removing character also Can remove ornaments and formal dress from skin.
Furthermore it is advantageous that have miniemulsion, wherein oil phase is that the least drop is i.e. less than 4 μ m in size The emulsion of the form of drop, because these miniemulsions have the cosmetic sense and generally than thick emulsion more of pleasant Stable.
These emulsions can be prepared (PIT emulsion) particularly by phase inversion temperature (PIT) technology, wherein constitutes the bead of oil phase Average-size is in given limit, and i.e. 0.1 μm is to 4 μm (100nm to 4000nm).Phase inversion temperature (PIT) (or PIT) The principle of emulsifying, theoretically, is well-known to those skilled in the art;It is in 1968 Year is described (J.Chem.Soc.Jpn., 1968,89,435) by K.Shinoda.Have shown that this emulsifying technology makes May obtain stable miniemulsion (K.Shinoda and H.Saito, J.Colloid Interface Sci., 1969,30, 258).Just this technology is applied in cosmetics as far back as Mitsui in 1972 et al. (" phase inversion temperature (PIT) method exists Application in cosmetics emulsifying " (" Application of the phase-inversion-temperature method to the emulsification of cosmetics”);T.Mitsui, Y.Machida and F.Harusawa, U.S. .Cosmet. Perfum.,1972,87,33)。
The principle of this technology is as follows: exceeding phase inversion temperature (PIT) (hydrophilic of emulsifying agent i.e. used and the parent of system Reach between oiliness balance temperature) at a temperature of prepare O/W emulsion (aqueous phase is introduced in oil phase);Higher At a temperature of, i.e. higher than phase inversion temperature (PIT) (> PIT), emulsion is water-in-oil type, and when it cools down, this breast Liquid inverts to become emulsion oil-in-water under phase inversion temperature (PIT), in advance experience microemulsion state.This method makes Must may be readily available diameter and be typically smaller than the emulsion of 4 μm.Live in the emulsifying surface of normally used oil-in-water type Property agent has the HLB (hydrophilic lipophilic balance) in the range of 8 to 18.These emulsifying agents, due to their two Parent's structure, is positioned at oil phase/water phase interface, and therefore makes scattered oil droplet stable.
However, it is difficult to produce the thin O/W emulsion comprising a large amount of oil phase, because this emulsion has destabilization Trend, this destabilization causes aqueous phase and oil phase coalescence and separates, discharging fuel-displaced.In order to improve these emulsions Stability, the concentration of emulsifying agent can be improved;But, the emulsifying agent of high concentration may result in coarse, tacky (clingy Or sticky) sensation, and for skin, eyes and scalp, cause innocuousness problem.
Especially, miniemulsion such as O/W nanoemulsions or microemulsion are due to its transparent or the most translucent outward appearance Special interest is caused in cosmetic product.
Such as, JP-A-H09-110635 discloses a kind of miniemulsion, and it (is made by using polyglyceryl fatty acid ester For surfactant) and C10-C22The combination of 2-hydroxy fatty acid and formed.Additionally, JP-A-H11-71256 is open A kind of miniemulsion, it is formed by using polyglyceryl fatty acid ester and the combination of glycine betaine.
Summary of the invention
Technical problem
It is an object of the invention to provide the compositions with big gauging, it has the transparent or the most translucent of emulsion , the outward appearance of preferably clear, there is color changeable effect and there is acceptable height cosmetic for many consumers Property (cosmeticity).
The solution of problem
The object above of the present invention can be realized by the compositions of nanoemulsions or microemulsion form, described compositions Comprising (a) at least one fat phase, (b) at least one nonionic surfactant, (c) comprises releasable coloring agent At least one microcapsule, and (d) aqueous phase.
Accompanying drawing is sketched
The accompanying drawing being intended to the present invention is described in infinite mode discussed further below, its representative is introduced into according to this The example of the bright microcapsule in cosmetic composition.
[Fig. 1] Fig. 1 is the schematic diagram of the typical structure of the variable color microcapsule that first embodiment of the invention is described, Wherein A1 represents core and B1, C1, D1 and E1 are the different layers that (concentrically) surrounds described core with one heart.
[Fig. 2] Fig. 2 is the microcapsule of the nucleocapsid structure showing the variable color microcapsule B as used by following embodiment 1 The schematic diagram of the first embodiment.
[Fig. 3] Fig. 3 is the schematic diagram of the typical structure of the microcapsule that second embodiment of the invention is described, Wherein A2 represents coloring core, and B2, C2, D2 and E2 are the different layers surrounding core A2 with one heart, in these embracing layers At least one be necessary and preferably include titanium dioxide granule, and other layer is optional.
[Fig. 4] Fig. 4 is that display comprises 3 layers: coloring core internal color layer (inner color layer) TiO2Granular layer The schematic diagram of nucleocapsid structure of variable color microcapsule of the second embodiment of microcapsule.It is included in the right of Fig. 4 Pigment core in Li corresponds to left side granule, and described pigment core includes pigment/lecithin layer (internal color layer) and interior Portion's pigment powder (internal coloring core).
[Fig. 5] Fig. 5 is that display comprises 2 layers: coloring core TiO2Second embodiment of the microcapsule of granular layer The schematic diagram of the nucleocapsid structure of variable color microcapsule.
Embodiment describes
Owing to the compositions of the present invention can be transparent or the most translucent, said composition is preferably for washing liquid (lotion) etc..Owing to dispersion phase is finely divided, the compositions of the present invention can provide skin moistening quality (emollient And slippery feeling (slipperiness) texture).Additionally, due to the compositions of the present invention contain comprise releasable The microcapsule of toner, said composition provides variable color to feel after being applied shearing or pressure by consumer simultaneously.
The compositions of the present invention has dispersion phase, and it is owing to comprising at least one microcapsule of releasable coloring agent Existence and there is less diameter.Therefore, said composition can be transparent or the most translucent nanoemulsions or Microemulsion form.
Hereinafter will in more detailed manner the compositions of the present invention be explained.
1-1. fat phase
The compositions of the present invention comprises at least one the fat phase mainly become by line of oils.Here, " oily " means in room Fatty compound in liquid form or material under temperature (25 DEG C), atmospheric pressure (760mmHg).Cosmetics generally make Those oil can be used alone or with a combination thereof use.These oil can be volatile or nonvolatile, excellent Select nonvolatile.This oil can be polar oil or non-polar oil.
This oil can be artificial oil or naturally-produced oil, such as vegetable oil and animal oil.
Vegetable oil can include, such as, and Semen Lini oil, Camellia oil, macadimia nut oil, Semen Maydis oil, ermine oil, olive Olive oil, American Avocado Tree oil, Flos Camelliae Japonicae caul-fat (sasanqua oil), Oleum Ricini, safflower oil, Jojoba oil, Oleum helianthi, Almond oil, Oleum Brassicae campestris, Oleum sesami, soybean oil and Oleum Arachidis hypogaeae semen.
Animal oil can include such as Squalene and squalane.
This oil can be hydrocarbon ils, silicone oil or fluorocarbon oil (fluoro oil).Hydrocarbon ils can include alkane oil, ester oil, ether oil and sweet Oil three ester oils.
Ester oil is the most saturated or unsaturated, straight or branched C1-C26Aliphatic mono acid or polyprotic acid are with full Sum or undersaturated, straight or branched C1-C26Aliphatic monohydric alcohol or the liquid ester of polyhydric alcohol, the carbon of described ester The sum of atom is more than or equal to 10.Preferably for the ester of monohydric alcohol, in the alcohol moiety of ester and acid moieties At least one is side chain.In the monoesters of monoacid and monohydric alcohol, can be mentioned that ethyl palmitate, Palmic acid second The own ester of base, isopropyl palmitate, dicaprylyl carbonate, myristic acid Arrcostab such as isopropyl myristate or lima bean Cool acetoacetic ester, Standamul 7061, different n-nonanoic acid 2-Octyl Nitrite, isononyl isononanoate, Dermol 105 And isostearyl neopentanoate.It is used as C4-C22Dicarboxylic acids or tricarboxylic acids and C1-C22The ester of alcohol, and single carboxylic Acid, dicarboxylic acids or tricarboxylic acids and non-saccharide C4-C26Dihydroxy, trihydroxy, tetrahydroxy or the ester of penta hydroxy group alcohol.Can Specifically mentioned: ethyl sebacate;Hamposyl L isopropyl ester;Dermol DIPS;Double (the 2-of decanedioic acid Ethylhexyl) ester;Diisopropyl adipate;Adipic acid-di-n-propyl ester;Dioctyl adipate;Double (the 2-second of adipic acid Base hexyl) ester;The different stearyl ester of adipic acid two;Double (2-ethylhexyl) ester of maleic acid;Citric acid three isopropyl ester;Fructus Citri Limoniae Acid three different cetyl;The different stearyl ester of citric acid three;Three glyceride lactates;Tricaprylin;Three (octyl groups 12 Alkanol) citrate;Three oleyl alcohol citrates;Neopentyl glycol two heptanoate;The different pelargonate of diethylene glycol two.As Ester oil, people can use C6-C30And preferably C12-C22The sugar ester of fatty acid and sugar diester.Term " sugared " means to contain Have several alcohol functional group, with and without aldehydes or ketones functional group and comprise at least 4 carbon atoms carry oxygen Compound based on hydrocarbon.These sugar can be monosaccharide, oligosaccharide or polysaccharide.The example bag of the suitably sugar that can be mentioned that Include sucrose (sucrose) (or sucrose, saccharose), glucose, galactose, ribose, fucose, maltose, Fructose, mannose, arabinose, xylose and lactose, and derivant, especially alkyl derivative, such as Methyl-derivatives, such as methyl glucoside.The sugar ester of fatty acid can be especially selected from previously described sugar and straight chain or Side chain, saturated or undersaturated C6-C30And preferably C12-C22The ester of fatty acid or the mixture of ester.If they Being undersaturated, these compounds can have one to three conjugation or unconjugated carbon-to-carbon double bond.This ester is the most optional From monoesters, diester, three esters, four esters and polyester and mixture thereof.These esters can be, such as, and oleate, the moon Cinnamic acid ester, cetylate, myristinate, behenic acid ester, cocos nucifera oil acid esters, stearate, linoleate, Linolenate, decanoin and arachidonate, or its mixture is such as, especially oil palm acid esters (oleopalmitate), oleostearin acid esters (oleostearate) and palmitate stearate (palmitostearate) mixed ester, And tetramethylolmethane four (thylhexoic acid) ester.More particularly, use monoesters and diester, and especially sucrose, Glucose or methyl glucoside monoleate or dioleate, stearate, behenic acid ester, oil palm acid esters, Linoleate, linolenate and oleostearin acid esters.The example that can be mentioned that is with title by Amerchol companyThe product sold, it is methyl glucose dioleate.As the example of preferred ester oil, can Mention, such as diisopropyl adipate, dioctyl adipate, caproic acid 2-Octyl Nitrite, ethyl laurate, pungent Acid cetyl, octanoic acid octyldodecyl, Dermol 105, myristyl propionate, 2 ethyl hexanoic acid 2- Octyl Nitrite, octanoic acid 2-Octyl Nitrite, caprylic/capric 2-Octyl Nitrite, methyl hexadecanoate, ethyl palmitate, Isopropyl palmitate, ethylhexyl palmitate, isohexyl laurate ester, lauric acid hexyl ester, Standamul 7061, Isopropyl isostearate, isopropyl myristate, Ceraphyl 140A, three (2 ethyl hexanoic acid) glyceride, four (2- Thylhexoic acid) pentaerythritol ester, succinic acid 2-Octyl Nitrite, ethyl sebacate and mixture thereof.
Triglyceride can include artificial triglyceride, such as, myristin, tripalmitin, Trilinolenin, trilaurin, tricaprin, tricaprylin, glycerol three (capric acid Ester/caprylate) and glycerol three (decanoin/caprylate/linolenate).
As silicone oil, can be mentioned that, such as straight chain organopolysiloxane such as dimethyl polysiloxane, aminomethyl phenyl gathers Siloxanes, methylhydrogenpolysi,oxane etc.;Ring-type organopolysiloxane such as octamethylcy-clotetrasiloxane, decamethyl D5, ten diformazan basic ring six siloxanes etc.;And mixture.Preferably, silicone oil gathers selected from liquid Dialkylsiloxane, especially liquid polydimethylsiloxane (PDMS) and the liquid comprising at least one aryl gather Organosiloxane.These silicone oil can also is that organically-modified.According to the spendable organically-modified silicon of the present invention Ketone be as defined above and their structure include one or more via group based on hydrocarbon connect organic The silicone oil of functional group.Organopolysiloxane is defined in the siloxanes chemistry of Walter Noll and technology in more detail (Chemistry and Technology of Silicones) (1968), in Academic Press.They can be volatility Or nonvolatile.Volatile or nonvolatile silicone oil can be used, as be at ambient temperature liquid or Pasty state comprise the volatile of straight chain or cyclic silicone chain or nonvolatile polydimethylsiloxane (PDMS), Particularly Cyclomethicone (cyclopolydimethylsiloxane) (Cyclomethicone, Cyclomethicone) such as cyclohexasiloxane;Comprise the polydimethylsiloxane of alkyl, alkoxyl or phenyl, described Alkyl, alkoxyl or phenyl are on the side chain of silicone chains or end, and described group has 2 to 24 carbon atoms; Phenyl siloxane such as phenyl trimethicone polysiloxanes (phenyl trimethicone), pheiiyldimetliyl polysiloxanes (phenyl dimethicone), phenyl trimethicone siloxy diphenyl siloxane, the poly-silica of diphenyldimethyl Alkane, diphenyl methyl diphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicate and polymethyl-benzene Radical siloxane.
Alkane oil is selected from:
-straight or branched, the most ring-type, C6-C16Lower paraffin hydrocarbon.The example that can be mentioned that include hexane, Hendecane, dodecane, tridecane and isoparaffin, such as 2-Methylpentadecane, Fancol ID and isodecane;With
-containing the straight or branched hydrocarbon more than 16 carbon atoms, such as liquid paraffin, paroline (petroleum jelly), poly decene and Parleam are such asAnd squalane.
Preferably, alkane oil can include straight or branched hydrocarbon such as mineral oil (such as, liquid paraffin), paraffin, all Intellectual circle or vaseline (petrolatum), naphthalene etc.;Parleam, Isoeicosane and decene/butylene copolymer; And mixture.Preferably, this oil is selected from the hydrocarbon ils under room temperature, atmospheric pressure in liquid form.
Preferably, this oil has low molecular weight, such as below 700g/mol, selected from having short hydrocarbon chain (C1-C12) Ester oil (such as isopropyl myristate, isopropyl palmitate, isononyl isononanoate and ethylhexyl palmitate), Hydrocarbon ils (such as Fancol ID, 2-Methylpentadecane and squalane), side chain and/or unsaturated fatty alcohol (C12-C30) type Oil, such as octyldodecanol, oleyl alcohol, and ether oil such as dicaprylyl ether.
This oil is selected from vegetable oil, animal oil, mineral oil, artificial oil, silicone oil and hydrocarbon ils, be preferably selected from ester oil, The hydrocarbon ils of ether oil, alkane oil and triglyceride oil.
The amount of the oil in the compositions of the present invention is unrestricted, and relative to the gross weight of compositions, can be 0.1 Weight % is to 50 weight %, preferably 0.5 weight % to 40 weight % and more preferably 5 weight % to 30 weight % In the range of.
1-2. nonionic surfactant
The compositions of the present invention comprises at least one nonionic surfactant.The nonionic of single type can be used Surfactant, but can be combined and use two or more different types of nonionic surfactants.
Nonionic surfactant is unrestricted, but can have 8.0 to 14.0, preferably 9.0 to 13.5 and more excellent Select HLB (hydrophilic lipophilic balance) value of 10.0 to 13.0.If using two or more non-ionic surfaces Activating agent, determines HLB value by the weight average of the HLB value of whole nonionic surfactants.
Nonionic surfactant is selected from:
(1) at a temperature of less than or equal to 45 DEG C, be the surfactant of fluid, selected from least one polyhydric alcohol and The ester of at least one fatty acid, described polyhydric alcohol selected from comprise 1 to 60 ethylene oxide unit Polyethylene Glycol, Anhydro sorbitol, the glycerol comprising 2 to 30 ethylene oxide units, comprise the poly-of 2 to 12 glycerol unit Glycerol, described fatty acid comprises at least one saturated or undersaturated, straight or branched C8-C22Alkyl chain,
(2) fatty acid or the mixed ester of fatty alcohol, carboxylic acid and glycerol,
(3) fatty acid ester of sugar and sugared fatty alcohol ether,
(4) at a temperature of less than or equal to 45 DEG C, be the surfactant of solid, selected from glycerol fatty acid ester, The fatty acid ester of anhydro sorbitol and the oxyethylation fatty acid ester of anhydro sorbitol, ethoxylated fat ether and second Epoxide fatty acid ester,
(5) ethylene oxide (A) and the block copolymer of propylene oxide (B), and
(6) silicone surfactant.
(1) it is that the surfactant of fluid can be particularly at a temperature of less than or equal to 45 DEG C:
-molecular weight is the isostearate of the Polyethylene Glycol of 400, by Unichema company with title PEG 400 Sell;
-two iso stearic acid of glycerine ester, are sold by Solvay company;
-comprise the glycerol monolaurate of 2 glycerol unit, Solvay company sell;
-sorbitan oleate, is sold with title Span 80 by ICI company;
-sorbitan isostearate, is sold with title Nikkol SI 10R by Nikko company;With
-α-butyl glucoside cocos nucifera oil acid esters or α-butyl glucoside decanoin, sold by Ulice company.
(2) mixed ester (it can be used as above-mentioned nonionic surfactant) of fatty acid or fatty alcohol, carboxylic acid and glycerol Can in particular selected from the fatty acid of the alkyl chain having containing 8 to 22 carbon atoms or fatty alcohol and 'alpha '-hydroxy acids and/ Or the mixed ester of succinic acid and glycerol.Described 'alpha '-hydroxy acids can be, such as citric acid, lactic acid, glycolic or Herba Marsileae Quadrifoliae Fruit acid and mixture thereof.
Can be used for the mixed ester in the nanoemulsions of the present invention derived from fatty acid or the alkyl chain of alcohol can be straight Chain or side chain, and saturated or undersaturated.They can particularly stearate, isostearate, linoleic acid Ester, oleate, behenic acid ester, arachidonate, cetylate, myristinate, laurate, the last of the ten Heavenly stems Acid esters, iso stearyl, stearyl, sub-oil base (linoleyl), oil base, mountain base, myristyl, lauryl or Octyl group chain, and mixture.
As the example of the mixed ester that can use in the nanoemulsions of the present invention, can be mentioned that by H ü ls company with name Claim glycerol and citric acid, lactic acid, the mixed ester (CTFA of mixture of linoleic plus oleic acid that Imwitor 375 sells Title: glycerol citrate/lactate/linoleate/oleate);By H ü ls company with title Imwitor 780K The succinic acid sold and the mixed ester (CTFA title: isooctadecanol two glycerol succinic acid ester) of isooctadecanol and glycerol; Mixed ester (the CTFA name of the citric acid sold with title Imwitor 370 by H ü ls company and stearic acid and glycerol Claim: Glyceryl stearate citrate);By Danisco company with title Lactodan B30 or Rylo LA30 The lactic acid sold and the mixed ester (CTFA title: glyceryl stearate lactate) of stearic acid and glycerol.
(3) fatty acid ester (it can be used as above-mentioned nonionic surfactant) of sugar is preferably being less than or equal to It it is solid and can be in particular selected from C at a temperature of 45 DEG C8-C22Fatty acid and sucrose, maltose, glucose or The ester of fructose or the mixture of ester, and C14-C22Fatty acid and the ester of methyl glucoside or the mixture of ester.
Form the C of the fat units of described ester8-C22Or C14-C22Fatty acid comprises and contains 8 to 22 or 14 respectively To the saturated of 22 carbon atoms or undersaturated linear alkyl chain.The fat units of described ester can be in particular selected from firmly Fat acid ester, behenic acid ester, arachidonate, cetylate, myristinate, laurate and decanoin And mixture.Stearate is preferably used.
As fatty acid and the example of the mixture of the ester of sucrose, maltose, glucose or fructose or ester, can carry And sucrose monostearate, sucrose distearate and sucrose tristearate and mixture thereof, as by Croda The product that company sells with title Crodesta F50, F70, F110 and F160;And the fatty acid that can be mentioned that and The example of the ester of methyl glucoside or the mixture of ester is with title Tego-care 450 by Goldschmidt company Methyl glucoside polyglycereol-3 distearate sold.Also can be mentioned that glucose or maltose monoesters, such as methyl O-hexadecanoyl group-6-D-glucoside (methyl o-hexadecanoyl-6-D-glucoside) and o-hexadecanoyl group-6-D-wheat Bud glucosides.
(3) fatty alcohol ether (it can be used as above-mentioned nonionic surfactant) of sugar can be less than or equal to 45 DEG C At a temperature of be solid and can be in particular selected from C8-C22Fat alcohol and glucose, maltose, sucrose or the ether of fructose Or the mixture of ether, and C14-C22Fatty alcohol and the ether of methyl glucoside or the mixture of ether.These are particularly Alkyl polyglucoside.
The C of the fat units of the ether that formation can use in the nanoemulsions of the present invention8-C22Or C14-C22Fat Alcohol comprises the saturated or undersaturated linear alkyl chain containing 8 to 22 or 14 to 22 carbon atoms respectively.Described The fat units of ether can be in particular selected from decyl, cetyl, mountain base, Semen arachidis hypogaeae base, stearyl, palmityl, meat Myristyl, lauryl, octyl group and hexadecanoyl group unit, and mixture, such as cetearyl.
As the fatty alcohol ether of sugar, such as, can be mentioned that alkyl polyglucoside, such as, divided by such as Henkel company The decyl glucoside do not sold with title Plantaren 2000 and Plantaren 1200 and lauryl glucoside, whale Wax stearyl glucoside (mixture optionally as with cetearyl alcohol), such as by SEPPIC company with title Montanov 68 sells, Goldschmidt company sell and by Henkel with title Tego-care CG90 Company sells with title Emulgade KE3302, and Semen arachidis hypogaeae base glucoside, such as with arachidic alcohol and mountain alcohol With the form of the mixture of Semen arachidis hypogaeae base glucoside, SEPPIC company sell with title Montanov 202.
The surfactant used is more particularly that sucrose monostearate, sucrose distearate or sucrose three are hard Fat acid ester and mixture, methyl glucoside polyglycereol-3 distearate and alkyl polyglucoside.
(4) at a temperature of less than or equal to 45 DEG C, for the fatty acid ester of glycerol of solid, (it can be used as above-mentioned non- Ionic surface active agent) can be in particular selected from by least one acid, (it is saturated that it comprises containing 12 to 22 carbon atoms Linear alkyl chain) and the ester of 1 to 12 glycerol unit formation.One or more in the fatty acid ester of these glycerol Plant and can be used in the present invention.
These esters can be in particular selected from stearate, behenic acid ester, Arachidate and cetylate and mixture thereof. Stearate and cetylate more preferably use.
As the surfactant that can use in the present invention, such as, can be mentioned that SY-Glyster MSW 750, two Stearate, tristearate and five stearates (CTFA title: Natrulon H-10 stearate, Natrulon H-10 Distearate, Natrulon H-10 tristearate, Natrulon H-10 five stearate), as divided by Nikko company The product do not sold with title Nikkol Decaglyn 1-S, 2-S, 3-S and 5-S, and two glyceryl monostearates (CTFA title: polyglycereol-2 stearate), such as the product sold with title Nikkol DGMS by Nikko company Product.
(4) for the fatty acid ester of anhydro sorbitol of solid (on it can be used as at a temperature of less than or equal to 45 DEG C The nonionic surfactant stated) it is selected from the C of anhydro sorbitol16-C22Fatty acid ester and the oxygen of anhydro sorbitol Vinylation C16-C22Fatty acid ester.They are by least one fatty acid and Sorbitol or ethoxylated sorbitan sugar alcohol Being formed, at least one fatty acid described comprises and contains saturated straight of at least one of 16 to 22 carbon atoms respectively Alkyl group chain.Described oxyethylation ester generally comprises 1 to 100 ethylene glycol unit and preferably 2 to 40 oxygen Change ethylene (EO) unit.
These esters can be in particular selected from stearate, behenic acid ester, Arachidate, cetylate and mixture thereof. Stearate and cetylate are preferably used.
As the example of the above-mentioned nonionic surfactant that can use in the present invention, can be mentioned that anhydrosorbitol Alcohol monostearate (CTFA title: sorbitan monostearate), is gone out with title Span 60 by ICI company Sell, Arlacel-40 (CTFA title: sorbitan palmitate), by ICI company with name Span 40 is claimed to sell and Arlacel-65 20EO (CTFA title: polysorbate65), Sold with title Tween 65 by ICI company.
(4) at a temperature of less than or equal to 45 DEG C, for the ethoxylated fat ether of solid, (it can be used as above-mentioned non- Ionic surface active agent) it is preferably and is contained 16 to 22 carbon by 1 to 100 ethylene oxide unit with at least one The ether that the aliphatic alcohol chain of atom is formed.The aliphatic chain of described ether can be in particular selected from mountain base, Semen arachidis hypogaeae base, stearyl With cetyl unit and mixture thereof, such as cetearyl.The example of the ethoxylated fat ether that can be mentioned that is bag Mountain alcohol ether (CTFA title: mountain alcohol polyethers-5, mountain containing 5,10,20 and 30 ethylene oxide units Alcohol polyethers-10, mountain alcohol polyethers-20, mountain alcohol polyethers-30), as by Nikko company with title Nikkol BB5, The product that BB10, BB20 and BB30 sell, and comprise stearic alcohol ether (the CTFA name of 2 ethylene oxide units Claim: stereth-2), such as the product sold with title Brij 72 by ICI company.
(4) at a temperature of less than or equal to 45 DEG C, for the ethoxylated fatty acid ester of solid, (it can be used as above-mentioned Nonionic surfactant) be by 1 to 100 ethylene oxide unit and at least one to contain 16 to 22 carbon former The ester that the fatty acid chain of son is formed.Aliphatic chain in described ester can be in particular selected from stearate, behenic acid ester, flower Give birth to acid esters and cetylate unit and mixture thereof.The example of the ethoxylated fatty acid ester that can be mentioned that is to comprise 40 The stearic ester of individual ethylene oxide unit, such as by ICI company with title Myrj 52 (CTFA title: PEG-40 Stearate) product sold, and comprise the behenic acid of 8 ethylene oxide units ester (CTFA title: PEG-8 behenic acid ester), the product such as sold with title Compritol HD5ATO by Gattefosse company.
(5) (it can be used as the nano-emulsion according to the present invention to the block copolymer of ethylene oxide (A) and propylene oxide (B) Surfactant in liquid) can be in particular selected from the block copolymer of formula (I) and mixture thereof:
[formula (I)]
HO(C2H4O)x(C3H6O)y(C2H4O)zH (I)
Wherein x, y and z are integers so that x+z is in the range of 2 to 100 and y is in the range of 14 to 60, And it is chosen more particularly from the block copolymer with the formula (IV) of the HLB value in the range of 8.0 to 14.
As (6) silicone surfactant that can be used according to the invention, such as, can be mentioned that at document Those disclosed in US-A-5364633 and US-A-5411744.
It is preferably the compound of formula (II) as (6) silicone surfactant of above-mentioned nonionic surfactant:
[formula (II)]
Wherein:
R1、R2And R3Represent C independently of one another1-C6Alkyl or group
-(CH2)x-(OCH2CH2)y-(OCH2CH2CH2)z-OR4, group R1、R2Or R3In at least one be not alkane Base;R4It is hydrogen, alkyl or acyl group;
A is the integer in the range of 0 to 200;
B is the integer in the range of 0 to 50;Condition is that A and B is not simultaneously equal to zero;
X is the integer in the range of 1 to 6;
Y is the integer in the range of 1 to 30;
Z is the integer in the range of 0 to 5.
In preferred embodiments, in the compound of formula (II), alkyl is methyl, and x is in 2 to 6 scopes In integer, and y is the integer in the range of 4 to 30.
As the silicone surfactant of formula (II), such as, can be mentioned that the compound of formula (III):
[formula (III)]
Wherein A is the integer in the range of 20 to 105, and B is the integer in the range of 2 to 10, and y It it is the integer in the range of 10 to 20.
Example as the silicone surfactant of formula (II), it is possible to mention the compound of formula (IV):
[formula (IV)]
H-(OCH2CH2)y-(CH2)3-[(CH3)2SiO]A’-(CH2)3-(OCH2CH2)y-OH (IV)
Wherein A' and y is the integer in the range of 10 to 20.
The compound of the spendable present invention is with title DC 5329, DC by Dow Corning company Those of 7439-146, DC 2-5695 and Q4-3667 sale.Described compound DC 5329, DC 7439-146 Being the compound of formula (II) with DC 2-5695, wherein, respectively, A is 22, and B is 2, and y is 12; A is 103, and B is 10, and y is 12;A is 27, and B is 3, and y is 12.
Compound Q 4-3667 is the compound of formula (III), and wherein A is 15 and y to be 13.
Preferably, nonionic surfactant is selected from:
-polyethylene glycol isostearate or oleate (ethylene oxide of 8 to 10mol),
The different cetyl ether of-Polyethylene Glycol, mountain base ether or iso stearyl ether (ethylene oxide of 8 to 10mol),
-comprise polyglycereol monolaurate or the dilaurate of 3 to 6 glycerol unit,
-comprise polyglycereol list (different) stearate of 3 to 6 glycerol unit,
-comprise the polyglycerol monooleate of 3 to 6 glycerol unit, and
-comprise the Plurol Oleique CC497 of 3 to 6 glycerol unit.
Preferably, nonionic surfactant is selected from polyglyceryl fatty acid ester and single or polyoxyalkylenated fatty acid ester.
Preferably, polyglyceryl fatty acid ester includes containing the polyglycereol that the 70% or more degree of polymerization is 4 or bigger Fatty acid and the ester of polyglycereol, preferably comprise poly-sweet between 4 and 11 of the degree of polymerization equal to or more than 60% Oil fatty acid and the ester of polyglycereol, and more preferably contain the degree of polymerization equal to or more than 30% be 5 poly-sweet The fatty acid of oil and the ester of polyglycereol.
Polyglyceryl fatty acid ester is selected from comprising 2 to 30 carbon atoms, preferably 6 to 30 carbon atoms and more The saturated or unsaturated acid of preferably 8 to 30 carbon atoms, the most saturated acid, such as lauric acid, oleic acid, The monoesters of stearic acid, isostearic acid, capric acid, octanoic acid and myristic acid, diester and three esters.
Polyglyceryl fatty acid ester can have derived from 2 to 10 glycerol, more preferably 3 or 4 to 6 glycerol and enter The polyglycereol part of one step more preferably 5 or 6 glycerol.
Preferably, polyglycereol (PG) fatty acid ester is selected from PG-4 laurate, PG-5 laurate, PG-5 Dilaurate, PG-5 oleate, PG-5 dioleate, PG-6 tri-caprylate, PG-5 myristinate, PG-5 tri-myristinate, PG-5 stearate, PG-5 isostearate, PG-5 trioleate, PG-6 are pungent Acid esters and PG-6 tri-caprylate.
Preferably, single oxygen alkylene or polyoxyalkylenated fatty acid ester have derived from 1 to 20 oxyalkylene, preferably 3 to 15 oxyalkylenes, and (gathering) oxyalkylene portions of more preferably 8 to 10 oxyalkylenes.
Oxyalkylene portions can derived from aklylene glycol such as ethylene glycol, propylene glycol, butanediol, pentanediol, oneself two Alcohol etc..Oxyalkylene portions can comprise between 1 and 100 and the oxidation of preferably between 2 and 50 some moles Ethylene and/or propylene oxide.Advantageously, nonionic surfactant does not comprise any oxypropylene units.
Single oxygen alkylene or polyoxyalkylenated fatty acid ester are selected from comprising 2 to 30 carbon atoms, and preferably 6 to 30 The saturated or unsaturated acid of individual carbon atom and more preferably 8 to 30 carbon atoms, the most saturated acid, as The monoesters of lauric acid, oleic acid, stearic acid, isostearic acid, capric acid, octanoic acid and myristic acid and diester.
The single oxygen alkylene that can be mentioned that or the example of polyoxyalkylenated fatty acid ester include saturated or unsaturated, straight Chain or side chain C2-C30, preferably C6-C30And more preferably C8-C22Acid and the ester of Polyethylene Glycol.
The single oxygen alkylene that can be mentioned that or the example of polyoxyalkylenated fatty acid ester include ethylene oxide and lauric acid, meat The adduct of the ester of myristic acid, Palmic acid, stearic acid, isostearic acid, oleic acid or behenic acid, and mixture, Those rolled into a ball especially with 8 to 20 oxyethylene groups, if PEG-8 to PEG-20 laurate is (as CTFA Title: PEG-8 laurate is to PEG-20 laurate);PEG-8 to PEG-20 myristinate (as CTFA title: PEG-8 myristinate is to PEG-20 myristinate);PEG-8 to PEG-20 Palmic acid Ester (as CTFA title: PEG-8 cetylate is to PEG-20 cetylate);PEG-8 to PEG-20 is hard Fat acid ester (as CTFA title: PEG-8 stearate is to PEG-20 stearate);PEG-8 to PEG-20 Isostearate (as CTFA title: PEG-8 isostearate is to PEG-20 isostearate);PEG-8 To PEG-20 oleate (as CTFA title: PEG-8 oleate is to PEG-20 oleate);PEG-8 is extremely PEG-20 behenic acid ester (as CTFA title: PEG-8 behenic acid ester is to PEG-20 behenic acid ester);And it is mixed Compound.
Preferably, cithrol be selected from PEG-8 isostearate, PEG-8 stearate, PEG-10 isostearate, PEG-10 oleate, the different cetyl ether of PEG-10, PEG-10 mountain base ether or PEG-10 iso stearyl ether and mixture thereof.Preferably nonionic surfactant is polyglycereol (PG) fatty acid ester.
Preferably, nonionic surfactant is selected from single oxygen alkylene or polyoxyalkylenated fatty acid ester, polyglycereol Fatty acid surfactants and the fatty acid ester of sugar (particularly sucrose).
The amount of the nonionic surfactant in the compositions of the present invention is unrestricted, and relative combinations thing is total Weight, can be in 0.1 weight % to 30 weight %, preferably 0.5 weight % to 15 weight % and more preferably 1 weight % To 10 weight %.
1-3. aqueous phase
The compositions of the present invention comprises at least one aqueous phase.Aqueous phase comprises water as key component.The amount of water is not subject to Limit, and the gross weight of relative combinations thing, can be 5 weight % to 99 weight %, preferably 10 weight % are to 95 Weight % and more preferably 15 weight % are to 90 weight %.
Aqueous phase can further include at least one organic solvent, organic solvent the most miscible with water.As organic Solvent, there can be mentioned, such as C1-C4Alkanol such as ethanol and isopropanol;Aromatic alcohol such as benzylalcohol and phenyl phenol; Its similar product;And mixture.The amount of organic solvent miscible with water, the gross weight of relative combinations thing, can Less than 10 weight %, preferably 5 weight % or less, and more preferably 1 weight % or less.
1-4. comprises the microcapsule of releasable coloring agent
Term used herein " microcapsule " refers to comprise at least one coloring agent of embedding and surround at least the one of core The spherical microcapsule of individual stratiform coating, described core is the most different from coating.Microcapsule is different from microsphere, micro- Ball is made up of spherical uniform matrix.
In embodiments, described " at least one stratiform coating " is laminated coating, preferably organic multilayer coating.
Outside term " Multi-layer microcapsule " refers to by the core surrounded by coating based on one or more internal layer and one The microcapsule of layer composition.Form one or more internal layer and this microcapsule of the laminated coating of this Multi-layer microcapsule Single outer layer can be formed by identical or different wall-forming organic compound.
This microcapsule comprises core that surrounded by coating based on a layer or more layers, also referred to as " kernel ". In preferred embodiments, this microcapsule is " multilamellar " microcapsule, comprises outside at least one internal layer and one Layer.The single outer layer forming one or more internal layer of laminated coating of Multi-layer microcapsule and this microcapsule can be by Identical or different wall-forming organic compound is formed.
In specific embodiments, internal layer is formed by identical wall-forming organic compound with outer layer, and then core Surrounded by one layer of coating.
In one embodiment, outer layer does not comprise any coloring agent.In another embodiment, outer layer comprises At least one coloring agent.
Term " wall-forming organic compound " refers to that organic compound as defined herein or two or more differences have The combination of machine compound, the component of the layer of its formation microcapsule.In preferred embodiments, " wall-forming organises Compound " comprise at least one polymer.
In specific embodiments, the gross weight of relative combinations thing, the coloring agent of encapsulation is with the work of the pigment of encapsulation Property material meter can be in 0.5 weight % to 20 weight %, especially in 1 weight % to 15 weight % and more particularly Amount in the range of 2 weight % to 12 weight % is present in the compositions of the present invention.
Microcapsule generally by preparation final stage and be attached to after filtration stage (if any) make up In product formula, to avoid microcapsules rupture.Preferably, microcapsule is added at a temperature of below 50 DEG C the most uniformly Mixing.Them are made to mix gently with oar (paddle) rather than homogenizer.
Microcapsule can have and contacts with aqueous phase, preferably connects with hydrophilizing agent (such as water, polyhydric alcohol, dihydroxylic alcohols, alcohol) The ability crushed it is easier to time tactile.Advantageously, microcapsule can be when contacting with this hydrophilizing agent as defined below Swelling.Advantageously, microcapsule is deformable when being administered on keratin material, and thus carries to user For soft feeling.Additionally, their small size contributes to not producing any uncomfortable or unfavorable sense when using Feel.
But, microcapsule is sufficiently flexible to rupture to discharge theirs when rubbing the most slightly or press skin Content, but, while it is true, be the most durable to avoid manufacturing and storing correspondent composition during The destruction of coating.
Additionally, microcapsule allows the compositions using conventional equipment to prepare the present invention, because in the fabrication process Device does not colours.
Thus, microcapsule causes special interest, because they can be covered during the storage of manufacture process and prolongation The primitive color of coloring agent of encapsulation, improve these coloring agent to degradation-resistant stability and prevent encapsulation Toner is undesirably discharged in compositions.
The gross weight of relative combinations thing, compositions can including at least 0.1 weight % to 20 weight %, preferably 0.5 Weight % is to 15 weight % and the microcapsule of more preferably 2 weight % to 10 weight %.
The preferably comprising of microcapsule is described more fully below.
1-4-1. comprises the first embodiment of the microcapsule of releasable coloring agent
In the first embodiment, usual microcapsule have diameter less than 800 μm, more preferably less than about 400 μm, Advantageously 1 μm to 300 μm, especially 5 μm are flat to 200 μm and more particularly 10 μm to 100 μm All particle diameters.
The microcapsule comprising releasable coloring agent is Multi-layer microcapsule.This microcapsule comprises:
-core, the most uncoloured core, comprise a kind of organic material, be preferably made up of a kind of organic material, and
-surround at least one stratiform coating of described core, this stratiform coating comprises at least one polymer, and at least A kind of coloring agent.Advantageously, it comprises at least one binding agent.
Preferably, microcapsule comprises at least two-layer, preferably at least one organic coloring internal layer and an organic outer layer, The color of described organic outer layer is different from the color of described organic coloring internal layer.
Preferably, described core comprises at least one monosaccharide or derivatives thereof as organic material, particularly monosaccharide- Polyhydric alcohol, is advantageously selected from mannitol, erythritol, xylitol, Sorbitol and mixture thereof, preferably Mannitol.
Advantageously, this stratiform coating surrounding core comprises at least one hydrophilic polymer, its selected from polysaccharide and Derivant, preferably comprises a type of sugar (ose) or the sugar of several type, preferably includes at least D-Glucose The several type of unit sugar many carbohydrates and their derivative, especially starch and derivant, cellulose or its derive Thing, and more preferably starch and derivant.
Preferably, microcapsule includes at least one material based on lipid, preferably has amphipathic characteristic, such as ovum Phospholipid, and especially hydrolecithin.
Advantageously, relative to the gross weight of microcapsule, core represents 10 weight % to 90 weight %, preferably 20 weights Amount % to 80 weight %, more preferably 30 weight % to 70 weight %, and even more preferably 40 weight % to 60 weight %.
Advantageously, relative to microcapsule, coloring agent represents 20 weight % to 90 weight %, preferably 30 weight % To 80 weight % and especially 50 weight % to 75 weight %.
Especially, described microcapsule at least includes:
-the kernel be made up of monosaccharide-polyhydric alcohol (preferably mannitol),
-color is different each other at least two layer,
-at least one hydrophilic polymer, is preferably chosen from polysaccharide or derivatives thereof and is more preferably selected from starch Or derivant, and advantageously, at least one material based on lipid, preferably amphipathic compound, and more preferably Phospholipid, even more preferably phosphate acyl glycerol (phosphoacylglycerol), such as hydrolecithin.
In one embodiment, each layer from microcapsule comprises at least one specific colorants or coloring agent Specific blends.In one embodiment, the outer layer from microcapsule comprises at least one specific coloring agent Or the specific blends of coloring agent.Especially, described coloring agent is pigment, is preferably chosen from metal-oxide.? In one embodiment, comprise iron oxides and titanium dioxide (TiO from a layer of microcapsule2) as coloring agent. In one embodiment, one layer from microcapsule only comprises TiO2As coloring agent.
Relative to the weight of compositions, the compositions of the present invention may also include the another of 0.1 weight % to 70 weight % Outer cosmetic composition, its selected from volatile and nonvolatile silicone oil or hydrocarbon ils, surfactant, filler, Other gelating agent, thickening agent, film former, polymer, preservative, silicone elastomer, imitative suntan (self-tanning agent), the other coloring agent of non-embedding, cosmetic active agent, pH adjusting agent, spice, UV filtering agent and mixture thereof.
1-4-1-1. core
In first embodiment of the invention, core is made up of at least organic material.The preferred diameter of size of core exists In 500nm to 150 μ m.Preferably, described core is solid form and/or crystal under room temperature, atmospheric pressure Form.In certain embodiments, organic material can have high water-soluble.
Preferably, core is water miscible or water dispersible.
In certain embodiments, core is uncoloured, i.e. it does not comprise colorant materials.
In certain embodiments, core is only made up of a kind of compound.This compound is organically and more preferably Ground is native compound.
In preferred embodiments, core is sugar-ol, is preferably monosaccharide-polyhydric alcohol, is advantageously selected from manna Sugar alcohol, erythritol, xylitol, Sorbitol.In certain embodiments, core is made up of mannitol, And be the most only made up of mannitol.In embodiment for the election, core comprises at least mannitol and extremely Few a kind of other composition, this other composition is preferably the polymer selected from hydrophilic polymer.Especially, This core can include mannitol and cellulosic polymer, starch polymer and their mixture, preferably it Mixture in select hydrophilic polymer.In preferred embodiments, cellulosic polymer is carboxylic first Base cellulose, and starch polymer is unmodified native starch, such as corn starch.
Core can be made up of the crystal seed (or crystal) of a kind of material in above-mentioned material.
Relative to the gross weight of microcapsule, preferably with 1 weight % to 50 weight %, preferably 4 weight % are to 40 Weight %, especially 5 weight % to 30 weight %, and the amount of more particularly 10 weight % to 20 weight % include core.
Relative to the gross weight of core, preferably with 2 weight % to 100 weight %, preferably 5 weight % are to 100 Weight %, and the amount of especially 100 weight % includes mannitol.
Relative to the gross weight of microcapsule, preferably with 1 weight % to 50 weight %, preferably 4 weight % are to 40 Weight %, especially 5 weight % to 30 weight %, and the amount of especially 10 weight % to 20 weight % include mannose Alcohol.
1-4-1-2. exterior layer (external layer)
As previously disclosed, core is advantageously surrounded by exterior layer, and this exterior layer preferably comprises at least one Layer and an outer layer).In the first embodiment, these layers extend concentrically about preferably relative to core.Described layer The most organically, at least one organic compound is i.e. comprised as wall-forming materials.Preferably, internal layer and/or Outer layer includes at least one polymer, and especially hydrophilic polymer.
(a) polymer
In the first embodiment, microcapsule, and especially exterior layer comprises selected from polysaccharide and derivant, propylene Acid or methacrylic acid homo thing or copolymer or its salt and ester, and the hydrophilic polymer of their mixture.
In preferred embodiments, microcapsule, and especially exterior layer comprises selected from polysaccharide and derivant, and The particularly hydrophilic polymer of starch polymer.
This polymer is advantageously selected from (gathering) (alkyl) (methyl) acrylic acid and their derivant, especially (gathers) (alkane Base) (methyl) acrylate and their derivant, it is preferably selected from alkyl acrylic/alkyl methacrylate copolymer With their derivant, and most preferably from Evonik Degussa with trade name EUDRAGIT RSPO provide Ethyl acrylate, methyl methacrylate and low content there is the copolymer of methacrylate of quaternary ammonium group.
Polysaccharide and derivant are preferably selected from chitosan polymer, chitin polymer, cellulosic polymer, starch Polymer, galactomannan, alginate, carrageenin, mucopolysaccharide and their derivant, and mixed Compound.
In preferred embodiments, exterior layer does not have microcrystalline Cellulose.
In particularly preferred embodiments, polysaccharide and their derivant are preferably selected from comprising a type of sugar Or the sugar of the type sugared, the most several of several type, especially at least as the D-Glucose unit of sugar Those, preferred starch polymer, cellulosic polymer and derivant and mixture thereof.
In preferred embodiments, microcapsule comprises at least one hydrophilic polymer, this hydrophilic polymer Selected from starch and derivant thereof, especially corn starch;Cellulose and its derivates;Methacrylic acid and/or methyl The copolymer of the homopolymer of acrylate and/or copolymer or (alkyl) acrylic acid and/or (alkyl) methacrylic acid and Their derivant, preferably their salt and their ester;And especially, capsule comprises poly-methyl methacrylate Ester.
In preferred embodiments, microcapsule comprises selected from starch and derivant thereof, especially corn starch extremely Few a kind of hydrophilic polymer.
According to the present invention can starch generally by material of vegetable origin (such as rice, Semen sojae atricolor, Rhizoma Solani tuber osi or Semen Maydis) produce Raw.Starch can be unmodified or that (with cellulose family ratio) is modified starch.In preferred embodiments, starch It is unmodified.
Methacrylic acid and/or the preferred homopolymer of methacrylate and/or copolymer are wherein metering system The copolymer of acid methyl ester and ethyl acrylate has those of the molecular weight of 750kDa to 850kDa.
Such as, cellulose derivative includes alkali cellulose carboxymethyl cellulose (CMC), cellulose esters and cellulose Ether and aminocellulose.In certain embodiments, cellulose is carboxymethyl cellulose (CMC).
In preferred embodiments, capsule includes at least starch derivatives (especially corn starch), poly-methyl-prop The copolymer of e pioic acid methyl ester, (alkyl) acrylic acid and/or (alkyl) methacrylic acid and they derivant (preferably it Salt and their ester) and/or cellulose derivative.
Preferably, microcapsule comprises the polymer not cross-linked.Polymer can be in a layer or several layers.? In another embodiment, polymer can be in core.Microcapsule can comprise polymer in core and/or layer.Specific Embodiment in, polymer is in core and layer.In embodiments, core is including at least as polymer Starch and/or cellulose derivative.When starch is included in core, it represents the main component of this core, i.e. The weight of starch is more than the respective amount of other compound of core.Polymer can represent 0.5 weight % of microcapsule extremely 20 weight %, especially represent 1 weight % to 10 weight % of microcapsule and preferably 2 weight % to 8 weight %.
The different layers forming coating can be based on same or different polymer.Advantageously, they will be by same poly- Compound is formed.On the contrary, each layer is by advantageously different colorings.This different color can be different by using Coloring agent obtains, and when for the coloring agent of two layers by time identical, can colour by using at least one The variable concentrations of agent obtains.
In certain embodiments, outer layer comprises at least one coloring agent.In another embodiment, outer layer Do not comprise any coloring agent.
(b) coloring agent
In the first embodiment, microcapsule and particularly exterior layer comprise coloring agent.
Term " coloring agent " includes being ratified in cosmetics by CTFA and FDA for cosmetic formulations Any organic or inorganic pigment or coloring agent.Therefore, term " coloring agent " refers to: organic pigment, as selected from crowd The synthesis of any one of well known FD&C or D&C dyestuff or natural dye;Inorganic pigment, such as burning Thing, or color lake such as color lake based on alkermes, barium, strontium, calcium or aluminum, and their any combination (blend). It is described in more detail below this based colorant.In specific embodiments, coloring agent can be water solublity or water-dispersible Property.In another embodiment, according to the present invention can coloring agent can be oil-soluble or oil-dispersing property Or there is in water limited dissolubility.In preferred embodiments, coloring agent is inorganic pigment, more preferably gold Belong to oxide.Advantageously, the coloring agent of Multi-layer microcapsule be chosen from Fe oxide, titanium dioxide, aluminium oxide, Native metal oxide (the primary metal of zirconium oxide, cobalt oxide, cerium oxide, nickel oxide, stannum oxide or zinc oxide Oxide), or composite oxides, it is more preferably selected from red iron oxide, quantity of yellow iron oxide or black iron oxides Iron oxides, or its mixture.
Described layer also can comprise the color lake of the toner corresponding to being fixed to substrate.This color lake is advantageously selected From following material, and their mixture:
-alkermes;
-azo, anthraquinone, indigo, ton, pyrene, quinoline, triphenyl methane, the organic pigment of fluorane coloring agent; In organic pigment, can be mentioned that with following trade mark numbering known those: D&C Blue No.4, D&C Brown No.1、D&C Green No.5、D&C Green No.6、D&C Orange No.4、D&C Orange No. 5、D&C Orange No.10、D&C Orange No.11、D&C Red No.6、D&C Red No.7、 D&C Red No.17、D&C Red No.21、D&C Red No.22、D&C Red No.27、D&C Red No.28、D&C Red No.30、D&C Red No.31、D&C Red No.33、D&C Red No.34、 D&C Red No.36、D&C Violet No.2、D&C Yellow No.7、D&C Yellow No.8、D&C Yellow No.10、D&C Yellow No.11、FD&C Blue No.1、FD&C Green No.3、FD&C Red No.40, FD&C Yellow No.5 and FD&C Yellow No.6;
-acid stain, such as azo, anthraquinone, indigo, ton, pyrene, quinoline, triphenyl methane and fluorane The water-insoluble sodium of coloring agent, potassium, calcium, barium, aluminum, zirconium, strontium, titanium salt, these coloring agent can comprise at least One carboxylic acid group or sulfonic group.
Organic color lake also can be protected by organic carrier (such as Colophonium or aluminum benzoate).
In the middle of organic color lake, we can it should be particularly mentioned those being known with following title: D&C Red No. 2 aluminum color lakes, D&C Red No.3 aluminum color lake, D&C Red No.4 aluminum color lake, D&C Red No.6 aluminum color Shallow lake, D&C Red No.6 barium color lake, D&C Red No.6 barium/strontium color lake, D&C Red No.6 strontium color lake, D&C Red No.6 potassium color lake, D&C Red No.6 sodium color lake, D&C Red No.7 aluminum color lake, D&C Red No.7 barium color lake, D&C Red No.7 calcium color lake, D&C Red No.7 calcium/strontium color lake, D&C Red No.7 Zirconium color lake, D&C Red No.8 sodium color lake, D&C Red No.9 aluminum color lake, D&C Red No.9 barium color lake, D&C Red No.9 barium/strontium color lake, D&C Red No.9 zirconium color lake, D&C Red No.10 sodium color lake, D&C Red No.19 aluminum color lake, 20D&C Red No.19 barium color lake, D&C Red No.19 zirconium color lake, D&C Red No.21 aluminum color lake, D&C Red No.21 zirconium color lake, D&C Red No.22 aluminum color lake, D&C Red No.27 Aluminum color lake, D&C Red No.27 aluminum/titanium/zirconium color lake, D&C Red No.27 barium color lake, D&C Red No.27 Calcium color lake, D&C Red No.27 zirconium color lake, D&C Red No.28 aluminum color lake, D&C Red No.28 sodium color Shallow lake, D&C Red No.30 color lake, 25D&C Red No.31 calcium color lake, D&C Red No.33 aluminum color lake, D&C Red No.34 calcium color lake, D&C Red No.36 color lake, D&C Red No.40 aluminum color lake, D&C Blue No.1 aluminum color lake, D&C Green No.3 aluminum color lake, D&C Orange No.4 aluminum color lake, D&C Orange No.5 aluminum color lake, D&C Orange No.5 zirconium color lake, D&C Orange No.10 aluminum color lake, D&C Orange No.17 barium color lake, D&C Yellow No.5 aluminum color lake, D&C Yellow No.5 zirconium color lake, D&C Yellow No.6 aluminum color lake, D&C Yellow No.7 zirconium color lake, D&C Yellow No.10 aluminum color lake, FD&C Blue No.1 aluminum color lake, FD&C Red No.4 aluminum color lake, FD&C Red No.40 aluminum color lake, FD&C Yellow No. 5 aluminum color lakes and FD&C Yellow No.6 aluminum color lake.
Corresponding to the chemical material each of in these toners of being initially mentioned by < cosmetics, washing Washing article and essence association>(<The Cosmetic, Toiletry, and Fragrance Association>) title of publishing Make<international cosmetic raw material dictionary and handbook>(<International Cosmetic Ingredient Dictionary and Handbook >) book of (1997 editions), page 371 to 386 and page 524 to 528 is mentioned, this book interior Hold and be incorporated to the most by reference in this specification.
In preferred embodiments, color lake is selected from: alkermes;With acid stain such as azo, anthraquinone, Indigo, ton, pyrene, quinoline, triphenyl methane and the water-insoluble sodium of fluorane coloring agent, potassium, calcium, Barium, aluminum, zirconium, strontium, titanium salt (at least one carboxylic acid group or sulfonic group can be included in view of these coloring agent);With Their mixture.
In preferred embodiments, color lake is selected from: alkermes and water-insoluble sodium, calcium, aluminium salt, and Their mixture.
As being combined with the color lake of carmine, we can mention goods number:
CARMIN COVALAC W 3508, CLOISONNE RED 424C and CHROMA-LITE MAGENTA CL4505。
Water-insoluble aluminium salt be preferably selected from FDC Yellow No.5 aluminum color lake, FDC Blue No.1 aluminum color lake, FDC Red No.40 aluminum color lake, FDC Red No.30 aluminum color lake, FDC Green No.5 aluminum color lake and it Mixture.As being combined with the compound in this inorganic color lake, can especially mention goods number: INTENZA FIREFLY C91-1211、INTENZA AZURE ALLURE C91-1251、INTENZA THINK PINK C91-1236。
Water-insoluble calcium salt is preferably selected from Red No.7 calcium color lake.As the chemical combination being combined with this inorganic color lake Thing, can especially mention goods number: INTENZA MAGENTITUDE C91-1234, INTENZA HAUTE PINK C91-1232、INTENZA RAZZLED ROSE C91-1231、INTENZA AMETHYST FORCE C91-7231、INTENZA PLUSH PLUM C91-7441、INTENZA ELECTRIC CORAL 30C91-1233, FLORASOMES-JOJOBA-SMS-10%CELLINI RED-NATURAL and their mixture.
Water-insoluble sodium salt is preferably selected from Red No.6 sodium color lake and Red No.28 sodium color lake and their mixing Thing.As being combined with the compound in this inorganic color lake, can especially mention goods number: INTENZA MANGO TANGO C91-1221 and INTENZA NITRO PINK C91-1235.
In embodiments, present in microcapsule coloring agent selected from inorganic pigment, organic pigment and theirs is mixed Compound, preferably the mixture of at least one inorganic pigment, more preferably at least inorganic pigment, even more preferably selects From metal-oxide, and in particular selected from iron oxides, titanium dioxide granule and their mixture, preferably it Mixture.
The compositions of the present invention can include the mixture of two or more coloring agent, and coloring agent is separately packaged In microcapsule and/or the one or more of blends of coloring agent are encapsulated in Multi-layer microcapsule.Specific at this Embodiment in, each layer of microcapsule can comprise the specific common of at least one specific coloring agent or coloring agent Mixed thing.In this particular, the compositions of the present invention comprises two or more and has different colours Microcapsule.
Skilled person will know how to select coloring agent and the combination of coloring agent, the color needed for producing Effect or color change.As it was earlier mentioned, microcapsule preferably comprises at least titanium dioxide in their coating And/or iron oxides, preferably at least titanium dioxide.In preferred embodiments, microcapsule is in their painting At least titanium dioxide and iron oxides is comprised in Ceng.In certain embodiments, the outer layer of microcapsule comprises two Titanium oxide, more preferably as unique coloring agent.
In specific embodiments, the outer layer of microcapsule comprises organic pigment or iron oxides.
The gross weight of microcapsule relatively, coloring agent is with in 20 weight % to 90 weight %, preferably 30 weight % extremely Amount in the range of 80 weight % and more preferably 50 weight % to 75 weight % exists.
In specific embodiments, microcapsule comprises the metal-oxide of chosen from Fe oxide and titanium oxide, phase Gross weight to microcapsule, it is with in 20 weight % to 90 weight %, preferably 30 weight % to 85 weight % also And more preferably 50 weight % exist to the amount in the range of 85 weight %.
Especially, relative to the gross weight of microcapsule, titanium oxide can be with 28 weight % to 80 weight %, excellent 30 weight % to 75 weight % and more preferably 30 weight % are selected to exist to 50 weight %.In particular In, relative to the gross weight of microcapsule, titanium oxide can be with 50 weight % to 80 weight %, especially 55 weight Amount % to 70 weight % and more particularly 55 weight % exist to 65 weight %.
Especially, relative to the gross weight of microcapsule, iron oxides can be with 5 weight % to 75 weight %, preferably 8 weight % exist to 65 weight %.In specific embodiments, relative to the gross weight of microcapsule, iron oxides Can be higher than 15 weight %, preferably above 30 weight % and especially 40 weight % deposit to the amount of 65 weight % ?.
In preferred embodiments, at least one layer, and the most in each layer, coloring agent is main composition, I.e. represent at least 40 weight % of layer, at least 75 weight % of preferably layer, more preferably at least the 95 of the gross weight of layer Weight %.
In preferred embodiments, the average thickness of titanium dioxide layer is in 5 μm to 150 μ m.
(c) binding agent or material based on lipid
Internal layer and/or outer layer also can advantageously comprise at least one binding agent, are preferably based on the material of lipid.At this In the particular of invention, this material based on lipid can have amphipathic characteristic, i.e. has nonpolar portion Divide and polar portion.
This material based on lipid can include at least one or several C12-C22Fatty acid chain, such as, is selected from Those of stearic acid, Palmic acid, oleic acid, linoleic acid, linolenic acid etc., and mixture.Preferably, these Fatty acid chain is hydrogenated.Finally, these fatty acid chains may be based on the nonpolar moiety of material of lipid.
This material based on lipid is preferably selected from phospholipid.These phospholipid are preferably selected from phosphate acyl glycerol, more excellent Choosing is selected from lecithin, and especially hydrolecithin.
Material based on lipid can represent 0.05 weight % of microcapsule to 5 weight %, represents microcapsule especially 0.1 weight % to 1 weight %.
By combination in microcapsule, there is the three kinds or more kind compound (example of different hardness and/or water solubility Such as sugar alcohol, polymer, material based on lipid), the microcapsule that possible regulation encapsulates toner ruptures on skin The required time, in order to the method being administered on skin by change or intensity, may regulation preferably coloring or Gradient pattern (gradation pattern).
Therefore, in preferred embodiments, laminated coating is including at least the starch and at least as polymer A kind of material (preferably lecithin) based on lipid.
In favourable embodiment, microcapsule includes at least one monosaccharide or derivatives thereof and at least one is many Sugar or derivatives thereof.
In preferred embodiments, microcapsule include the core comprising monosaccharide derivatives and comprise polysaccharide (or its derive Thing) coating, this polysaccharide (or derivatives thereof) includes the sugared, the most some of a type of sugared or several type The sugar of type.
In a more preferred embodiment, microcapsule includes comprising monosaccharide polyalcohol and (is preferably selected from mannitol, red Moss sugar alcohol, xylitol, Sorbitol) core, and comprise the coating of polysaccharide (or derivatives thereof), this polysaccharide (or its Derivant) comprise as sugared at least one or more kinds of D-Glucose unit.
In preferred embodiments, the three kinds or more kind coloring agent during microcapsule is included in different layers.
In preferred embodiments, microcapsule additionally comprises binding agent, is selected from phospholipid, is advantageously selected from Phosphate acyl glycerol and the material based on lipid in particular selected from lecithin.
In specific embodiments, microcapsule includes mannitol, starch polymer and material based on lipid.
With reference to Fig. 1, in preferred embodiments, the present invention advantageously provides variable color microcapsule, it comprises:
I) core (A), preferably has diameter and is less than 800 μm, more preferably less than about 400 μm, is advantageously 1 μm To 300 μm, it is 5 μm to 200 μm and is more particularly the size of 10 μm to 100 μm especially, It is preferably without any coloring agent, and comprises at least one the organic core being preferably selected from least one sugar alcohol, described Preferred monosaccharide-the polyhydric alcohol of sugar alcohol, is advantageously selected from mannitol, erythritol, xylitol and Sorbitol;
Ii) surround a ground floor (B) of described core, comprise:
-at least one coloring agent, preferably iron oxides, and
-binding agent, selected from polymer and material based on lipid, preferably their mixture;
Iii) surround a second layer (C) of ground floor (B), preferably there is 5 μm thickness to 500 μm, comprise:
-titanium dioxide granule, and
-binding agent, selected from polymer and material based on lipid, preferably their mixture;
Iv) optionally, surround a third layer (D) of the second layer (C), comprise:
-at least one coloring agent, and
-binding agent, selected from polymer and material based on lipid, preferably their mixture;
V) optionally, surround third layer (D) (if having third layer) or surround the second layer one the 4th of (C) Layer (E), comprises:
-at least one wall-forming polymer, is preferably selected from: polysaccharide, such as cellulose derivative, especially cellulose ether and Cellulose esters;(gathering) (alkyl) (methyl) acrylic acid and derivant thereof, especially (gather) (alkyl) (methyl) acrylate And derivant;And it is preferably selected from alkyl acrylic/alkyl methacrylate copolymer and their derivant.
In preferred embodiments, polymer is the parent selected from starch and derivant thereof, particularly corn starch Waterborne polymeric.
As the example of the microcapsule of the commercially available compositions for the present invention, we can mention by The following microcapsule that Korea Particle Technology KPT produces with following business name:
-from the Magic50-BW0105 of KPT: comprise mannitol, iron oxides is red, iron oxides is yellow, Iron oxides is black, hydrolecithin, titanium dioxide, the light gray spherical microcapsule of Semen Maydis (Semen Maydis) starch, tool There is 60-200 mesh particle diameter.
1-4-2. comprises the second embodiment of the microcapsule of releasable coloring agent
In this second embodiment, microcapsule comprises:
-core, it includes at least one coloring core and at least one internal color layer final, and
-shell, what it had that at least one surrounds described core crushes (pressure-breakable) parietal layer, optional Exterior color layer and optional outermost shell.
In preferred embodiments, microcapsule includes selected from inorganic pigment, being preferably selected from metal-oxide, such as ferrum Oxide and the coloring agent of titanium oxide.
Preferably, coloring core includes being advantageously selected from least one metal-oxide, more advantageously selected from least one Plant at least one inorganic pigment of iron oxides.
Preferably, parietal layer can be crushed and include being advantageously selected from least one metal-oxide, more advantageously selected from extremely At least one inorganic pigment of few a kind of titanium oxide.
Preferably, this type of iron oxides is located at least in colouring in core, and titanium oxide is located at least in surrounding described core Crushed parietal layer in.
Compared to the gross weight of microcapsule, microcapsule comprises the coloring agent of at least 70 weight %, preferred inorganic pigments, The mixture of preferred inorganic pigments, preferably metal-oxide such as iron oxides and titanium oxide.
Generally, coloring agent microcapsule mean diameter (diameter) of at most about 800 microns used according to the invention.Right For skin care applications, the mean diameter (diameter) of this coloring agent microcapsule preferably less than about 400 microns.Have Profit ground, mean diameter (diameter) is in about 10 to 350 micrometer ranges.Preferably mean diameter will be that 50 μm are to 800 μm, and particularly 60 μm are to 400 μm.
Advantageously, microcapsule has about 18 to 270 mesh (about 1000 μm are to 53 μm), and the most about 25 Mean diameter to 170 mesh (about 710 μm are to 90 μm).
For the skin care compositions and methods of the present invention, relative to the gross weight of compositions, microcapsule Amount will be in the range of 0.1 weight % to 5 weight %, preferably 0.2 weight % to 3 weight %.
For the make-up composition of the present invention, relative to the gross weight of compositions, the amount of microcapsule will In 0.5 weight % to 20 weight %, preferably 1 weight % to 15 weight %, more preferably 2 weight % to 10 weight % In the range of.
In specific embodiments, relative to the gross weight of compositions, the coloring agent of encapsulation is with the pigment of encapsulation Active substances can be in 0.5 weight % to 20 weight %, particularly 1 weight % to 15 weight % and more special It not that the amount in the range of 2 weight % to 12 weight % is present in the compositions of the present invention.
They generally in the final stage prepared and will be attached to cosmetics after filtration stage (if any) In formula, to avoid rupturing.Preferably, the microcapsule of present invention temperature below 50 DEG C is added and uniformly mixes Close.Them are made to mix gently with oar rather than homogenizer.
In certain aspects of the present disclosure, more than 60%, preferably more than 70%, especially more than 80% and more special Not Duo Yu 90% microcapsule by pressing with hands or instrument, friction, wiping and/or after cleaning 1 minute, excellent Select the implosion of 1 to 40 second, particularly 1 to 30 second and more particularly 1 to 20 second with the internal coloring of release Agent.But, described ratio and time limit are not the most crucial.
1-4-2-1. core (coloring agent and binding agent or material based on lipid)
In this second embodiment, the core of this microcapsule comprises coloring core, and it comprises at least one coloring agent and has At least one binding agent of profit ground, such as based on lipid material.
Coloring agent is not particularly limited, and kinds described above is preferably used.
Binding agent be preferably selected from least one hydrophilic polymer, at least one material based on lipid and they Mixture, preferably their mixture.Typically, it is difficult to by only using coloring agent component or granule not to use Any binding agent forms coating layer (coating layer).Even if there is no the coating of binding agent additionally, difficulty formed Layer, this coating layer can be easily damaged or rupture or any component or granule can easily removals from coating layer.Cause This, can use binding agent to promote coating process and to improve the ruggedness of coating layer.This binding agent is selected from viscosity Polymeric material, it can play the effect of wall-forming materials (wall-forming polymer material).
In the present invention, binding agent be preferably selected from least one wall-forming materials, material based on lipid and they Mixture.It is highly preferred that binding agent is to comprise the polymer as wall-forming materials and as coated substrate (coating The mixture of both based on lipid base).
Coated substrate refers to hydrophilic coating substrate, hydrophobic coating substrate or coated substrate based on lipid.Due to Hydrophilic coating substrate can be extracted together with coloring agent and hydrophobic coating substrate is due to its strongest film character The sensation that there is foreign substance can be produced, coated substrate of based on lipid is preferably used.
In specific embodiments, this material based on lipid can have amphipathic characteristic, i.e. has nonpolar Part and polar portion.
This material based on lipid can include at least one or several C12-C22Fatty acid chain, such as, is selected from Stearic acid, Palmic acid, oleic acid, linoleic acid, linolenic acid etc. and mixture thereof.Preferably, these fatty acid chains It is hydrogenated.Finally, these fatty acid chains may be based on the nonpolar moiety of material of lipid.
Material based on lipid is the amphiphilic material in a molecule with both polar portion and nonpolar moiety Material, and include, such as, selected from stearic acid, Palmic acid, oleic acid, linoleic acid, linolenic acid and mixture thereof C12-C22Fatty acid chain.This fatty acid chain can be hydrogenated, and is optionally formed the non-of material based on lipid Polar portion.
Material based on lipid is selected from phospholipid such as phosphatidylcholine, PHOSPHATIDYL ETHANOLAMINE, phosphatidic acid or phosphatidyl Serine, sphingolipid such as S1P or sphingomyelins and ceramide, preferably ceramide or lecithin, its For mixture of phospholipids, especially hydrolecithin.
The amount of material based on lipid can be by considering wall-forming polymer and other component such as coloring agent and/or two The type of titan oxide particles and amount determine.But, generally speaking, for the gross weight of each layer, based on fat The amount of the material of matter is selected from 0.1 weight % to 30 weight %, and 0.2 weight % is to 25 weight % especially, and preferably 0.3 Weight % is to 20 weight % and more preferably 0.4 weight % to 20 weight %.When the amount of material based on lipid is less than 0.1 During weight %, crushability or solvability may reduce, and when it is more than 25 weight %, ruggedness may fall Low or processing and store during stability may reduce.
In the present invention, wall-forming polymer is selected from hydrophilic polymer.Term " hydrophilic polymer " refers to can With the polymer that water or alcoholic compound (especially selected from lower alcohol, dihydroxylic alcohols and polyhydric alcohol) form hydrogen bond, especially There are those of O-H, N-H and S-H key in the molecule.
Hydrophilic polymer is selected from following polymer or its mixture:
-acrylic or methacrylic acid homopolymer or copolymer or its salt and ester, and especially: by Allied Colloid The product that company sells with title Versicol F or Versicol K;By Ciba-Geigy company with title Ultrahold 8 The product sold;And the polyacrylic acid of Synthalen K type;(right with polyacrylic salt, especially sodium salt Should be in INCI title sodium acrylate copolymer) and more particularly sold with title Luvigel EM by BASF AG Crosslinking sodium polyacrylate (corresponding to INCI title sodium acrylate copolymer (with) caprylic/capric triglyceride);
-the acrylic acid sold with title Reten by Hercules company with its sodium-salt form and the copolymerization of acrylamide Thing, the sodium polymethacrylate sold with title Darvan No.7 by Vanderbilt company and by Henkel The sodium salt of the multi-hydroxy carboxy acid that company sells with title Hydagen F;
-polyacrylic acid/alkyl acrylate copolymer, preferably modification or unmodified carboxy vinyl polymer; The most particularly preferred copolymer is acrylate/C10-C30Alkyl acrylate copolymer (INCI title: acrylic acid Ester/C10-30Alkyl acrylate cross-linked polymer), such as by Lubrizol company with trade name Pemulen TR1, The product that Pemulen TR2, Carbopol 1382 and Carbopol ETD2020, Carbopol Ultrez 21 sell, And even more preferably Pemulen TR-2;
-alkyl acrylic/alkyl methacrylate copolymer and their derivant, particularly their salt and it Ester, such as from Evonik Degussa with trade name EUDRAGIT RSPO provide acrylic acid second The copolymer of the methacrylate with quaternary ammonium group of ester, methyl methacrylate and low content;
-the AMPS that sold by Clariant company (neutralizes and highly cross-linked polyacrylamide base first by ammonia part Base propane sulfonic acid);
-AMPS/ acrylamide copolymer, product Sepigel or Simulgel such as sold by SEPPIC company, Especially INCI title polyacrylamide (with) C13-C14Isoparaffin (with) copolymer of laureth-7;
The polyoxyethylated AMPS/ alkyl methyl of-Aristoflex HMS type as sold by Clariant company Acrylate copolymer (crosslinking or noncrosslinking);
-anion, cation, both sexes or non-ionic chitin or chitosan polymer;
-cellulosic polymer and their derivant, preferably in addition to alkylcellulose, selected from hydroxy ethyl fiber Element, hydroxypropyl cellulose, hydroxymethyl cellulose, ethylhydroxyethylcellulose and carboxymethyl cellulose and also There is quaternized cellulose derivative;In preferred embodiments, cellulosic polymer is carboxymethyl cellulose;
-final modified starch polymer and their derivant;In preferred embodiments, starch polymer For native starch;
-polyvinyl, such as polyvinyl pyrrolidone, methyl vinyl ether and the copolymer of maleic anhydride, Vinyl acetate and the copolymer of the copolymer of .beta.-methylacrylic acid, vinyl pyrrolidone and vinyl acetate, vinyl Ketopyrrolidine and the copolymer of caprolactam, polyvinyl alcohol;
The most modified polymer of-natural origin, such as galactomannan and derivant thereof, such as Konjac glucomannan (konjac gum), gellan gum, locust bean gum, fenugreek gum, Indian tragacanth (karaya gum), Tragacanth, I Primary glue, acacin (acacia gum), guar gum, hydroxypropyl guar gum, use methyl carboxylic acids sodium are group modified Hydroxypropyl guar gum (Jaguar XC97-1, Rhodia), guar hydroxypropyltrimonium ammonium chloride and xanthan gum Derivant;
-alginate and carrageenin;
-glycosaminoglycans (glycoaminoglycan), hyaluronic acid and derivant thereof;With
-mucopolysaccharide, such as hyaluronic acid and chondroitin sulfate and mixture thereof.
Preferably, the hydrophilic polymer of the present invention is selected from polysaccharide and their derivant, acrylic acid or methyl Acrylic acid homopolymer and/or copolymer or its salt and ester and their mixture.
Polysaccharide and their derivant be selected from chitosan polymer, chitin polymer, cellulosic polymer, Starch polymer, galactomannan, alginate, carrageenin, mucopolysaccharide and their derivant and Its mixture.
Polysaccharide and their derivant are preferably selected from starch polymer.
Preferably, hydrophilic polymer be selected from corn starch, polymethyl methacrylate, cellulose or its spread out Biological such as carboxymethyl cellulose (CMC), cellulose esters and ether and aminocellulose and mixture thereof.
Preferably, hydrophilic polymer be selected from corn starch, polymethyl methacrylate, they derivant, And mixture.
Methacrylic acid and/or the preferred homopolymer of methacrylate and/or copolymer are wherein metering system The copolymer of acid methyl ester and ethyl acrylate has those of the molecular weight of 750kDa to 850kDa.
The hydrophilic polymer being used as wall-forming materials in the present invention is not crosslinking.
The amount of polymer or wall-forming polymer can be by considering coloring agent, titanium dioxide granule and/or based on lipid The type of material and amount determine.But, generally speaking, for the gross weight of each layer, polymer in each layer Or the amount of wall-forming polymer is selected from 0.1 weight % to 30 weight %, 0.2 weight % is to 25 weight % especially, preferably 0.3 weight % to 20 weight % and more preferably 0.4 weight % are to 20 weight %.When the content of material based on lipid is less than During 0.1 weight %, crushability or solvability may reduce, and when it is more than 25 weight %, ruggedness may Stability during reducing or processing and store may reduce.This hydrophilic polymer described in this section Can serve as both shell polymeric and binding agent.
This core can be such as by comprising at least one coloring agent, at least one gathering as wall-forming materials in a solvent The spray drying of the solution of compound and at least one material based on lipid or fluidized-bed process with granule, powder, Prepared by the form of particle (granule), microsphere and microcapsule.
Coloring core, and the size of more generally core is not particularly limited, and can be according to the final microcapsule needed Properly select.Such as, colour core, and the size of more generally core can be special more than 20 μm or bigger It not 30 μm or bigger, preferably 40 μm or bigger, more preferably 50 μm or bigger, and less than 800 μm Or less, particularly 700 μm or less, preferably 600 μm or less, more preferably 500 μm or less.
Relative to total radius of microcapsule, the radius of core is more than 50%, especially greater than 60%, preferably greater than 70%, And more preferably greater than 80%.Such as, the ratio between nuclear radius and thickness of the shell can be 1:0.05 to 1:0.5.
For the election, relative to the gross weight of microcapsule, the amount of core can be more than 30 weight %, and especially greater than 40 Weight %, preferably greater than 50 weight %, and more preferably greater than 60 weight %.Therefore, microcapsule has in granule There is the coloring agent of heavy load amount.
This core can have one or more internal color layer surrounding coloring core.Internal color layer can be to be positioned at Color core and each layer that can crush between parietal layer.
Internal color layer includes, such as, and the first internal color layer, the second internal color layer and the 3rd internal color Layers etc., coloring agent contained in the most each internal color layer and binding agent are same to each other or different to each other.It is being preferable to carry out In scheme, this coloring core can comprise one or two internal color layer, preferably one internal color layer.
When this core has coloring core and during internal color layer, can be by comprising at least one coloring agent and preferably at least A kind of binding agent coloring core solution pelletize formed coloring core, can by with comprise at least one coloring agent with The solution coating coloring karyomorphism of the internal color layer of a kind of binding agent becomes internal color layer.Coating process Can be carried out by fluid bed coating process.
The thickness of internal color layer is not particularly limited and can properly select according to the final microcapsule needed.Example As, colour core, and the thickness of more generally core can be more than 20 μm or bigger, particularly 40 μm or bigger, Preferably 60 μm or bigger, more preferably 80 μm or bigger, and less than 200 μm or less, particularly 160 μm Or less, preferably 120 μm or less, more preferably 100 μm or less.
For the election, the gross weight of relatively core, the amount of internal color layer can be 20 weight % to 80 weight %, special 30 weight % are not to 70 weight %, and preferably 40 weight % are to 60 weight %.
In specific embodiments, this coloring core without binding agent and is comprised the inside face of coloring agent and binding agent Chromatograph surrounds, and thus contained in this core pigment will be easier to dispersion when microcapsules rupture.
In coloring core, can will not scatter or divide with layer by coloring agent in coating process and/or after removal of the solvent From amount use binding agent, and relative to coloring core gross weight, generally can selected from 1 weight % to 30 weight %, Preferably 2 weight % are to 25 weight %, and 5 weight % are to 20 weight % especially, and more particularly 5 weight % are extremely The amount of 15 weight % uses.
In preferred embodiments, relative to the gross weight of core, coloring agent, and preferred pigments, even more preferably ferrum Oxide, with at least 70 weight %, especially at least 75 weight %, preferably at least 80 weight %, the most extremely Few 85 weight %, as 80 weight % are present in core to the amount of 99 weight %.
In preferred embodiments, relative to the gross weight of microcapsule, coloring agent, and preferred pigments, more preferably Iron oxides, with at least 30 weight %, especially at least 35 weight %, preferably at least 40 weight %, such as 40 weights The amount of amount % to 60 weight % exists.
Relative to the gross weight of microcapsule, the amount of the iron oxide particle in this microcapsule can be that 20 weight % are to 60 Weight %, preferably 25 weight % are to 55 weight %, and more preferably 30 weight % are to 50 weight %.It is highly preferred that Relative to the gross weight of microcapsule, the amount of the iron oxide particle in this microcapsule can be that 30 weight % are to 58 weights Amount %, preferably 35 weight % are to 55 weight %, and more preferably 40 weight % are to 50 weight %.
1-4-2-2. can crush parietal layer or titanium dioxide granule layer
Microcapsule has the crushed parietal layer comprising at least one coloring agent.Coloring agent is preferably selected from inorganic pigment, It is more preferably selected from metal-oxide, and even more preferably selected from titanium dioxide granule.
Preferably, it is included in the coloring agent that can crush in parietal layer and is different from the coloring agent being included in coloring core, example As being all metal-oxide different from each other.
In preferred embodiments, titanium dioxide granule disperses in this layer and mutual by binding agent discontinuously Connect.
Term " can crush " or " crushable " refers to pressing with hands or instrument such as cloth, sponge or paper, rubbing Can be easily manufactured when wiping, wiping and/or scouring and rupture.
The titanium dioxide granule layer that can crush can comprise titanium dioxide granule and binding agent, and described binding agent can wrap Containing wall-forming materials.
In the crushed parietal layer of the present invention, it is believed that the titanium dioxide granule being embedded in wall-forming materials will be with irreversible Mode is destroyed and can be crushed parietal layer, and promotes or improve disintegrate or the dissolving of described parietal layer.In addition, it is further anticipated that, two Titan oxide particles plays an important role for the sensation of intensity, durability, crushing property and the acquisition of this parietal layer.
Such as, this can crush parietal layer and can be formed through the following steps:
A titanium dioxide granule and binding agent are dissolved or dispersed in suitable solvent by (), comprise titanium dioxide to produce Titanium granule and the solution of binding agent,
B () has the granule of internal color layer with the solution coating obtained in above (a), and
C () is optionally by middle to above (b) the gained particle drying obtained.
Described coating can be carried out by using bed process, but if necessary, it is possible to utilize other coating process. About suitable solvent available in above-mentioned steps, it may be mentioned that water or low boiling point solvent, such as dichloromethane, first Alcohol and ethanol.
This titanium dioxide granule layer (its thickness can become according to the amount of titanium dioxide used and/or the type of binding agent) Can have 10 μm or bigger, preferably 20 μm or bigger, more preferably 30 μm or bigger, particularly 40 μm or Bigger, usual 300 μm or less, preferably 250 μm or less, more preferably 200 μm or less, and especially It is the thickness of 150 μm or less.
For can crushing the gross weight of parietal layer, this amount that can crush the titanium dioxide granule in parietal layer is preferably selected from 50 weight % are to 99 weight %, and more preferably 60 weight % are to 98 weight %, and even more preferably 70 weight % are to 97 Weight %, and especially 80 weight % to 95 weight %.Preferably, described coloring agent, and particularly titanium dioxide The amount of titanium granule represent can crush parietal layer less than 100%.
Relative to the gross weight of microcapsule, the amount of the titanium dioxide granule in this microcapsule is preferably selected from 20 weight % To 60 weight %, preferably 25 weight % are to 55 weight %, and more preferably 30 weight % are to 50 weight %.
Colour the coloring agent (preferably iron oxides) in core and coloring agent (the preferably titanium dioxide that can crush in parietal layer Grain) all it is present in microcapsule the coloring agent (and preferably iron oxides) as (such as) colours in core with respective total amount It is more than or equal to 1 relative to the weight ratio of the coloring agent (preferably titanium dioxide granule) that can crush in parietal layer.
Iron oxides and titanium dioxide granule all with respective total amount be present in microcapsule as iron oxides relative to The weight ratio of titanium dioxide granule is more than or equal to 1.
Average diameter or the size of titanium dioxide granule are not particularly limited, but have usual 10nm to 20 μm, Preferably 50nm to 10 μm, more preferably 100nm to 5 μm, and particularly 150nm to 5 μm average straight Footpath.The average diameter less than 10nm of titanium dioxide granule or size may result in and can crush ability reduction, and greatly Average diameter in 20 μm can make it difficult to form titanium dioxide granule layer.There is first less than above-mentioned scope Footpath but there is the titanium dioxide granule of the second particle diameter in above-mentioned particle size range and be applicable to the present invention.
Exterior color layer optional for 1-4-2-3.
Microcapsule is additionally contained in the optional exterior color layer that can crush on titanium dioxide granule layer.Can be by using There is the solution of coloring agent and binding agent, such as, form this by bed process coating titanium dioxide granule layer Exterior color layer.Coloring agent and binding agent in exterior color layer can be with those phases for internal color layer Same or different.
Generally speaking, it is provided that exterior color layer is to give and the white produced by titanium dioxide granule layer and/or inside The visual color that the color of color layers is different.Therefore, the coloring agent in exterior color layer can not disturb and clean The amount of the color shown by internal color layer during microcapsule uses.
Relative to the gross weight of core, the amount of exterior color layer can be 1 weight % to 60 weight %, preferably 2 weight % To 50 weight %, more preferably 3 weight % are to 40 weight %, and particularly 4 weight % are to 30 weight %.But, Relative to the gross weight of the coloring agent in internal color layer, the amount of the coloring agent in exterior color layer can be 0.01 weight Amount % to 5 weight %, preferably 0.05 weight % to 4.5 weight %, more preferably 0.1 weight % to 4 weight %, and Particularly 0.5 weight % is to 3.5 weight %.
If the color of exterior color layer is not disturbed the color of internal color layer, can additionally improve exterior color layer In the amount of coloring agent.Those skilled in the art can be by considering the face of coloring agent contained in internal color layer Normal complexion amount and required color to be shown and select the coloring agent in exterior color layer in a suitable manner Color and amount.
The thickness of exterior color layer is not particularly limited and can properly select according to the final microcapsule needed.Example As, exterior color layer can have more than 20 μm, particularly 40 μm, preferably 60 μm, and more preferably 80 μm, With less than 200 μm, particularly 150 μm, preferably 120 μm, and the thickness of more preferably 100 μm.
1-4-2-4. outermost shell
Microcapsule can be included in the protectiveness outermost that can crush on titanium dioxide granule layer or other exterior color layer Layer shell, to protect microcapsule from the impact of moisture in air or guarantee that microcapsule is outstanding at carrier during storing It is long-time stability in the solution.
Outermost shell can be made up of at least one polymer, and preferably can be by selected from least one following polymer Make: polysaccharide and their derivant, acrylic or methacrylic acid homopolymer or copolymer or its salt and ester, Polystyrene-maleic anhydride copolymer and their mixture, the most poly-(methyl) acrylate, cellulose ether, Cellulose esters and their derivant, and their mixture.
For the gross weight of microcapsule, the amount of outermost shell is selected from 0.1 weight % to 20.0 weight % and preferably Selected from 0.5 weight % to 15 weight %.When the amount of outermost shell is less than 0.1 weight %, shell coating is probably unintentionally Justice, and when it is more than 20.0 weight %, the sensation that there is foreign substance may be caused.
The thickness of outermost shell is not particularly limited and can properly select according to the final microcapsule needed.Example As, outermost shell can have more than 20 μm, especially 30 μm, preferably 40 μm and more preferably 50 μm and be less than 200 μm, especially 150 μm, preferably 120 μm and the thickness of more preferably 90 μm.
Can will be described later as other example of the polymer that outermost shell is implemented and can be used for the present invention's Be given during binding agent in microcapsule.
1-4-3. method
Microcapsule can be produced by conventional method known in the field in coating or encapsulation field (domain), Described side includes balling-up (pelletization), pelletize, coating etc..Such as, microcapsule can be by as at WO01/35933 Mixture (activating agent, pigment, polymer, solvent) with inclusion compound disclosed in WO2011/027960 And be dried the step acquisition to form capsule, or pass through such as pelletize disclosed in FR2841155 and pass through The step being spray-dried coating obtains or obtains by having been used in the fluidization in food and pharmaceutical industry ?.Can quote the example in WO08/139053, preparation includes the spherical of the concentric layer of sugar core and pharmaceutically active agents Body multilamellar.By dipping or pulverize or injection carries out fixing on core of pharmaceutically active agents, and applying the subsequently Ground floor it was dried before two layers.
Preferably, introducing the microcapsule in the compositions of the present invention is to obtain by the fluidization described below , and preferably by the fluidization acquisition described below, at least partly obtain.The spy of bed process Levying and be compared with spray drying, it obtains real capsule, and described spray drying obtains by particle aggregation shape The granular solid matter that becomes or obtain nuclear material random dispersion to the substrate in polymer.Especially, fluid bed side is used Method allows the substantially spherical microcapsule with substantially spherical core, and described microcapsule is surrounded by circumference At least one layer and the preferably circumference of described core surround at least one outer layer encirclement of internal layer.
Such as, ' Fluid-Bed Coating, Teunou, E.;Poncelet,2005,D.Food Science and Technology (BocaRaton, FL, United States), volume 146, prints (Issue) Encapsulated and Powdered Foods, discloses bed process in the 197-212 page.Skilled person will know how to adjust Joint allows reproduction according to air capacity, amount of liquid and the temperature of the microcapsule of the present invention.
Preferably bed process includes W ü rster method and/or tangential spraying (tangential spray) method.With become Ball method is different, and this type of method allows the ball-type capsule with the core surrounded by one or more circumferential layer.
By combination in microcapsule, there are two or more compound (examples of different hardness and/or water solubility Such as polymer, material based on lipid) and titanium dioxide granule, regulation may encapsulate the microcapsule of toner at skin Rupture the required time on skin, in order to the method being administered on skin by change or intensity, may regulate preferably Coloring or gradient pattern.
Preferably, this laminated coating comprises at least starch as polymer, and at least one material based on lipid Material and preferably lecithin.
Preferably, this microcapsule comprises additionally in selected from phospholipid, is advantageously selected from phosphate acyl glycerol and particularly ovum The material based on lipid of phospholipid.
Preferably, this microcapsule includes the coloring agent (for color) that three kinds or more kind is different.It is further preferred that Described coloring agent is inorganic pigment, and even more preferably metal-oxide.
In the present invention, the preparation of coating solution used in fluid bed coating process can use organic solvent. This organic solvent is not particularly limited, but preferably includes dichloromethane, methanol, ethanol and mixture thereof.May Use any organic solvent, as long as its solubilized or disperse described polymer and/or material based on lipid, have Less than the boiling point of the boiling point of water, and there is low-residual toxicity.
Microcapsule for the present invention is obtainable through the following steps, and obtains the most through the following steps:
(a-1) preparation comprises the granule of at least one coloring agent and the coloring core (A-1) of at least one binding agent, and
(a-2) optionally with the coloring core of preparation in a kind of solution coating above-mentioned steps (a-1), dissolve in described solution Or disperse those identical or different coloring agent used with above-mentioned steps (a-1) and binding agent, internal to be formed Color layers (A-2),
B () is coated with the granule of preparation, titanium dioxide in described solution in above-mentioned steps (a-1) or (a-2) with a kind of solution Titanium granule and binding agent are formed and can crush parietal layer (B),
(c-1) optionally use the granule obtained in a kind of solution coating above-mentioned steps (b), dissolve in described solution or divide Dissipate those identical or different coloring agent used with above-mentioned steps (a-1) or (a-2) and binding agent, outside to be formed Color layers (C-1),
(c-2) optionally with the granule obtained in a kind of solution coating above-mentioned steps (b) or (c-1), molten in described solution Solve or be dispersed into shell polymeric, to form outermost shell.
The present invention will be further explained by means of the following examples, but be not limited to them.
The character of 1-4-4 microcapsule
Microcapsule is stable in the present compositions, the most at high temperature, is greater than or equal to 40 DEG C At a temperature of, such as stablize in the baking oven of 45 DEG C 1 month, preferably two months and the most preferably three months; Or in the baking oven of 60 DEG C, stablize 15 days.
Preferably, microcapsule presents suitable softening kinetics.It is highly preferred that with in formula other change Compound contacted after at least three hours, the hardness (hardness) of microcapsule be advantageously 5 to 50 grams, more preferably 6 To 20 grams and even more preferably 7 to 10 grams.This hardness and the combination including this microcapsule for preparation The commercial run of thing adapts.Such value of softening kinetics and hardness allows not only to provide microcapsule attractive in appearance, And the compositions of overall aesthetic is provided.
Especially, compositions can cause different tones (shades) or color gradient according to the intensity of friction.As Being measured in CIE experimental system 1976, compositions can advantageously present high chrominance C *.
The surfactant that 1-5. is other
In addition to above (b), the compositions of the present invention can further include the surfactant that at least one is other. The other surfactant of single type can be used, but can be combined and use two or more different types of separately Outer surfactant.
As other surfactant, at least one ionic surface active agent can be used.Described ion surface is lived Property agent is selected from cationic surfactant, anion surfactant and amphoteric surfactant, is preferably selected from Anion surfactant and amphoteric surfactant and more preferably anion surfactant.
1-5-1. cationic surfactant
Cationic surfactant is unrestricted.Cationic surfactant optionally selected from polyoxyalkylenated primary, Secondary or tertiary fatty amine salt, quaternary ammonium salt and mixture thereof.
The example of the quaternary ammonium salt that can be mentioned that includes, but are not limited to those of following logical formula V:
[formula (V)]
Wherein R1、R2、R3And R4May be the same or different, selected from containing 1 to 30 carbon atom and optionally containing There are straight chain and the branched-chain aliphatic group of hetero atom such as oxygen, nitrogen, sulfur and halogen.Described aliphatic group is selected from, example Such as alkyl, alkoxyl, C2-C6Polyoxyalkylenes, alkylamidoalkyl, (C12-C22) alkylamide (C2-C6) alkyl, (C12-C22) acetate alkyl ester group and hydroxyalkyl;With aromatic group such as aryl and alkylaryl;And X-Selected from halogenation Thing, phosphate, acetate, lactate, (C2-C6) alkyl sulfate and alkyl-or alkylaryl-sulfonate;Miaow The quaternary ammonium salt of oxazoline;Bi-quaternary ammonium salt;With the quaternary ammonium salt comprising at least one ester functional group.
Above-mentioned can be used on includes but not limited to according to the quaternary ammonium salt in the compositions of the present invention, tetraalkyl chlorine Change ammonium, such as dialkyl dimethyl ammonium chloride and alkyl trimethyl ammonium chloride, wherein said alkyl comprise about 12 to 22 carbon atoms, such as mountain base trimethyl ammonium chloride, VARISOFT TA100, cetyltrimethylammonium chlorine Change ammonium and benzyl dimethoylstearyl ammonium chloride;Palmitamide hydroxypropyltrimonium chloride;And stearamide propyl Dimethyl (myristyl acetate) ammonium chloride (stearamidopropyldimethyl (myristyl acetate) ammonium Chloride), by Van Dyk company with titleSell.
In one embodiment, the cationic surfactant that can use in the present compositions is selected from season Ammonium salt, such as, selected from mountain base trimethyl ammonium chloride, CTAB, Quaternium-83, Quaternium-87, Quaternium-22, mountain amido propyl-2,3-dihydroxypropyl alkyl dimethyl ammonium chloride, Petiolus Trachycarpi Amidopropyltrimonium chloride and SAPDMA.
1-5-2. anion surfactant
Anion surfactant is unrestricted.Anion surfactant can be in particular selected from the albumen of plant origin Matter or the anionic derivative of fibroin, phosphate ester (phosphate) and alkyl phosphate, carboxylate, sulfosuccinic Acid esters (sulphosuccinate), amino acid derivativges, alkyl sulfate (alkyl sulphate), alkyl ether sulphate, Sulfonate, isethionate, taurate, alkyl sulfoacetate (alkyl sulphoacetate), polypeptide, The anionic derivative of alkyl polyglucoside, and their mixture.
1) anionic derivative of the protein of plant origin is the protein hydrolysate comprising hydrophobic group, For described hydrophobic group, it may be naturally occurring in protein or by protein and/or proteolysis Product adds with the reaction of hydrophobic compound.Described protein is plant origin or derived from silk, and institute State hydrophobic group and specifically for aliphatic chain, such as, can contain the alkyl chain of 10 to 22 carbon atoms.As plant The anionic derivative of the protein in source, can particularly mention and comprise the alkyl with 10 to 22 carbon atoms The Fructus Mali pumilae of chain, Semen Tritici aestivi, Semen sojae atricolor or oat egg white matter hydrolyzate, and their salt.Described alkyl chain can be special It is lauryl chain, and described salt can be sodium, potassium and/or ammonium salt.
Accordingly, as comprising the protein hydrolysate of hydrophobic group, can be mentioned that such as protein hydrolysate Salt, wherein said protein is the fibroin modified by lauric acid, as by Kawaken with title Kawa Silk The product sold;The salt of protein hydrolysate, wherein said protein is the wheat protein modified by lauric acid, Such as potassium salt (the CTFA title: lauroyl wheat amino acid sold with title Aminofoam W OR by Croda Potassium), and sodium salt (the CTFA title: lauroyl Semen Tritici aestivi ammonia sold with title Proteol LW 30 by Seppic Base acid sodium);The salt of protein hydrolysate, wherein said protein comprises and has 10 to 22 carbon atoms The avenin of alkyl chain, and the salt of more particularly protein hydrolysate, wherein said protein is by the moon The avenin that cinnamic acid is modified, such as the sodium salt sold with title Proteol OAT (30% aqueous solution) by Seppic (CTFA title: lauroyl Herba bromi japonici amino acid sodium);Or comprise the Herba Marsileae Quadrifoliae of the alkyl chain with 10 to 22 carbon atoms The really salt of protein hydrolysate, as sold with title Proteol APL (water/ethylene glycol solution of 30%) by Seppic Sodium salt (CTFA title: cocos nucifera oil acyl Fructus Mali pumilae amino acid sodium).Also can mention by Seppic with title Proteol SAV 50S sell with sarcosine sodium neutralize lauroyl amino acid (aspartic acid, glutamic acid, glycine, Alanine) mixture (CTFA title: cocoamido acid sodium).
2) as phosphate ester and alkyl phosphate, can be mentioned that such as monoalkyl phosphoric acid esters and dialkyl phosphate, as By Kao Chemicals with titleThe lauryl phosplate sold, the potassium of 1-isobutyl-3,5-dimethylhexylphosphoric acid Salt, by Cognis with titleThe monoesters sold and the mixture (mainly diester) of diester, by Cognis is with titleSell octylphosphonic acid monoesters and the mixture of diester, by Condea with TitleEthoxylation (EO of 7mol) the 2-butyl octyl phosphoric acid sold Monoesters and the mixture of diester, by Uniqema with numberingWith List (the C sold12-C13) potassium salt of alkyl phosphate or triethanolamine salt, by Rhodia Chimie with TitleThe Tryfac 5573 potassium sold, and by Uniqema with title The cetyl phosphate potassium that Arlatone MAP 160K sells.
3) can be mentioned that as carboxylate:
-amido ether carboxylate (AEC), such as lauryl amido ether carboxylic acid sodium (3EO), by Kao Chemicals With titleSell;
-polyoxyethylenated carboxylic acids salt, such as oxyethylation (6EO) sodium laureth carboxylate (65/25/10 C12-C14-C16), by Kao Chemicals with titleSell, be derived from the poly-of olive oil Oxyethylation and carboxymethylated fatty acid, by Biologia E Tecnologia with titleSell, Or oxyethylation (6EO) tridecyl ether carboxylic acid sodium, by Nikkol with titleGo out Sell;With
-(such as potassium hydroxide, sodium hydroxide, triethanolamine, N-METHYL-ALPHA-L-GLUCOSAMINE, rely ammonia with organic or inorganic alkali Acid and arginine) neutralize there is C6To C22The salt (soap) of the fatty acid of alkyl chain.
4) as amino acid derivativges, can specifically mentioned amino acid whose alkali metal salt, such as:
-sarcosinate, such as sodium lauroyl sarcosine, by Ciba with titleSell or by Seppic is with titleSelling, myristoyl-N-methylaminoacetic acid sodium, by Nikkol with title Sell, or palmitoyl sarcosine sodium, by Nikkol with title Sell;
-alanine salt, such as N-lauroyl-N-methyl nitrosourea base sodium propionate, by Nikkol with title Sell or by Kawaken with titleSell, or N-Laurel Acyl-N-methylalanine triethanolamine, by Kawaken with titleSell;
-glutamate, Glu, such as single cocos nucifera oil acyl glutamic acid triethanolamine, by Ajinomoto with title Selling, lauroyl glutamate triethanolamine, by Ajinomoto with title Sell;
-aspartate, such as N-lauroyl aspartic acid triethanolamine and N-myristoyl aspartic acid three ethanol The mixture of amine, by Mitsubishi with titleSell;
-glycine derivative (glycinate), such as N-sodium cocoyl glycinate, by Ajinomoto with titleSell with Amilite GCK 12;
-citrate (citrates), such as the lemon acid monoester of oxyethylation (9mol) cocoanut oil alcohol, by Goldschmidt Sell with title Witconol EC 1129;With
-galacturonic acid hydrochlorate, such as dodecyl D-galactoside alduronic acid sodium (sodium dodecyl D-galactoside uronate), Soliance sell.
5) as sulfosuccinate, can be mentioned that such as oxyethylation (3EO) Laurel (70/30C12/C14) alcohol list sulphur Base succinate, by Witco with titleWithSell, C12-C14The disodium salt of half sulfosuccinate of alcohol, by Zschimmer Schwarz with title Selling, oxyethylation (2EO) oleoyl amido sulfosuccinate disodium, by Cognis with name ClaimSelling, oxyethylation (5EO) lauramide list sulfosuccinate, by Sanyo With titleSell, oxyethylation (10EO) lauryl citrate list sulfosuccinate Disodium salt, by Witco with titleSell, or castor oil acid single ethanol amide list sulfo group Succinate, by Witco with titleSell.It is used as polydimethylsiloxane sulphur Base succinate, such as PEG-12 dimethyl polysiloxane sulfosuccinate disodium, by MacIntyre with title Mackanate-DC 30 sells.
6) as alkyl sulfate, can be mentioned that such as lauryl sulfate ester triethanolamine (CTFA title: TEA Lauryl sulfate ester salt), such as the product sold with title Empicol TL40FL by Huntsman or by Cognis The product sold with title Texapon T42, this product is with 40% in aqueous.Also can mention lauryl sulfur Acid esters ammonium (ammonium lauryl sulphate, CTFA title: lauryl sulfate ester ammonium), as by Huntsman The product sold with title Empicol AL 30FL, it is with 30% in aqueous.
7) as alkyl ether sulphate, can be mentioned that such as lauryl ether sulfates sodium (CTFA title: lauryl alcohol gathers Ether sodium sulfovinate), as sold with title Texapon N40 and Texapon AOS 225UP by Cognis, Or lauryl ether sulfates ammonium (CTFA title: laureth sulfuric ester ammonium), as by Cognis with title Standapol EA-2 sells.
8) as sulfonate, can be mentioned that such as alpha-alkene sulfonate, such as alpha-olefin sodium sulfonate (C14-C16), by Stepan is with titleSell, by Witco with titleWithSell or by Stepan with titleSell, secondary alkene Hydrocarbon sulfonate sodium (secondary sodium olefinsulphonate), by Clariant with title Sell;Or linear alkyl arylsulfonates, such as sodium xylene sulfonate, by Manro with title WithSell.
9) as isethionate, can be mentioned that acyl-hydroxyethyl sulfonate, such as sodium cocoyl isethionate, As by Jordan with titleThe product sold.
10) as taurate, can be mentioned that the sodium salt of palm-kernel oil N-methyltaurine, by Clariant with titleSell;N-acyl-N-methyl taurate, such as N-cocos nucifera oil acyl-N methyl taurine sodium, By Clariant with titleSell or by Nikkol with titleGo out Sell, by Nikkol with titleSell methyl stearyl sodium taurocholate or with title The PMT sodium sold.
11) anionic derivative of alkyl polyglucoside can particularly available from alkyl polyglucoside citrate, Tartrate, sulfosuccinate, carbonic ester and glycerin ether.Can be mentioned that such as cocos nucifera oil acyl poly glucoside (1,4) winestone The sodium salt of acid esters, by Cesalpinia with titleSell, cocos nucifera oil acyl poly glucoside (Isosorbide-5-Nitrae) The disodium salt of sulfosuccinate, by Seppic with titleSell, or cocos nucifera oil acyl poly glucoside The sodium salt of (Isosorbide-5-Nitrae) citrate, by Cesalpinia with titleSell.
The most described amino acid derivativges can be acylglycine derivatives or glycine derivative, particularly acyl group Glycinate.
Acylglycine derivatives or glycine derivative be selected from acylglycine salt (acyl glycine salt or Acyl glycinate) or glycinate (glycine salt or glycinate), and in particular selected from following.
I) formula R-HNCH2The acylglycine salt of COOX
Wherein
-R represents acyl group R'C=O, wherein R', and it represents saturated or unsaturated, the hydrocarbon chain of straight or branched, Preferably comprise 10 to 30 carbon atoms, more preferably 12 to 22 carbon atoms, even more preferably 14 to 22 Carbon atom and preferably 16 to 20 carbon atoms, and
-X represents selected from the such as ion of alkali metal (such as Na, Li or K, preferably Na or K), alkaline-earth metal (example Such as Mg) ion, ammonium and the cation of their mixture.
Described acyl group can be in particular selected from lauroyl, myristoyl, mountain acyl group, palmityl, stearoyl Base, isostearoyl base, olive oil acyl group (olivoyl), cocoyl or oleoyl and their mixture.
Preferably, R is cocoyl.
Ii) glycinate of formula (VI) under:
[formula (VI)]
Wherein:
-R1Represent saturated or undersaturated, the hydrocarbon chain of straight or branched, its comprise 10 to 30 carbon atoms, Preferably 12 to 22 carbon atoms and preferably 16 to 20 carbon atoms;R1It is advantageously selected from lauryl, meat Myristyl, palmityl, stearyl, cetyl, cetearyl or oil base and their mixture, and excellent Choosing is selected from stearyl and oil base,
-R2Group, it is identical or different, represents R " OH group, R " be containing 2 to 10 carbon atoms, The alkyl of preferably 2 to 5 carbon atoms.
As the compound of formula (VI), can be mentioned that the compound such as with INCI title sodium cocoyl glycinate, Such as, such as, Ajinomoto the Amilite GCS-12 sold, or cocos nucifera oil acyl glycine potassium, such as, example As, from the Amilite GCK-12 of Ajinomoto.
As the compound of formula (VI), dihydroxy ethyl oil base glycinate or the sweet ammonia of dihydroxy ethyl stearyl can be used Hydrochlorate.
1-5-3. amphoteric surfactant
Amphoteric surfactant is unrestricted.Both sexes or zwitterionic surfactant are it may be that such as (unrestricted Property inventory), amine derivative such as aliphatic secondary amine or tertiary amine, and the most quaternized amine derivative, wherein aliphatic group Group be comprise 8 to 22 carbon atoms and comprise at least one water-soluble anionic group (such as, carboxylate, sulphur Hydrochlorate, sulfate, phosphate or phosphonate) straight or branched.
In amido amine carboxylation derivant, can be mentioned that the product sold with title Miranol, as special in the U.S. Profit the 2nd, 528, No. 378 and the 2nd, 781, No. 354 describes and ranges CTFA dictionary, the third edition, 1982 (its Disclosure is incorporated herein by) in both sexes base carboxyl glycinate and both sexes base carboxyl propionate title Under, respective structure is:
R1-CONHCH2CH2-N+(R2)(R3)(CH2COO-)
Wherein: R1Represent acid R present in hydrolysis cocos nucifera oil1The alkyl of-COOH, heptyl, nonyl or hendecane Base,
R2Represent beta-hydroxyethyl, and
R3Represent carboxymethyl;With
R1'-CONHCH2CH2-N(B)(C)
Wherein: B representative-CH2CH2OX',
C representative-(CH2)z-Y', wherein z=1 or 2,
X' represents-CH2CH2-COOH group ,-CH2-COOZ’、-CH2CH2-COOH、-CH2CH2-COOZ’ Or hydrogen atom,
Y' represents-COOH ,-COOZ' ,-CH2-CHOH-SO3Z ' or-CH2-CHOH-SO3H group,
Z' represents alkali metal or the ion of alkaline-earth metal such as sodium, ammonium ion or be produced from the ion of organic amine, and
R1' represents acid R present in cocos nucifera oil or hydrolysis Semen Lini oil1' the alkyl of-COOH, alkyl, such as C7、 C9、C11Or C13Alkyl, C17Alkyl and isomeric form thereof, or undersaturated C17Group.
The most described amphoteric surfactant is selected from (C8-C24)-alkyl both sexes base Monoacetate, (C8-C24) alkyl two Property base diacetin, (C8-C24) alkyl both sexes base list propionate and (C8-C24) alkyl both sexes base dipropionate.
These compounds are classified as CTFA dictionary, the 5th edition, and 1993, cocos nucifera oil acyl both sexes base oxalic acid disodium (Disodium Cocoamphodipropionate), lauroyl both sexes base oxalic acid disodium (Disodium Lauroamphodiacetate), octyl group both sexes base oxalic acid disodium (Disodium Caprylamphodiacetate), pungent Acyl both sexes base oxalic acid disodium (Disodium Capryloamphodiacetate), cocos nucifera oil acyl both sexes base disodium beclomethasone, Lauroyl both sexes base propanoic acid disodium, octyl group both sexes base disodium beclomethasone, octyl group both sexes base disodium beclomethasone, Laurel Acyl both sexes base dipropionic acid and cocos nucifera oil acyl both sexes base dipropionic acid are under one's name.
By way of example, can be mentioned that by Rhodia Chimie company with trade nameConcentrate The cocos nucifera oil acyl both sexes base diacetin sold.
Preferably, described amphoteric surfactant can be glycine betaine.
Betaine type amphoteric surfac-tant is preferably selected from alkyl betaine, alkyl amidoalkyl betaines, alkane Base sulfobetaines, alkyl phosphate betaines (alkylphosphobetaine) and alkyl amidoalkyl sulfo group are sweet Dish alkali, particularly (C8-C24) alkyl betaine, (C8-C24) alkylamidoalkyl (C1-C8) alkyl betaine, (C8-C24) Alkyl sulfo betaines, and (C8-C24) alkylamidoalkyl (C1-C8) alkyl sulfo betaines.An embodiment In, the amphoteric surfactant of betaine type is selected from (C8-C24) alkyl betaine, (C8-C24) alkylamidoalkyl (C1-C8) Alkyl sulfo betaines, (C8-C24) alkyl sulfo betaines and alkyl (C8-C24) phosphate ester glycine betaine.
The limiting examples that can be mentioned that includes ranging CTFA dictionary, the 9th edition, cocoyl Radix Betae in 2002 Alkali, lauryl betaine, cetyl betaine, cocoyl/oleamidopropyl betaine, cocamidopropyl third Base glycine betaine, palmityl amido CAB, stearoyl amido CAB, cocoamidoethyl are sweet Dish alkali, Cocamidopropyl hydroxyl sulfo betaine, oleamidopropyl hydroxyl sulfo betaine, cocoyl Hydroxyl sulfo betaine, lauryl hydroxyl sulfo betaine and cocoyl sulfobetaines compound under one's name, single Solely or as mixture.
Betaine type amphoteric surfac-tant is preferably alkyl betaine and alkyl amidoalkyl betaines, especially It is coco betaine and cocamidopropyl betaine.
The gross weight of relative combinations thing, the amount of other surfactant (if use) can be 0.01 weight % extremely 20 weight %, preferably 0.10 weight % is to 10 weight %, and more preferably 1 weight % is to 5 weight %.
1-5-4. polyhydric alcohol
The compositions of the present invention also can comprise at least one polyhydric alcohol.The polyhydric alcohol of single type can be used, but can It is applied in combination two or more different types of polyhydric alcohol.
Term " polyol " herein refers to the alcohol with two or more hydroxyls, and do not contain sugar or its Derivant.The derivant of sugar includes the sugar alcohol obtained by one or more carbonyl of reducing sugar, and wherein One or more hydrogen atom in its one or more hydroxyl is by least one substituent group (such as alkyl, hydroxyl Alkyl, alkoxyl, acyl group or carbonyl) substituted sugar or sugar alcohol.
Described polyhydric alcohol can be C2-C12Polyhydric alcohol, preferably C2-9Polyhydric alcohol, it comprises at least 2 hydroxyls, and Preferably 2 to 5 hydroxyls.
Described polyhydric alcohol can be polyhydric alcohol that is natural or that synthesize.Described polyhydric alcohol can have straight chain, side chain or ring Shape molecular structure.
Described polyhydric alcohol is selected from glycerol and dihydroxylic alcohols, more preferably propylene glycol, butanediol, pentanediol, hexanediol, Dipropylene glycol, diglycol, Sensiva SC50, Flos Magnoliae glycol, glycol ethers, preferably single the third two Alkyl (the C of alcohol, dipropylene glycol or tripropylene glycol1-C4) ether or monoethylene glycol, diglycol or Alkyl (the C of triethylene-glycol1-C4) ether, and mixture, even more preferably polyhydric alcohol is glycerol and/or butanediol.
Relative to the gross weight of compositions, described polyhydric alcohol can be in 0.01 weight % to 30 weight %, and preferably 0.1 weight % to 20 weight %, as the amount in the range of 1 weight % to 10 weight % exists.
1-5-5. thickening agent
The compositions of the present invention also can comprise at least one thickening agent.The thickening agent of single type can be used, but can It is applied in combination two or more different types of thickening agents.
Described thickening agent is selected from as follows:
I () associative thickeners, it for comprising both hydrophilic units and hydrophobic unit, such as, comprises at least one Plant C8-C30Aliphatic chain and the amphiphilic thickening agent of at least one hydrophilic units;
(ii) acrylate homopolymer cross-linked;
(iii) (methyl) acrylic acid and (C1-C6) copolymer of crosslinking of alkyl acrylate;
(iv) comprise in ethylenic beta-unsaturated esters monomer and ethylenic unsaturated acyl amine monomers at least one non-from Sub-homopolymer and copolymer;
(v) acrylate homopolymers and ammonium acrylate and the copolymer of acrylamide;
(vi)C12-C30Fatty alcohol;
(vii) (not) modified carboxy vinyl polymer, as by Goodrich company with title Carbopol (CTFA name Claim: carbomer, Carbomer) product sold;Polyacrylate;
(viii) polymethacrylates, as by Guardian company with title Lubrajel and Norgel and by The product that Hispano Chimica company sells with title Hispagel;
(ix) polyacrylamide, optionally crosslinking;
X 2-acrylamide-2-methylpro panesulfonic acid polymer that () neutralizes and copolymer, such as by Clariant company Poly-(the 2-third sold with title Hostacerin AMPS (CTFA title: polypropylene acyl group dimethyltaurine ammonium) Acrylamide base-2-methyl propane sulfonic acid);
(xi) anionic copolymer of the crosslinking of acrylamide and AMPS, it is the form of W/O emulsion, as by SEPPIC company is with title Sepigel 305 (CTFA title: polyacrylamide/C13-C14Isoparaffin/lauryl alcohol Polyethers-7) and with title Simulgel 600 (CTFA title: acrylamide/acryloyl dimethyl tauric acid sodium is altogether Polymers/2-Methylpentadecane/polysorbate80) sell those;
(xii) polysaccharide biopolymer, such as xanthan gum, guar gum, tragon, arabic gum, hard Portugal gather Sugar, chitin and chitosan derivant, carrageenin, gellan gum, alginate;
(xiii) cellulose such as microcrystalline Cellulose, carboxymethyl cellulose, hydroxymethyl cellulose and hydroxypropyl cellulose, And mixture, it is preferably selected from acrylate/C10-C30Alkyl acrylate cross-linked polymer, such as Carbopol ultrez 20、Carbopol ultrez 21、Permulen TR-1、Permulen TR-2、Carbopol 1382、 Carbopol ETD 2020, carbomer such as Synthalen K, carbopol 980, acryloyl dimethyl tauric acid Ammonium/stereth-8 methacrylate copolymer such as Aristoflex SNC, acrylate copolymer are such as Carbopol Aqua SF-1, acryloyl dimethyl tauric acid ammonium/stereth-25 methacrylate crosslinking Polymer such as Aristoflex HMS, acryloyl dimethyl tauric acid ammonium such as Arisfoflex AVC and xanthan gum Such as Keltrol CG;And also not only facilitate the suitable viscosity of maintenance, further help in and very well prepare Capsule suspension liquid and further helping in so that it is stable for storage life, and contribute to providing thoroughly Any polymer of lightness.
Thickening agent is preferably selected from associative thickeners, polysaccharide and (not) modified carboxy vinyl polymer such as starch, Huang Virgin rubber (xanthene gum) and carbomer.
The viscosity of the compositions of the present invention is not particularly limited.Viscosity can be (excellent with viscometer or flow graph at 25 DEG C Choosing has tapered planar (cone-plan) geometry) measure.Preferably, the compositions of the present invention is at 25 DEG C And 1s-1Under viscosity can be such as at 1Pa.s to 2000Pa.s, and in the range of preferably 1Pa.s to 1000Pa.s.
Relative to the gross weight of compositions, thickening agent can in 0.001 weight % to 10 weight %, and preferably 0.01 Weight % is to 10 weight %, and even more preferably amount in the range of 0.1 weight % to 5 weight % exists.
1-5-6. activating agent
For being particularly useful for the application of nursing skin or cosmetic skin, the compositions of the present invention can include at least one Activating agent.
These activating agents are selected from wetting agent (moisturizer), shading/sunscreen (sunscreen/sunblock Agent), anti-wrinkle agent, vitamin (such as B3, B8, B12 and B9), decorticating agent (desquamating agent), Decolorising agent, antioxidant etc..
Such as, wetting agent (or wetting agent) that can be specifically mentioned includes Sorbitol, polyhydric alcohol, preferably C2-C8, And more preferably C3-C6Polyhydric alcohol, the most such as glycerol, propylene glycol, 1,3 butylene glycol, pentanediol, hexanediol, Dipropylene glycol, diglycol and diglycerol, and mixture, glycerol and derivant thereof, glycol ethers are (especially It contains 3 to 16 carbon atoms), such as MPG, dipropylene glycol or tripropylene glycol (C1-C4) alkyl Ether, monoethylene glycol, diglycol or triethylene-glycol (C1-C4) alkyl ether, urea and derivant thereof, especially It is sold by National Starch Hydrovance (2-ethoxy urea), lactic acid, hyaluronic acid, AHA, BHA, pidolic acid sodium (sodium pidolate), xylitol, serine, sodium lactate, Ectoin (ectoin) And derivant, Chitosan-phospholipid complex, collagen, plankton, by Sederma company with title Moist 24 extracts of Imperata cylindra sold, acrylate homopolymer, such as from NOF Corporation 'sBeta glucan and the carboxymethyl β-Portugal especially from Mibelle-AG-Biochemistry Polysaccharide sodium;By Nestle with titleThe passionflower oil of sale, Fructus Pruni oil (apriot oil), Semen Maydis oil Mixture with Testa oryzae oil;C-glycosides derivatives, described at patent application WO02/051 828, And particularly to contain the solution form of 30 weight % active materials in water/propylene glycol mixture (60/40 weight %) C-β-D-xylopyranoside-2-hydroxy propane, as by Chimex with trade nameThe product manufactured Product;The musk rose oil sold by Nestle;By Engelhard Lyon company with title Marine Filling The collagen of the marine source that Spheres sells and the spheroid (lacking atelocollagen, Atelocollagen) of chondroitin sulfate;Thoroughly Bright matter acid spheroid, as sold by Engelhard Lyon company;Arginine, argan oil (argan And mixture oil).
Preferably, will use selected from following wetting agent: glycerol, urea and derivant thereof, especially by National Starch sellsC-glycosides derivatives, as described at patent application WO 02/,051 828 Those, and particularly with in water/propylene glycol mixture (60/40 weight %) containing the active material of 30 weight % The C-β-D-xylopyranoside-2-hydroxy propane of solution form, as by Chimex with trade name The product manufactured;Argan oil and mixture thereof.
More preferably will use glycerol.
Relative to the gross weight of described compositions, wetting agent can be in 0.1 weight % to 15 weight %, especially Amount in the range of 0.5 weight % to 10 weight % or even 1 weight % to 6 weight % is present in compositions.
Opacifier (or sunscreen) is the important skin-protection product for preventing photoaging and skin carcinoma.There are two class shadings Agent: UVA sunscreen, the UV radiation that it is generally blocked in 320 to 400nm wave-length coverage, and UVB Opacifier, it is generally blocked in the radiation in 290 to 320nm wave-length coverage.
The compositions of the present invention is included in activated organic in UVA and/or UVB region and/or inorganic UV Shading composition, it is hydrophilic and/or oleophylic.Especially, the UV shading composition of the present invention can have 8.0 to The dissolubility of 9.5.This type of UV shading composition has good plasticizer function.
Advantageously, the UV opacifier of the present invention can have the molecular weight of 150 to 500g/mol and containing hydrophobic position Point and benzene nucleus or the electron resonance group that is combined with polar sites.
Hydrophilic and/or lipophile organic UV shading composition are in particular selected from dibenzoylmethane derivative;Cinnamic acid Derivant;Salicyclic acid derivatives;Benzophenone derivates;β, β-diphenylacrylate;P-aminophenyl Formic acid (PABA) derivant;Mixture with them.
As the example of organic UV shading composition, can be mentioned that those represented with their INCI title following:
-para-amino benzoic acid derivant:
-PABA,
-PABA ethyl ester,
-dihydroxypropyl PABA ethyl ester,
-dimethyl PABA the Octyl Nitrite sold with trade mark " Escalol 507 " especially by ISP,
-PABA glyceride,
-dibenzoylmethane derivative:
-butylmethoxy hexichol the first sold with trade mark " Parsol 1789 " especially by Hoffmann-LaRoche Acyl methane,
-isopropyl dibenzoyl methane,
-salicyclic acid derivatives:
-the homosalate (Homosalate) sold with trade mark " Eusolex HMS " by Rona/EM Industries,
-the ethylhexyl salicylate sold with trade mark " Neo Heliopan OS " by Haarmann and Reimer,
-dipropylene glycol the salicylate sold with trade mark " Dipsal " by Scher,
-TEA the salicylate sold with trade mark " Neo Heliopan TS " by Haarmann and Reimer,
-cinnamic acid derivative:
-methoxy cinnamic acid the second sold with trade mark " Parsol MCX " especially by Hoffmann-LaRoche The own ester of base,
-methoxycinnamate isopropyl propionate,
-the methoxycinnamate sold with trade mark " Neo Heliopan E 1000 " by Haarmann and Reimer Isoamyl valerate,
-cinoxate (Cinoxate),
-DEA methoxycinnamate hydrochlorate,
-methyl cinnamic acid diisopropyl ester,
-glyceryl ethylhexoate dimethoxy-cinnamic acid ester,
-β, β-diphenylacrylate:
-the octocrilene (octocrylene) sold with trade mark " Uvinul N539 " especially by BASF;
-the etocrilene (etocrylene) sold with trade mark " Uvinul N35 " especially by BASF,
-benzophenone derivates:
-the BP-1 sold with trade mark " Uvinul 400 " by BASF,
-the BP-2 sold with trade mark " Uvinul D50 " by BASF,
-the BP-3 sold with trade mark " Uvinul M40 " by BASF or oxybenzone (oxybenzone),
-the UVINUL MS 40 sold with trade mark " Uvinul MS40 " by BASF,
-benzophenone-5,
-benzophenone-6 sold with trade mark " Helisorb 11 " by Norquay,
Mixture with them.
Preferably UV shading composition is selected from cinnamic acid derivative, β, β-diphenylacrylate, bigcatkin willow Acid derivative and their mixture.
Preferably UV shading composition is in particular selected from ethylhexyl methoxy cinnamate, octocrilene and salicylic acid second The own ester of base and their mixture.
Can specifically mentioned by BASF AG with trade nameThe methoxy cinnamic acid second sold The own ester of base, by SYMRISE company with trade nameThe ethylhexyl salicylate sold With by SYMRISE company with trade nameThe octocrilene sold.
The gross weight of relative combinations thing, the compositions of the present invention can comprise 0.1 weight % to 30 weight %, such as 0.5 weight % to 20 weight %, the UV of such as 1 weight % to 15 weight % and for example, at least 1 weight % hides Light component.
Anti-wrinkle agent: can be mentioned that ascorbic acid and derivant thereof, such as magnesium L-ascorbyl-2-phosphate and ascorbic acid glucose Glycosides;Tocopherol and derivant thereof, such as tocopherol acetas;Nicotinic acid and precursor thereof, such as nicotiamide;Ubiquinone;Paddy The sweet peptide of Guang and precursor thereof, such as L-2-oxothiazoiium quinoline-4-carboxylic acid;C-glycoside compounds and derivant thereof, as especially Described below: plant extract, and especially Crithmum maritimum and the extract of Folium olive;And also plant Thing albumen and hydrolyzate thereof, such as rice or soybean protein hydrolysate;Sargassum extract, and especially Thallus Laminariae (Thallus Eckloniae) Extract;Bacterial extract;Sapogenin (sapogenin), such as diosgenin and the Wild yam comprising sapogenin (Dioscorea) extract of the extract of plant, especially dioscorea japonica;'alpha '-hydroxy acids;Beta-hydroxy acid, such as bigcatkin willow Acid and 5-positive decoyl salicylic acid;Oligopeptide and false dipeptides and acyl derivative, especially { 2-[acetyl group-(3-tri- Trifluoromethylphenyl) amino]-3-methylbutanoylamino acetic acid and by Sederma company with trade name Matrixyl 500 and Matrixyl 3000 lipopeptids sold;Lycopene;Manganese salt and magnesium salt, especially manganese gluconate and Magnesium gluconate;And mixture;
Decorticating agent: can be mentioned that beta-hydroxy acid, especially salicylic acid and deriving in addition to 5-positive decoyl salicylic acid thereof Thing;Urea;Glycolic, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid;4-(2-ethoxy) piperazine-1- Propane sulfonic acid (HEPES);The Flos Sophorae Immaturus (Saphora japonica) extract;Mel;2-Acetamido-2-deoxy-D-glucose;Methyl Glycine sodium diacelate, 'alpha '-hydroxy acids (AHA), beta-hydroxy acid (BHA), and mixture;
Decolorising agent: can be mentioned that ceramide, vitamin C and derivant thereof, particularly vitamin C G, dimension are raw Element CP and 3-O ethyl vitamin C;α-and β-arbutin;Ferulic acid;Kojic acid;Resorcinol and derivant thereof; D-acyl sulfhydryl ethylamine sulfonic acid calcium;Thioctic acid;Ellagic acid;Vitamin B3;Symwhite-337, such as, come From Symrise companyKiwi fruit (Fructus actinidiae chinensis, the Actinidia sold by Gattefosse Chinensis) juice, Paeonia suffruticosa (Paeonia suffructicosa) root extract, as by Ichimaru Pharcos company with name ClaimSell product, brown sugar (Caulis Sacchari sinensis, Saccharum officinarum) extract, as by Molasses extract, undecylenic acid and 11 carbon that Taiyo Kagaku company sells with title Molasses Liquid The mixture of enoyl-phenylalanine, as from Seppic
Antioxidant: can more particularly mention tocopherol and ester thereof, especially tocopherol acetas;EDTA;Anti- Bad hematic acid and derivant thereof, especially magnesium L-ascorbyl-2-phosphate and ascorbic acid glucoside;Chelating agen, as BHT, BHA, N, N '-bis-(3,4,5-trimethoxy benzyl) ethylenediamine and salt thereof;And mixture.
The gross weight of relative combinations thing, these activating agents can in 0.001 weight % to 20 weight %, preferably 0.01 Weight % is present in compositions to the amount in the range of 10 weight %, and more preferably 0.01 weight % to 5 weight % In.
The preparation of 1-6. compositions and character
The compositions of the present invention can be prepared by conventionally mixing mentioned component.Conventional method includes using High pressure homogenisers mixing (high-energy method).For the election, compositions can be by low-yield method such as phase inversion temperature (PIT) Prepared by method (PIT), inversion of phases concentration (PIC), self emulsifying etc..Preferably, compositions is by low-yield method Prepare.
Nonionic surfactant with oil ratio can be 0.25 to 6, preferably 0.3 to 3, and more preferably 0.4 to 1.5。
The compositions of the present invention is nanoemulsions or microemulsion form.Can be in two ways (i.e. with wide meaning With the meaning with relatively narrower) mention " microemulsion ".It is to say, exist in which that microemulsion refers to comprise and has oil The thermodynamically stable isotropism of the ternary system of three kinds of compositions of property component, aqueous components and surfactant A kind of situation (" sense stricto microemulsion ") of single liquid phase, and exist in which, the typical case of thermodynamic instability Emulsion system in, microemulsion comprise additionally in present due to their less particle diameter transparent or semitransparent outside See those these type of emulsions another kind of situation (" sensu lato microemulsion ") (Satoshi Tomomasa et al., Oil Chemistry, volume 37, o.11 (1988), the 48-53 page).As used herein " microemulsion " Refer to " sense stricto microemulsion ", the single liquid phase of the most thermodynamically stable isotropism.
Microemulsion refers to that O/W (oil-in-water) type microemulsion that wherein oil is dissolved by micelle, wherein water pass through anti-glue W/o type (Water-In-Oil) type microemulsion that bundle dissolves or the association body (associations) of wherein surfactant molecule Quantity becomes and makes aqueous phase and oil phase both of which have any one in the bicontinuous microemulsions of continuous structure greatly State.
Described microemulsion can have dispersion phase, and described dispersion phase has to be measured by laser granulometry 100nm or less, preferred 50nm or less and the number average diameter of more preferably 20nm or less.
" nanoemulsions " this refers to the emulsion that it is characterized in that having the dispersion phase of the size less than 350nm, Described dispersion phase by can optionally form the nonionic table of the liquid crystalline phase of lamellar type in dispersion phase/continuous phase interface The hat (crown) of face activating agent is stablized.In the case of there is not specific opacifying agent, nanoemulsions saturating Lightness stems from the small size of dispersion phase, and this small size is by means of using mechanical energy and particularly high pressure homogenisers Obtain.
Nanoemulsions can be separated by their structural area with microemulsion.Specifically, microemulsion is Thermodynamically stable Dispersion, it is micelle formation by the most oil-overflow nonionic surfactant.Additionally, microemulsion need not Prepared by substantial amounts of mechanical energy.
Microemulsion can have dispersion phase, described dispersion phase have the 300nm measured by laser granulometry or 200nm or less less, preferred and the number average diameter of more preferably 150nm or less.
The compositions of the present invention can be O/W nanoemulsions or microemulsion, W/O nanoemulsions or microemulsion or double Continuous emulsion form.Preferably, the compositions of the present invention is O/W nanoemulsions or microemulsion form.
In preferred embodiments, the compositions of the present invention can be O/W emulsion form.In this case, Oil can be number average bead diameter be 300nm or less, preferably 10nm to 200nm, and more preferably 20nm to 150 The drops of nm.
Mastersizer 2000 particle instrument (being sold by Malvern Instruments) is used to measure oil by optical diffraction The average-size of phase drop.These measure dilution in the 1%SDS (sodium lauryl sulphate) solution in water Carry out in emulsion.Computer program allows to average diameter D [4.3] (μm) obtained by volume and (sees operator Guide, Malvern Instruments, in December, 1998, page 61 to 67).
Average-size D [4.3] (μm) of the drop of the oil phase of the compositions of the present invention at 10nm to 150nm, and In the range of more preferably 20nm to 140nm.
The compositions of the present invention is particularly stable, especially room temperature and even 37 DEG C or 45 DEG C, under atmospheric pressure During 2 months, and they present optimal cosmetic character.It is true that the compositions of the present invention presents Suitable mobility: they are easily handled, and be also easy to use and spread on skin.
These compositionss also present cosmetic use needed for quality: they be not viscosity, soft-touch and Give resilient sensation.Therefore, the compositions of the present invention also has and meets consumer cosmetic as the most relatively low viscous Desired advantage in terms of degree and more preferable emollient.
The compositions of the present invention can be " color-changing composition ".Term " color-changing composition " refers to such compositions: Color before wherein using from use after color different, this difference is visible for naked eyes.
Especially, this color-changing composition can with according to CIE laboratory system 1976 (before using/use rear Δ E) value Aberration Δ E is associated.By equation restriction Δ E:
[Math.1]
&Delta;E * = ( ( L 1 - L 2 ) 2 + ( a 1 - a 2 ) 2 + ( b 1 - b 2 ) 2 :
Wherein L1、a1、b1It is the parameter in the chrominance space of the first color (compositions before using), and L2、 a2、b2It is the second color (being administered on keratin material and compositions after homogenization on keratin material) Parameter.Spectrophotometer can be passed through or utilize chromosphere (Chromasphere) (compositions for being administered on skin) Measure these values.The color-changing composition of the present invention is characterized by having more than 1, especially greater than or equal to 2, excellent Selection of land more than or equal to before 3 use/use rear Δ E.
The compositions of the present invention can have transparent or the most translucent outward appearance, the outward appearance of preferably clear.In other words Saying, the present composition includes the microcapsule comprising releasable coloring agent at transparent medium.
Transparency can be measured (such as, with having 2 by the absorbance measured in visual field with absorption spectrometer It is average that the V-550 (JASCO) in the pond that mm is wide measures as transmission of visible light (between 400 and 800nm) Transparency).Described mensuration is carried out in undiluted compositions.Blank distilled water determines.
The compositions of the present invention preferably has more than 50%, preferably greater than 60%, more preferably greater than 70% and And the transparency of even more preferably greater than 75%.
In preferred embodiments, the compositions of the present invention comprises microcapsule;The most uncoloured microcapsule, Outer layer is white or transparent, and when outer layer is transparent, it is seen that internal layer be white.For the present invention Purpose, term " transparent compositions " refer to light through wavelength 750nm at least 40% and not scattered light Compositions, wherein scattering of light angle is less than 50 ° and the compositions of the most about 5 °.Transparent composition can pass through ripple At least the 50% of the light of long 750nm, especially at least 60% and especially at least 70%.
According to following scheme, utilize the Cary 300 from Varian company to scan UV-visible spectrophotometer and enter Row light transmission measurement:
-compositions is poured in square (square-sided) spectrophotometer little Chi of length of side 10mm;
-then, and indoor at 20 DEG C in thermostatic control, keep composition sample 24 hours;
-then, on spectrophotometer, by scanning wavelength in the range of 700nm to 800nm, measure Through the light of composition sample, carry out this mensuration in the transmission mode;
-then, it is determined that pass through the percentage ratio of the light of composition sample at the wavelength of 750nm.
Transparent composition, when they are placed on a blank sheet of paper the front of the black line thick for diameter 2mm drawn During 0.01m, it is allowed to this line is seen;On the contrary, opaque compositions, the most nontransparent compositions, do not allow this line It is seen.
The compositions (preferably cosmetic foundation or skin coloring products) of the present invention provides strong moisturizing to feel, frost shape Quality, has the sensation as snug as a bug in a rug in application and the most naturally cosmetic results after application. Finally, all these features help to provide skin-care effect perception (creaminess and moisturizing) and cosmetical efficacy (suitably Coverage rate and naturally light) the best balance.Additionally, the compositions of the present invention can present shading effect Really.Advantageously, in the presence of aqueous phase, microcapsule is deformable.Advantageously, micro-within compositions Capsule is rupturable under the pressure being administered on keratin material.
2. method and purposes
The invention still further relates to be administered to the above compositions skin, hair, mucosa, fingernail, eyelashes, Cosmetic method on eyebrow or scalp.
The invention still further relates to the above compositions be used as or for health and/or skin of face and/or mucosa And/or scalp and/or hair and/or fingernail and/or eyelashes and/or the care product of eyebrow and/or clean product and/or Cosmetic product and/or the purposes of makeup removal products.
In other words, the compositions of the present invention can be used as above product.Or, the combination of the present invention Thing can use as the composition (element) of above product.Such as, the compositions of the present invention can add to any other Become subassembly to form above product in composition or with any other.
Prepare these compositionss according to conventional methods.Such compositions can be face and/or body care or The form of cosmetic product, and the cream that is such as placed in tank can be modulated to or be placed in pipe or fluid that pump moves in bottle Form.
In specific embodiments, said composition comprises at least one 2-acrylamido-2-methyl-prop sulphur neutralized Acid polymer and copolymer and a kind of polysaccharide biopolymer.
Statement " transparent water-bearing media " means to allow light through and obstructed superrefraction or reflection cause Jie of deviation Matter.The transparency of water-bearing media can use scopometer to measure.Such as can use from HACH company is portableModel measures the transparency scope of compositions.When turbidity measurements is 0 and 250 It time between NTU, it is believed that compositions is transparent, and it is 250 to 1000NTU for turbidity value, it is believed that group Compound is translucent.
Time before the black line thick for 0.01m being placed on blank sheet of paper a diameter of 2mm drawn, said composition shows Revealing this black line, this is contrary with opaque compositions, say, that opaque compositions will not appear black line.This The compositions of invention preferably comprises water and comprises the Multi-layer microcapsule of releasable coloring agent.Preferred embodiment party In case, the compositions of the present invention comprises at least one hydrophilic or lipophile gel and at least one water solublity moistens Skin agent and/or there is the lipid of polar portion.In preferred embodiments, the compositions of the present invention comprises at least The two kinds of different Multi-layer microcapsule comprising releasable coloring agent.
Microcapsule can not destroy microcapsule with being gently mixed introducing in final step after preparing gel.
The transparent composition with microcapsule so obtained presents purely and clean outward appearance, at-20/20 DEG C (5 Secondary circulation), room temperature (25 DEG C, 2 months), there is perfection under 37 DEG C (2 months) and 45 DEG C of (2 months), atmospheric pressure Stability.Microcapsule release pigment in application and do not feel any granule.There is provided after application Perfect and uniform cosmetic results.
The compositions of the present invention is preferably transparent, and alternatively somewhat colour.In this case, originally The compositions of invention comprises the coloring agent of at least one non-embedding, is preferably based on the gross weight of all compositions, its Amount is less than 1 weight %.
The compositions of the present invention alternatively comprises oil and the gel cream of surfactant or the form of emulsified gel.
In another embodiment, the present invention relates to comprise product and the test kit of applicator of more than one definition. Described applicator is selected from conventional use of applicator.
The compositions of the present invention can such as be used by finger or use applicator.Container preferably with include configure with Applying said compositions is applied in combination at least one applicator using assembly of keratin substances.
Said composition mainly comprises water, at least one nonvolatile oil, at least one O/W emulsifying agent and microcapsule.
In entire disclosure (including claims), term " comprises one " and " including one " is interpreted as Respectively with " comprising at least one " and " including at least one " synonym, unless otherwise mentioned.
Term " ... and ... between " and " from ... extremely ... " it is understood to include bound, unless otherwise detailed instructions.
The present invention is illustrated in more detail by following embodiment.Unless otherwise mentioned, the amount of instruction is expressed as The mass percent of active material.
Embodiment
The present invention will be more fully described by embodiment, but, described embodiment should not be construed as and limits this Bright scope.
Formulation Example
1:SUNSOFT A-121E (is provided by Taiyo Kagaku)
2:MAGIC30-BW0105 (is provided by KPT)
(1) preparation of compositions
According to following methods preparation embodiment 1 and comparative example 1:
Prepare oil phase (mixture of ethylhexyl palmitate+polyglycereol-5 laurates+preservative), and by oil phase It is heated to about 75 DEG C.It follows that prepare aqueous phase (water+methyl stearyl sodium taurocholate+glycerol+butanediol), And by heated aqueous to about 75 DEG C.Then, aqueous phase is added in oil phase.After completing emulsifying, to mixture Middle interpolation thickening agent phase (acrylate/C10-30 alkyl acrylate cross-linked polymer).Then, mixture is cold But to room temperature.For embodiment 1, in mixture, at room temperature add MAGIC30-BW0105.
According to following methods preparation comparative example 2:
Prepare aqueous phase (water+glycerol+butanediol), and by heated aqueous to about 75 DEG C.Add in mixture and increase Thick dose of phase (acrylate/C10-30 alkyl acrylate cross-linked polymer).Then mixture is cooled to room temperature. In mixture, at room temperature add MAGIC30-BW0105.
(2) evaluation of technique effect
I () observes (outward appearance)
Outward appearance is evaluated by Visual Observations Observations.
(ii) there is no the transparency of the main body of MAGIC30-BW0105
The V-550 (JASCO) with pond wide for 2mm is used to measure transparency.Transparency=transmission of visible light (between 400 and 800nm's) is average.
(iii) particle diameter
VASCO-2 (CORDOUAN TECHNOLOGIES) is used to measure particle diameter under the conditions of undiluted. Computer program allows to obtain average diameter by specified intensity.
(iv) coverage rate
At blackOn at 1mg/cm3Applied color is measured under concentration (thickness).This value passes through Δ L* Display.Δ L* value is the lowest, it is achieved the biggest coverage rate.
(v) sensory testing
Cosmetic in order to evaluate, 5 panellists carry out sensory testing.Panellists is with regard to skin moistening Property and humidity for evaluate each compositionss with 5 grades.
Emollient
5: very skin moistening
4: quite skin moistening
3: relatively skin moistening
2: not skin moistening
1: the most not skin moistening (dermal sensation is the hardest)
Humidity
5: the wettest
4: the wettest
3: wetter
2: the wettest
1: the wettest
Table 1
The pattern being applied to keratin material has the technique effect observed
As from result above it is clear that find the cosmetic composition according to the O/W emulsion form of the present invention There is less oil droplet, and therefore, in the presence of microcapsule, provide the outward appearance with preferable transparency.
Comparative example 1 is the formula for comparing with embodiment 1, is that comparative example 1 does not has micro-glue Capsule.Can be summarized according to embodiments of the invention 1 micro-by the comparison between embodiment 1 and comparative example 1 Obtain clear gel in the presence of capsule, and transparency is equal to the formula that do not has microcapsule.The grain of embodiment 1 Footpath is below 150nm, and compositions is nanoemulsions.
Comparative example 2 is the formula of aqueous clear gel.(transparent nanoemulsion coagulates to this means embodiment 1 Glue) exceed comparative example 2 (clear aqueous gel) in coverage rate and organoleptic properties's (emollient and humidity) aspect.

Claims (22)

1. nanoemulsions or the compositions of microemulsion form, comprising:
(a) at least one fat phase;
(b) at least one nonionic surfactant;
(c) at least one comprise the microcapsule of releasable coloring agent;With
(d) at least one aqueous phase.
Compositions the most according to claim 1, it is o/w emulsion.
Compositions the most according to claim 1 and 2, it also includes at least one polyhydric alcohol, is preferably selected from Glycerol and dihydroxylic alcohols, more preferably propylene glycol, butanediol, pentanediol, hexanediol, dipropylene glycol, a contracting Diethylene glycol, Sensiva SC50, Flos Magnoliae glycol, glycol ethers, preferably MPG, dipropylene glycol or Alkyl (the C of tripropylene glycol1-C4) ether or the alkyl of monoethylene glycol, diglycol or triethylene-glycol (C1-C4) ether, and mixture, the most described polyhydric alcohol is glycerol and/or butanediol.
Compositions the most according to any one of claim 1 to 3, wherein said nonionic surfactant Selected from single oxygen alkylene or polyoxyalkylenated fatty acid ester, polyglyceryl fatty acid ester surfactant and sugar particularly sugarcane The fatty acid ester of sugar.
Compositions the most according to claim 4, wherein said polyglyceryl fatty acid ester has derived from 4 to 6 The polyglycereol part of individual glycerol, more preferably 5 or 6 glycerol.
Compositions the most according to any one of claim 1 to 5, wherein total relative to described compositions Weight, the amount of nonionic surfactant be 0.1 weight % to 30 weight %, preferably 0.5 weight % to 15 weight %, And more preferably 1 weight % to 10 weight %.
Compositions the most according to any one of claim 1 to 6, wherein said fat include mutually oil phase and Described grease separation, from vegetable oil, animal oil, mineral oil, artificial oil, silicone oil and hydrocarbon ils, is preferably selected from ester oil, ether Oil, alkane oil, the hydrocarbon ils of triglyceride oil, even more preferably have the oil of the molecular weight of less than 700.
Compositions the most according to claim 7, wherein relative to the gross weight of described compositions, described oil Amount be 0.1 weight % to 50 weight %, preferably 0.5 weight % is to 40 weight %, and more preferably 5 weight % are to 30 Weight %.
Compositions the most according to any one of claim 1 to 8, it also includes thickening agent, preferably selects From:
(i) associative thickeners;(ii) acrylate homopolymer cross-linked;(iii) (methyl) acrylic acid and (C1-C6) alkyl The copolymer of the crosslinking of acrylate;(iv) ethylenic beta-unsaturated esters monomer and ethylenic unsaturated amides list are comprised The nonionic homopolymer of at least one in body and copolymer;(v) acrylate homopolymers and ammonium acrylate and third The copolymer of acrylamide;(vi)C12-C30Fatty alcohol;(vii) (not) modified carboxy vinyl polymer;(viii) poly-first Base acrylate;(ix) polyacrylamide, optionally crosslinking;X 2-acrylamido-2-methyl-prop sulphur that () neutralizes Acid polymer and copolymer;(xi) anionic copolymer of the crosslinking of acrylamide and AMPS, it is W/O Emulsion form;(xii) polysaccharide biopolymer;(xiii) cellulose, is more preferably selected from (i) associative thickeners, (vii) (not) modification carboxy vinyl polymer and (ix) polysaccharide.
Compositions the most according to any one of claim 1 to 9, wherein total relative to described compositions Weight, water with in 5 weight % to 99 weight %, preferably 10 weight % to 95 weight % and even more preferably 15 weight % Amount to 90 weight % exists.
11. compositionss according to any one of claim 1 to 10, wherein said microcapsule includes:
(A) core, the most uncoloured core, it includes a kind of organic material, and
(B) surround at least one stratiform coating of described core, layered coating include at least one polymer, At least one coloring agent and advantageously at least one binding agent.
12. according to the compositions according to any one of claim 1 to 11, relative to the gross weight of described compositions Amount, it include 0.1 weight % to 20 weight %, and preferably 0.5 weight % is to 15 weight %, and more preferably 2 weight % To (c) microcapsule described in 10 weight %.
13. according to the compositions according to any one of claim 1 to 12, wherein said (c) microcapsule described Core includes that at least one monosaccharide or derivatives thereof, as described organic material, is particularly advantageously selected from mannose Monosaccharide-the polyhydric alcohol of alcohol, erythritol, xylitol, Sorbitol and mixture thereof, preferably mannitol.
14. at least wrap according to the compositions according to any one of claim 1 to 13, wherein said (c) microcapsule Include:
-the kernel be made up of the preferred mannitol of monosaccharide-polyhydric alcohol,
-there is at least two layer of mutually different colors,
-at least one hydrophilic polymer, is preferably selected from polysaccharide or their derivant, and is more preferably selected from Starch or derivatives thereof, and advantageously at least one material based on lipid, preferably amphipathic compound, more preferably Phospholipid, and even more preferably phosphate acyl glycerol such as hydrolecithin.
15. include according to the compositions according to any one of claim 1 to 14, wherein said (c) microcapsule:
A) core (A), preferably has diameter less than 800 μm, more preferably less than about 400 μm, is advantageously 1 μm To 300 μm, 5 μm to 200 μm especially, and the size of even more particularly 10 μm to 100 μm, it is excellent Choosing does not comprise any coloring agent, and includes at least one organic core, is preferably selected from least one sugar alcohol, preferably has Sharply selected from mannitol, erythritol, xylitol and the monosaccharide-polyhydric alcohol of Sorbitol;
B) ground floor (B) of described core is surrounded, comprising:
-at least one coloring agent, preferably iron oxides, and
-binding agent, it is selected from polymer and material based on lipid, preferably their mixture;
C) surround a second layer (C) of described ground floor (B), preferably there is 5 μm thickness to 500 μm, Comprising:
-titanium dioxide granule, and
-binding agent, it is selected from polymer and material based on lipid, preferably their mixture;
D) an optional third layer (D) of the described second layer (C) is surrounded, comprising:
-at least one coloring agent, and
-binding agent, it is selected from polymer and material based on lipid, preferably their mixture;
E) described third layer (D) is surrounded, if any, or surround optional one of the described second layer (C) 4th layer (E), comprising:
-at least one wall-forming polymer, it is preferably selected from polysaccharide such as cellulose derivative, particularly cellulose Ether and cellulose esters, selected from (gathering) (alkyl) (methyl) acrylic acid and derivant thereof, especially (gather) (alkyl) (methyl) Acrylate and derivant thereof, and be preferably selected from alkyl acrylic/alkyl methacrylate copolymer and they Derivant.
16. according to the compositions according to any one of claim 1 to 15, the institute within wherein said compositions It is rupturable for stating microcapsule under the pressure being administered to keratin material.
17. according to the compositions according to any one of claim 1 to 16, the most described microcapsule total Weight, described core represents 10 weight % to 90 weight %, preferably 20 weight % to 80 weight %, more preferably 30 weights Amount % to 70 weight %, and even more preferably 40 weight % to 60 weight %.
18. according to the compositions according to any one of claim 1 to 17, the most described microcapsule, Described coloring agent represents 20 weight % to 90 weight %, and preferably 30 weight % are to 80 weight %;And especially 50 weight % are to 75 weight %.
19. according to the compositions according to any one of claim 1 to 18, present in wherein said microcapsule Described coloring agent, selected from inorganic pigment, organic pigment and their mixture, is preferably at least a kind of inorganic pigment, The more preferably at least mixture of inorganic pigment, even more preferably selected from metal-oxide, and in particular selected from ferrum oxygen Compound, titanium dioxide granule and their mixture, preferably their mixture.
20. compositionss according to any one of claim 1 to 10, wherein said microcapsule includes:
(A) core, preferably has the size in 20 μm to 800 μ m, and it includes at least one coloring agent Preferably at least a kind of binding agent, described coloring agent preferably includes to be preferably selected from least one nothing of iron oxides Machine pigment, and
(B) surrounding the parietal layer crushed of described core, it includes at least one coloring agent and preferably at least Planting binding agent, described coloring agent preferably at least includes titanium dioxide granule,
Wherein, compared with the gross weight of described microcapsule, described microcapsule includes the coloring of at least 70 weight % Agent.
21. according to the compositions according to any one of claim 1 to 20, at least the one of wherein said microcapsule Individual layer is obtained by bed process.
22. for nursing and/or the cosmetic method of keratin material of making up, and it includes according to claim 1 It is administered on described keratin material particularly on skin to the compositions any one of 21.
CN201480070567.4A 2013-12-26 2014-12-24 Transparent composition containing oil and microcapsules Pending CN105848626A (en)

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