CN101132834B - Rinse-off or wipe-off skin cleansing compositions - Google Patents
Rinse-off or wipe-off skin cleansing compositions Download PDFInfo
- Publication number
- CN101132834B CN101132834B CN200680007132.0A CN200680007132A CN101132834B CN 101132834 B CN101132834 B CN 101132834B CN 200680007132 A CN200680007132 A CN 200680007132A CN 101132834 B CN101132834 B CN 101132834B
- Authority
- CN
- China
- Prior art keywords
- compositions
- skin
- mixture
- composition
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Cosmetics (AREA)
Abstract
Methods of cleansing skin comprise the steps of contacting the skin with a cleansing compositions comprising a fatty ester in combination with a lipid, and either rinsing the composition from the skin with water or wiping the composition from the skin with a dry or damp substrate. The cleansing compositions can comprise at least 8%, by weight of the composition, of fatty ester and/or further comprise a nonionic surfactant and less than about 50%, by weight of the composition, of an alcohol solvent such as ethanol, isopropanol, or mixtures thereof. The methods and compositions provide skin cleansing and hydration benefits.
Description
Invention field
The present invention relates to method and the Cleasing compositions of cleaning skin, described compositions comprises the combination of aliphatic ester and lipoid.Described compositions and method provide skin clean and moisturizing beneficial effect.
Background of invention
Personal cleansing product in particular for the product of cleaning skin of face, is popular consumer goods in the Vehicles Collected from Market.Above-mentioned facial cleansing product tries hard to realize some cleaning beneficial effects, such as makeup removing, except Exfoliating Scrub, unimpeded pore, removal sebum etc.Although many facial cleansing products can effectively provide these the cleaning beneficial effect, many product Diazolidinyl Ureas or cause skin dehydration and become the drying.When being used for cleaning skin, even water itself also can cause skin dehydration.
Therefore, many consumers had both adopted the facial cleansing product that can realize cleaning beneficial effect, and then adopting provides the moisturizing beneficial effect and prevent xerodermatic skin moistening product to skin.
Therefore, still need to research and develop skin cleansing compositions, in particular for the skin cleansing compositions of facial cleansing.Described compositions can provide effective skin clean effect, improves simultaneously the skin moisture-keeping effect, and strong smooth foam is provided, and is easy to water flush away from the skin, or with doing or wet substrate is wiped from skin.
Summary of the invention
The present invention relates in cleaning skin, also provide compositions and the method for skin moisture-keeping beneficial effect.Described compositions comprises the combination of aliphatic ester and lipoid usually, with at washing-off type or wipe provide in the type Cleasing compositions cleaning and the moisturizing beneficial effect.Method of the present invention generally includes: make the present composition and contact skin, and water is with described compositions flush away from the skin, or with doing or wet substrate is wiped described compositions from skin.
In one embodiment, the present composition comprises by weight of the composition at least 8% aliphatic ester, with at washing-off type or wipe skin clean and moisturizing beneficial effect are provided in the type compositions, in particular for from skin except degreasing (as making up).
In one embodiment, the present composition comprises non-ionic surface active agent, so that described compositions is easy to from the skin flush away or otherwise removes.Described non-ionic surface active agent preferably has about 8 to about 20 average HLB.These compositionss are tending towards high degree of water, and comprise by weight of the composition the alcoholic solvent less than about 50% content, such as ethanol, isopropyl alcohol or their mixture.
In one embodiment, the present composition also comprises hydrophobic structure reagent.Described hydrophobic structure reagent is conducive to form gel network in the present composition, it is tending towards providing dense sliding sense at skin, and makes product be able to good application and can be to the skin injury.
Detailed Description Of The Invention
The present invention relates to method and Cleasing compositions for cleaning skin.Described compositions comprises aliphatic ester and the especially combination of high-modulus lipoid of lipoid.Described compositions also comprises many optional members, such as hydrophobic structure reagent, cationic surfactant, non-ionic surface active agent, amphoteric surfactant, anion surfactant, wetting agent, cracking-off agent, polymeric viscosifier, siloxanes, silicone elastomer, aqueous carrier and other optional member and their mixture.
Aliphatic ester
In the present composition, mix aliphatic ester so that skin clean and skin moisture-keeping beneficial effect to be provided.Aliphatic ester also can be used for strengthening the spreadability of lipoid, and can be used for reducing the lipoid typical case with cohesiveness.Described aliphatic ester can with the lipoid premix, or can they separately be added in products warm or when cooling.
The present composition will typically comprise by weight of the composition at least about 1%, preferably at least about 5%, more preferably at least about the aliphatic ester of 8% content.In the present composition content of aliphatic ester preferably be no more than by weight of the composition about 40%, preferably be no more than about 30%, more preferably no more than about 20%.In one embodiment, the present composition comprises by weight of the composition greater than 8%, is preferably greater than about 10% aliphatic ester.
Aliphatic ester of the present invention comprises the aliphatic ester oil of straight chain and side chain.Described aliphatic ester oil comprises one or two ester group in molecule.The common aliphatic ester oil that one class can be used among the present invention is fatty-acid monoester and polyester, such as Octanoic acid, hexadecyl ester, different octyl pelargonate, lactic acid myristyl ester, the lactic acid cetyl, isopropyl myristate, myristic acid myristyl ester, Dermol DIPS, IPIS, the isostearyl isostearate ester, two n-nonanoic acid propylene glycol esters, different n-nonanoic acid 2-Octyl Nitrite, stearic acid 2-Octyl Nitrite, isopropyl lanolate, BMDBM, malic acid two iso stearyl esters, neopentanoic acid iso stearyl ester, isopropyl palmitate, the adipic acid isopropyl ester, butyl stearate, different n-nonanoic acid ethyl hexyl ester, decyl oleate, the isostearic acid cholesteryl ester, glyceryl monostearate, distearin, glyceryl tristearate, lactic acid alkyl ester, citric acid Arrcostab and tartaric acid Arrcostab; Sorbitol ester etc.Preferred aliphatic ester is isopropyl palmitate and/or IPIS.
Described ester preferably has and is lower than about 100 milli Pascals (" mPa "), even more preferably less than about 75mPa, even more preferably less than about 50mPa, most preferably is lower than the viscosity of about 40mPa.
Fat-based individuality in the described ester preferably comprises and is no more than about 22 carbon atoms, more preferably no more than about 18 carbon atoms, more preferably no more than about 16 carbon atoms.For having greater than for the independent alkyl of 17 carbon atoms, be preferably side chain or undersaturated alkyl chain.The total number of carbon atoms is preferably less than about 30 in the aliphatic ester, even is more preferably less than approximately 25, even is more preferably less than about 23.
Lipoid
The present composition also comprises lipoid so that the skin moisture-keeping beneficial effect to be provided.Suitable lipoid comprises oil and high-modulus lipoid.High-modulus lipoid typical case among the present invention comprises oil and oily structural agent.By making the combination of lipoid and aliphatic ester of the present invention can obtain to have the compositions that strengthens skin clean and skin moisture-keeping beneficial effect.As previously mentioned, can be with lipoid and aliphatic ester premix during present composition preparation process.
The typical case mixes by weight of the composition about 0.1% to about 20%, preferred about 0.5% to about 15% in the present composition, more preferably from about 1% lipoid to about 10% content.Preferably, the ratio typical case of lipoid and aliphatic ester is no more than about 20: 1, more preferably no more than about 10: 1, more preferably no more than about 5: 1, more preferably no more than about 2: 1.Preferably, the ratio typical case of lipoid and aliphatic ester is at least about 1: 15, even more preferably at least about 1: 10, even more preferably at least about 1: 8, even more preferably at least about 1: 4.
Multiple oil is suitable for being incorporated in the compositions of the present invention as lipoid.The oil that one class can be used for herein is the triglyceride of triglyceride and modification.These comprise vegetable oil, for example Jojoba oil, soybean oil, Canola oil, Oleum helianthi, safflower oil, Testa oryzae oil, American Avocado Tree oil, almond oil, olive oil, Oleum sesami, peach kernel oil, Oleum Ricini, Oleum Cocois and ermine oil.Also can use synthetic triglyceride.The triglyceride of modification comprises that such as triglyceride derivative material ethoxylation and maleinization precondition is that they are liquid.The patent ester blend also suits, as by Finetex with trade name FINSOLV
Those that sell, it is thylhexoic acid glyceride.
Another kind of oil is the liquid polyester that is formed by dicarboxylic acids and glycol reaction.The embodiment that is applicable to polyester of the present invention is with trade name PURESYN by ExxonMobil
The polyester that ESTER sells.
It is liquid and semisolid hydrocarbon that Equations of The Second Kind is applicable to oil of the present invention.These comprise the oil of straight chain and side chain, such as the synthetic hydrocarbon of liquid paraffin, Squalene, squalane, mineral oil, low viscosity, as by ExxonMobil with trade name PURESYN
The poly alpha olefin that PAO sells and with trade name PANALANE
Or INDOPOL
The polybutene of selling.Highly branched lightweight (low viscosity) hydrocarbon ils also suits.
Lipoid of the present invention can be the high-modulus lipoid that comprises oil (as previously described those) and oily structural agent.Multiple oily structural agent is suitable to be incorporated in the high-modulus lipoid of the present invention.Described oily structural agent can be the organic or inorganic structural agent.Be applicable to the group that the following material of the optional freedom of embodiment of organic oil structural agent of the present invention forms: fat, fatty acid, fatty amine, natural and synthetic wax, block copolymer and their mixture of natural or modification.The block polymer that is applicable to this application can be with trade name KRATON by Shell
Those that sell.The group that the following material of the optional freedom of inorganic structure reagent forms: the silicon dioxide of hydrophobically modified, the clay of hydrophobically modified and their mixture.The limiting examples of inorganic structure agent is the BENTONE that derives from Rheox
27V, BENTONE
38V or BENTONE
GEL MIO V; And the CAB-O-SIL that derives from Cabot Corporation
TS720 or CAB-O-SIL
M5.
Described structural agent can be natural or synthetic crystalline wax.Mineral wax, animal wax or plant (vegetable) wax all is described to native paraffin.Synthetic wax is described to from those waxes of raw material synthesized polymer or the native paraffin of chemical modification.
Wherein, spendable natural crystalline wax is petroleum base wax, such as paraffin and microwax.Usually about 360 to the scope of about 420 (about 26 to about 30 carbon atoms), the type of long-chain (molecular weight mostly is about 600 most) also is available to the molecular weight of paraffin and have more.Typical fusing point is about 52 ℃ (126
) to about 57 ℃ (134
), the high molecular type has approximate about 77 ℃ (170
) fusing point.Paraffin is frangible, and the adding of oil is tending towards weakening its structure (reduction hot strength).The fusing point of microwax is about 63 ℃ (145
) to about 91 ℃ (195
).It is tiny and irregular that the microwax crystal is tending towards, and comprise following some types: lamellar, the crystallization of transition shape and needle-like.
Other suitable oily structural agent comprises the wax derived from animal or plant.Animal wax can derive from these things such as Apis, insecticide or whale.These waxes include but not limited to Cera Flava, white beeswax, shellac wax, spermaceti and lanocerin.Vegetable wax can be derived from bean, leaves and berry.Plant or vegetable wax can comprise bayberry, candelilla wax, Brazil wax, Cotton Gossypii, esparto wax, fir, jaqan, ouricury, Petiolus Trachycarpi, Testa oryzae oil, Caulis Sacchari sinensis, the straight cool and Oleum Cocois of meat.
Available in the synthetic crystalline wax is wax, polymerization-alpha-olefin and the artificial animal wax of crystalline polymer such as polyethylene, Fischer-Tuo Jinxi wax (such as polymethylene), chemical modification.For example, available silicon Cera Flava is the Cera Flava that has been chemically modified.
In addition, oily structural agent can also be natural or synthetic hydrogenated oil and fat.The oil of hydrogenation can be rapeseed oil, castor wax and a lot of other the oil of palm-kernel oil, the hydrogenation of Oleum Cocois, the hydrogenation of vegetable oil, the hydrogenation of hydrogenation.
Vaseline is unique hydrocarbon materials, because its typical case comprises oil (such as mineral oil) and oily structural agent (such as paraffin and/or microwax).Therefore, vaseline self has consisted of as described in the present invention high-modulus lipoid, and is the preferred high-modulus lipoid of the present invention.Vaseline also can with other lipoid blend of the present invention.Its semi-solid characteristic can be aborning and can be by formulator by being regulated with other lipoid blend.
High-modulus lipoid typical case of the present invention has at least about 50, preferably at least about 100, more preferably at least about 125, more preferably at least about 150 lipoid modulus value.The lipoid modulus value of lipid materials can be measured according to lipoid modulus measuring method as herein described.
Contain water hydrophobic structure reagent
The present invention is optional comprise be no more than by weight of the composition about 20%, preferably be no more than about 10%, more preferably no more than about 7.5% contain water hydrophobic structure reagent, it is preferably selected from the group that is comprised of following material: C
16To C
30Saturated fatty alcohol, comprise about 1 C to about 5 moles of ethylene oxide
16To C
30Saturated fatty alcohol, C
16To C
30Saturated dihydroxylic alcohols, C
16To C
30Saturated mono glycerin ether, C
16To C
30Saturated hydroxy-fatty acid and their mixture, its fusing point that has is at least about 40 ℃.The present invention is optional but preferably comprise by weight of the composition at least 0.5%, more preferably at least 1%, even more preferably at least 2% contain water hydrophobic structure reagent, it is preferably selected from the group that is comprised of following material: C
16To C
30Saturated fatty alcohol, comprise about 1 C to about 5 moles of ethylene oxide
16To C
30Saturated fatty alcohol, C
16To C
30Saturated dihydroxylic alcohols, C
16To C
30Saturated mono glycerin ether, C
16To C
30Saturated hydroxy-fatty acid and their mixture, its fusing point that has is at least about 40 ℃.The stability that these structuring reagent can be used for assisting the formation of compositions rheology characteristic and help compositions of the present invention.Specifically, describedly contain the formation that water hydrophobic structure reagent is tending towards assisting gel with liquid crystal structure network structure in the compositions of the present invention.The present composition preferably comprises gel network really." gel network " of the present invention typical case comprises and contains water hydrophobic structure reagent and surfactant.It is good that gel network in the compositions of the present invention is tending towards the butterfat sense that provides abundant and product is used, and skin is not damaged.
The suitable hydrophobic structure reagent of the present invention is selected from the group that is comprised of following material: stearyl alcohol, spermol, 16/octadecanol, tetradecanol, arachidic alcohol, docosanol, stearic acid, Palmic acid, on average have about 1 to the polyglycol ether of the stearyl alcohol of about 5 ethylene oxide units, on average have about 1 polyglycol ether to the spermol of about 5 ethylene oxide units, emulsifing wax (for example, available from the POLAWAX of Croda
NF) and their mixture.Preferred structuring reagent is selected from the group that is comprised of following material: stearyl alcohol, spermol, docosanol, stearyl polyoxyethylene ether-2 and their mixture.Above-mentioned hydrophobic structure reagent can provide as mixture with other hydrophobic structure reagent and/or surfactant.
Cationic surfactant
Compositions of the present invention is optional to comprise by weight of the composition about 0.1% to about 15%, and more preferably from about 0.2% to about 10%, most preferably from about 0.5% to about 5% cationic surfactant.Cationic surfactant can be used in the present composition, to help forming gel network in the present composition, although the formation of gel network does not need cationic surfactant.
The non-limiting example that can be used for cationic surfactant of the present invention comprises the cation ammonium salt, for example has those of following chemical formula:
R wherein
1Be selected from and have about 12 alkyl to about 22 carbon atoms, or be selected from and have about 12 aryl or alkaryls to about 22 carbon atoms; R
2, R
3And R
4Be independently selected from hydrogen, have about 1 to the alkyl of about 22 carbon atoms or have about 6 aromatic groups to about 22 carbon atoms, aryl or alkaryl; And X is anion, is selected from chloride ion, bromide ion, iodide ion, acetate, phosphate radical, nitrate anion, sulfate radical, methyl ester sulfate radical, ethyl ester sulfate radical, tosylate, lactate, citrate, ethanol acid group, glutamate and their mixture.Through checking, cationic surfactant can be via the protonation of amine in-situ generation.In addition, described alkyl also can comprise ehter bond or hydroxyl or amino substituent group (for example, alkyl can comprise Polyethylene Glycol and polypropylene glycol part).The preferred embodiment of cationic surfactant comprises VARISOFT TA100 and/or two palmityl alkyl dimethyl ammonium chlorides.
Other suitable cationic surfactant comprises protonated amine.Cationic protonated amine can be primary amine, secondary amine or tertiary amine (preferred secondary amine or tertiary amine), and it depends on particular types and the selected pH of compositions of the present invention.The limiting examples of cationic protonated amine comprises the amino diemethylamine of stearoyl, cocos nucifera oil acylamino-diemethylamine, the amino diemethylamine of lauroyl, Lexamine O 13, palmityl aminopropyl dimethylamine and their mixture.
Non-ionic surface active agent
In compositions of the present invention, can choose and preferably mix non-ionic surface active agent wantonly to strengthen the ability of washing compositions of the present invention from skin.When existing, the amount of mixing the non-ionic surface active agent in the compositions of the present invention is typically about 0.01% by weight of the composition to about 4%, is preferably about 0.1% to about 3%, and more preferably about 0.2% to about 2%.
Some that can be used in the non-ionic surface active agent of the present invention are but that generalized definition is long-chain alcohol such as C
8-30Those of the condensation product of alcohol and sugar or starch polymer, i.e. glucosides.These chemical compounds can be used chemical formula (S)
n-O-R represents that wherein S is sugar moieties, and such as glucose, sucrose, fructose, mannose or galactose, n is about 1 to about 1000 integer, and R is C
8-30Alkyl.The embodiment of long-chain alcohol of alkyl of can deriving comprises decanol, spermol, stearyl alcohol, lauryl alcohol, myristyl alcohol, oleyl alcohol etc.The preferred embodiment of these surfactants comprises those materials, and wherein S is glucose moiety, and R is C
8-20Alkyl, and n is about 1 to about 9 integer.The commercially available embodiment of these surfactants comprises available from the decyl poly glucoside of Cognis and lauryl poly glucoside.
Other useful ionic surfactant pack is drawn together the condensation product of sorbitol and fatty acid.Limiting examples comprises tween (Tween), span (Span) and polysorbate.
Other useful ionic surfactant pack is drawn together the condensation product (that is, the alkylene oxide ester of fatty acid) of alkylene oxide and fatty acid.These materials have general formula R CO (X)
nOH, wherein R is the C10-30 alkyl, X is-OCH
2CH
2-(namely derived from ethylene glycol or oxirane) or-OCH
2CHCH
3-(namely derived from propylene glycol or expoxy propane), and n is about 6 to about 100 integer.The limiting examples of the non-ionic surface active agent that these alkylene oxides are derived comprises ceteth-6, ceteth-10, ceteth-12, cetearyl polyoxyethylene ether-6, cetearyl polyoxyethylene ether-10, cetearyl polyoxyethylene ether-12, stearyl polyoxyethylene ether-6, stearyl polyoxyethylene ether-10, stearyl polyoxyethylene ether-12, the PEG-6 stearate, the PEG-10 stearate, the PEG-12 stearate, the PEG-20 tristerin, PEG-80 tallow acid glyceride, the PPG-10 tristerin, the PEG-30 glyceryl cocoate, the PEG-80 glyceryl cocoate, PEG-200 tallow acid glyceride, the PEG-8 dilaurate, the PEG-10 distearate, and their mixture.
Other useful non-ionic surface active agent also comprises polyhydroxy fatty acid amide surfactant.A kind of preferred polyhydroxy fatty acid amide surfactant is Cortex cocois radicis alkyl N-methyl glucosamine amide.Method for the preparation of the compositions that comprises polyhydroxy fatty acid amide is disclosed in for example by Thomas Hedley﹠amp; Co., Ltd. is in the british patent specification 809,060 of announcement on February 18 nineteen fifty-nine; The United States Patent (USP) of authorizing E.R.Wilson 2,965,576 of nineteen sixty December announcement on the 20th; The United States Patent (USP) of authorizing A.M.Schwartz 2,703,798 that announce March 8 nineteen fifty-five; In the United States Patent (USP) of authorizing Piggott 1,985,424 of announcing in 25th with December in 1934.
The limiting examples of suitable non-ionic surface active agent comprises: Polyethylene Glycol 20 sorbitans, one laurates (TWEEN-20), Polyethylene Glycol 5 soyasterols, stearyl polyoxyethylene ether-20, stearyl polyoxyethylene ether-21, cetearyl polyoxyethylene ether-20, cetearyl polyoxyethylene ether-12, PPG-2 methyl glucose ether distearate, ceteth-10, polysorbate 80, cetyl phosphate, the cetyl potassium phosphate, cetyl p diethylaminobenzoic acid hydramine, polysorbate 60, tristerin, the PEG-100 stearate, polyoxyethylene 20 sorbitan trioleate (polysorbate 85), sorbitan one laurate, polyoxyethylene 4 lauryl ether sodium stearates, polyglyceryl-4 isostearate, lauric acid hexyl ester, cetyl p diethylaminobenzoic acid hydramine, tristerin, the PEG-100 stearate, and their mixture.Preferred non-ionic surface active agent is to be selected from those of the group that is comprised of following material: stearyl polyoxyethylene ether-21, cetearyl polyoxyethylene ether-20, cetearyl polyoxyethylene ether-12, Tween-60, tween 80, sucrose cocos nucifera oil acid esters, stearyl polyoxyethylene ether-100, PEG-100 stearate, PEG-1000 stearate and their mixture.
Non-ionic surface active agent can be used for promoting comprising the flushing performance of the compositions of gel network.The average HLB value that preferred non-ionic surface active agent typical case has will be at least about 8, preferably at least about 9, and more preferably at least about 10, more preferably at least about 11, and more preferably at least about 12.In addition, it is about 20 that the average HLB value that preferred non-ionic surface active agent has will be not more than, preferably be not more than about 18, more preferably no more than about 16, and more preferably no more than about 14.
In addition, be used for promoting the preferred nonionic surfactants of compositions flushing performance of the present invention, especially comprise those of gel network, have C
8To C
16, preferred C
10To C
14, and more preferably C
10To C
12Alkyl chain length.The limiting examples of such non-ionic surface active agent comprises C
8-C
14Glucamide, C
8-C
14Alkyl polyglucoside, C
8-C
14Alkyl polyglucoside, and C
8-C
14Alkyl ethoxylate.
Amphoteric surfactant
Compositions of the present invention can be chosen wantonly and comprise by weight of the composition about 0.1% to about 20%, and more preferably from about 0.2% to about 10%, most preferably from about 0.5% to about 5% amphoteric surfactant.
Term used herein " amphoteric surfactant " also is intended to comprise zwitterionic surfactant, and it is the subset of amphoteric surfactant.
Multiple amphoteric surfactant can be used in the compositions of the present invention.Be particularly useful be as aliphatic secondary amine and tertiary amines derived thing by broadly described those, preferably wherein nitrogen is the cation state, wherein said aliphatic group can be straight chain or side chain, and wherein in the group comprises ionogenic water solubilizing group, such as carboxyl, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical.
The limiting examples that is used for the amphoteric surfactant of compositions of the present invention is disclosed in " Detergentsand Emulsifiers " (North America version (1986)) of the McCutcheon that Allured Publishing Corporation publishes and " Functional Materials " (North America version (1992)) of McCutcheon.
The limiting examples of zwitterionic surfactant comprises those that are selected from the group that is comprised of following material: betanin, sulfobetaines, hydroxyl sulfo betaine, alkyl imino acetate, iminodiacetic alkanoate, amino-alkane hydrochlorate and their mixture.
Preferred amphoteric surfactant comprises N-lauroyl amido ethyl-N hydroxyethyl oxalic acid disodium, N-lauroyl amido ethyl-N hydroxyethyl sodium acetate, cetyl dimethyl betaine (being cetyl betaine), cocoamidopropyl, cocos nucifera oil acylamino-propyl hydroxy sulfobetaines, or their mixture.Wherein, especially preferred cetyl dimethyl betaine (being cetyl betaine).
Anion surfactant
Compositions of the present invention optionally comprises by weight of the composition about 0.1% to about 20%, and more preferably from about 0.2% to about 10%, most preferably from about 0.5% to about 5% anion surfactant.
The limiting examples that can be used for the anion surfactant in the present composition is disclosed in " Detergentsand Emulsifiers " North America version (1986) of the McCutcheon of allured Publishing Corporation announcement; " FunctionalMaterials " North America version (1992) of McCutcheon; In the United States Patent (USP) 3,929,678 of authorizing the people such as Laughlin of announcing in 30th with December in 1975.All above-mentioned documents are incorporated herein by reference.
Multiple anion surfactant can be used for the present invention.The non-limiting example of anion surfactant comprises alkanoyl isethionate and alkyl sulfate and alkyl ether sulfate.Alkanoyl isethionate typical case has RCO-OCH
2CH
2SO
3The M chemical formula structure, wherein R has about 10 alkyl or alkenyls to about 30 carbon atoms, and M is water-soluble cationic, such as ammonium, sodium, potassium and triethanolamine.The non-limiting example of these isethionates comprises those alkanoyl isethionates, and it is selected from the group that is comprised of following material: Ammonium cocoyl isethionate, cocoyl sodium isethionate, lauroyl sodium isethionate, stearoyl sodium isethionate and their mixture.
Alkyl sulfate and alkyl ether sulfate typical case have respectively ROSO
3M and RO (C
2H
4O)
xSO
3The M chemical formula structure, wherein R has about 10 alkyl or alkenyls to about 30 carbon atoms, and x is about 1 to about 10, and M is water-soluble cationic, such as ammonium, sodium, potassium and triethanolamine.Another kind of suitable anion surfactant is the water soluble salt of organic sulfur acidification reaction product, has following general formula:
R
1-SO
3-M
R wherein
1Be selected from the group that is formed by following groups: have about 8 to about 24, the preferred about 10 radical of saturated aliphatic alkyl to the straight or branched of about 16 carbon atoms; And M is cation.Other anion synthetic surfactant also comprises and is designated as Succinamate, contains about 12 these classes to alkene sulfonic acid ester and the b-oxyalkyl chain alkyl sulfonic acid ester of about 24 carbon atoms.The example of these materials is sodium lauryl sulfate and ammonium lauryl sulfate.
Other anionic species comprises sarcosinate, and its non-limiting example comprises sodium lauroyl sarcosine, cocoyl sodium sarcosinate and Hamposyl L ammonium.
Other can be used for anionic species of the present invention is fatty acid soaps (be alkali metal salt, for example sodium salt or potassium salt).This fatty acid typically contains has an appointment 8 to about 24 carbon atoms, preferred about 10 to about 20 carbon atoms.The fatty acid that is used for soapmaking can be obtained by natural source, for example derives from the glyceride (for example, Petiolus Trachycarpi oil, Oleum Cocois, soybean oil, Oleum Ricini, Adeps Bovis seu Bubali, Adeps Sus domestica, etc.) of plant or animal.Fatty acid also can be made by synthetic.Soap is described in more detail in the United States Patent (USP) 4,557,853 of above quoting.
Other anionic materials comprise phosphate, for example monoalkyl, dialkyl group and trialkyl phosphate.
Other anionic species comprises and meets chemical formula RCON (CH
3) CH
2CH
2CO
2The alkanoyl sarcosinate of M structure; wherein R has about 10 alkyl or alkenyls to about 20 carbon atoms; and M is water-soluble cationic, and such as ammonium, sodium, potassium and trialkanolamine (such as triethanolamine), its preferred embodiment is sodium lauroyl sarcosine.
The non-limiting example that preferably can be used for anion surfactant of the present invention comprises and being selected from by the following group that those form: sodium lauryl sulfate, ammonium lauryl sulfate, cetyl ammonium sulfate, cetyl sodium sulfate, stearyl sodium sulfate, Ammonium cocoyl isethionate, lauroyl sodium isethionate, sodium lauroyl sarcosine and their mixture.
The anion surfactant that preferably can be used for this paper is sodium lauryl sulfate.
Wetting agent
Multiple wetting agent can be chosen wantonly for the present composition, and its content is about 0.1% to about 20% by weight of the composition, and more preferably about 0.5% to about 10%, most preferably is about 1% to about 5%.
The non-limiting example of wetting agent comprises and is selected from the group that is comprised of following material: guanidine; Glycolic and glycollate (such as ammonium salt and tetraalkylammonium salt); Lactic acid and lactate (such as ammonium salt and tetraalkylammonium salt); Any (such as Aloe gel) in the various ways Aloe; Polyhydroxy-alcohol is such as sorbitol, glycerol (being glycerol), hexanetriol, propylene glycol, butanediol, hexanediol etc.; Polyethylene Glycol; Sugar and starch; The derivant of sugar and starch (such as the alkoxylate glucose); Hyaluronic acid; The lactamide monoethanolamine; The acetamide monoethanolamine; And their mixture.Also available is propoxylated glycerol described in the nineteen ninety United States Patent (USP) 4,976,953 of authorizing the people such as Orr announced in 11st of December, and described document is incorporated herein by reference.
The wetting agent that preferably can be used for this paper is glycerol (being glycerol).
Cracking-off agent
The present composition also optionally comprises cracking-off agent.Described cracking-off agent is derived from multiple particulate material, comprises derived from those of inorganic source, organic source, natural source and synthetic source.
When existing, the typical amounts of graininess cracking-off agent of the present invention is about 0.1% to about 20% by weight of the composition, is preferably about 0.25% to about 10%, more preferably about 0.5% to about 5%.The non-limiting example of these materials is selected from following material: the Semen Armeniacae Amarum coarse powder, Alumina, aluminium oxide, aluminium silicate, the Fructus Pruni powder of seeds, attapulgite, Fructus Hordei Vulgaris powder, bismuth oxychloride, boron nitride, calcium carbonate, calcium phosphate, calcium pyrophosphate, calcium sulfate, cellulose, Chalk, chitin, clay, the corn cob coarse powder, the corn cob powder, Semen Maydis flour, hominy grits, corn starch, kieselguhr, dicalcium phosphate, dicalcium phosphate dihydrate, bleaching earth, Shionox, hydroxyapatite, ferrum oxide, the Jojoba oil powder, Kaolin, Fructus Luffae, magnesium trisilicate, Muscovitum, microcrystalline Cellulose, Montmorillonitum, bran of Fagopyrum esculentum Moench, oat flour, oat meal, enucleation peach powder, the Semen Caryae Cathayensis shell powder, polybutene, polyethylene, polyisobutylene, polymethylstyrene, polypropylene, polystyrene, polyurethane, nylon, special teflon (being politef), many halogenated olefins, the Pumex Testa oryzae, the rye (Secale cereale L.) face, sericite, Silicon stone, silk, sodium bicarbonate, sodium aluminosilicate, large bean flour, synthetic li-montmorillonite, Talcum, stannum oxide, titanium dioxide, tricalcium phosphate, the Endocarpium Juglandis powder, Testa Tritici, Semen Tritici aestivi powder, wheaten starch, Zirconium orthosilicate., and their mixture.The granule of also usefully being made by the polymer (for example, copolymer, terpolymer etc.) that mixes wherein has polyethylene/polypropylene copolymers, polyethylene/propylene/isobutylene copolymers, polyethylene/styrol copolymer and their mixture.Typically, can process polymer beads and mixing of polymer particles to destroy impurity and so on by oxidation technology.Polymer beads and mixing of polymer particles also can be chosen wantonly with multiple common cross-linking agent crosslinked, and the limiting examples of described cross-linking agent comprises the allyl ether of butadiene, divinylbenzene, methylene-bisacrylamide, sucrose, the allyl ether of tetramethylolmethane and their mixture.Other embodiment that can be used as granule comprises wax and resin, such as paraffin, Brazil wax, ceresine, candelilla wax, Lauxite and so on.When this type of wax and resin were used for this paper, importantly these materials were solid under environment and the skin temperature around.
Wherein, the water-insoluble particulate material that is preferably used as this paper cracking-off agent is synthetic polymer particle.Can be used for synthetic polymer particle of the present invention and be selected from the group that is formed by following material: polybutene, polyethylene, polyisobutylene, polymethylstyrene, polypropylene, polystyrene, polyurethane, its oxidized derivatives, nylon, politef and their mixture.The non-limiting example of suitable cracking-off agent comprises with trade name A-C oxidic polyethylene Zhu Shi and is sold by Honeywell and with commodity ACCUSCRUB
TMThe globule city is sold by Accutech, the oxidic polyethylene pearl of LLC.
Coated interference pigment
The present composition also optionally comprises coated interference pigment.Coated interference pigment is to have nacreous pigment, and it can make by the surface that is coated with granular substrate material with the thin film bag.Granular substrate material is generally strip.Described thin film is the transparent or semitransparent material with high index of refraction.High-index material shows to have the pearly-lustre color, and this is by producing from the incident illumination of strip substrate/coating interface reflection with from the mutual interference effect between the incident illumination of coating surface reflection.When existing, compositions of the present invention preferably comprise be no more than by weight of the composition about 20%, more preferably no more than about 10%, even more preferably no more than about 7%, also more preferably no more than about 5% coated interference pigment.When existing, compositions of the present invention preferably comprises by weight of the composition at least about 0.01%, more preferably at least about 0.05%, even more preferably at least about 0.1%, also more preferably at least about 0.2% coated interference pigment.
In one embodiment, described coated interference pigment surface is hydrophobic or by hydrophobically modified.Contact angle is larger, and the hydrophobicity of coated interference pigment is just larger.Described coated interference pigment preferably has at least about 60 degree, more preferably at least about 80 degree, even more preferably at least about 100 degree, also more preferably at least about 110 contact angles of spending.Can according to the granule contact angle method of testing described in the U.S. Provisional Application serial number 60/658,687 (lawyer's file number 9933P) of submitting on March 4th, 2005, measure the contact angle of described coated interference pigment.The coated interference pigment of hydrophobically modified (" HMIP ") can make HMIP be entrained in the dispersion oil phase, and HMIP is deposited greatly.In a preferred embodiment, described compositions comprises HMIP and disperses oil phase.HMIP is preferably about 1: 1 to about 1: 70 with the weight rate that disperses oil phase, and more preferably from about 1: 2 to about 1: 50, also more preferably from about 1: 3 to about 1: 40, most preferably from about 1: 7 to about 1: 35.
When being mixed with product, described HMIP preferably is entrained in and disperses in the oil phase.This must make described oil phase granularity greater than HMIP usually.In a preferred embodiment of the present invention, described oil phase granule only comprises a small amount of HMIP in every part of oil particles.This is more preferably less than 10 preferably less than 20, most preferably less than 5.These parameters, the relative size of oil droplet and HMIP and every part of HMIP granule approximate number that the dispersed oil granule is contained can be measured by using by the visual detection of optical microscope.
Can by pre-composition or respectively, HMIP and oil be mixed in the described compositions.In situation about adding respectively, in the course of processing of preparation, hydrophobicity pigment is assigned in the oil phase.By described total particle weighing scale, the hydrophobic coating content of HMIP of the present invention is preferably and is no more than about 20% weight, more preferably is no more than about 15% weight, even more preferably is no more than about 10% weight.By described total particle weighing scale, the hydrophobic coating content that HMIP of the present invention has is preferably at least about 0.1% weight, more preferably at least about 0.5% weight, even more preferably at least about 1% weight.The limiting examples that can be used for the hydrophobic surface treatments of this paper comprises siloxanes, acrylate silicone copolymers, acrylate polymer, alkyl silane, three isostearic acid titanium isopropyl esters, sodium stearate, magnesium myristate, perfluor alcohol phosphate ester, the poly-methyl isopropyl ether of perfluor, lecithin, Carlow bar wax, polyethylene, chitosan, lauroyl lysine, cerolipoid extract and their mixture, preferred siloxanes, silane and stearate.Surface disposal facility comprises U.S.Cosmetics, KOBO Products Inc. and Cardre Inc..
Coated interference pigment in the present composition is sheet-like particle.Sheet-like particle in the present composition has and is no more than about 5 μ m, more preferably no more than about 2 μ m, also more preferably no more than the thickness of about 1 μ m.The sheet-like particle of the present composition has preferably at least about 0.02 μ m, more preferably at least about 0.05 μ m, even more preferably at least about 0.1 μ m, also more preferably at least about the thickness of 0.2 μ m.
Granularity typical case has determined opacity and gloss.Can measure granularity by the diameter thickness of measuring particulate matter.The ultimate range that term used herein " diameter " refers to cross the particulate matter major axis.Can be by any suitable method known in the art, the Particle Size Analyzer Mastersizer2000 as being made by Malvern Instruments measures diameter.Coated interference pigment in the present composition preferably has at the most about 200 μ m, more preferably 100 μ m at the most, even more preferably about 80 μ m at the most, the also more preferably average diameter of about 60 μ m at the most.The coated interference pigment of the present composition preferably has at least about 0.1 μ m, more preferably at least about 1.0 μ m, even more preferably at least about 2.0 μ m, also more preferably at least about the diameter of 5.0 μ m.
The coated interference pigment of the present composition comprises multiple structure.The granule center is that refractive index (RI) is usually less than 1.8 flat substrate.Multiple particle matrix can be used for this paper.Limiting examples is natural mica, synthetic mica, graphite, Talcum, Kaolin, alumina wafer, bismuth oxychloride, titanium dioxide silicon chip, sheet glass, pottery, titanium dioxide, CaSO
4, CaCO
3, BaSO
4, borosilicate and their mixture, preferred Muscovitum, silicon dioxide and alumina wafer.
Can be at the surface of above-mentioned substrate coating thin film or plural layers.Thin film is made by high-refraction material.The refractive index of these materials is usually more than 1.8.
There are various thin film to can be used for this paper.Limiting examples is TiO
2, Fe
2O
3, SnO
2, Cr
2O
3, ZnO, ZnS, ZnO, SnO, ZrO
2, CaF
2, Al
2O
3, BiOCl and their mixture, or be the form of stratum disjunctum, preferred TiO
2, Fe
2O
3, Cr
2O
3, SnO
2For multiple structure, thin film can be comprised of all high-index materials, or alternately is comprised of the thin film with high and low RI material, and with high RI thin film as top layer.
Interference colours are functions of film thickness, can be different with the difference of material for the thickness of concrete color.To TiO
2; the layer of 40nm to 60nm thickness or the integral multiple of this layer can provide silver color, and the layer of 60nm to 80nm thickness can provide yellow, and the layer of 80nm to 100nm thickness can provide redness; the layer of 100nm to 130nm thickness can provide blueness, and the layer of 130nm to 160nm thickness can provide green.Except interference colours, other transparent absorption pigment is also precipitable at TiO
2The top of layer or precipitate simultaneously with the TiO2 layer.Common material is redness or black iron oxide, ferric ferrocyanide, chromium oxide or carmine.Except the brightness of coated interference pigment, the color of coated interference pigment also has significant impact the people aspect the sensation of the colour of skin.Usually, preferred color is silver color, gold, redness, green or their combination.
The non-limiting example that can be used for the coated interference pigment of this paper comprises that by Persperse Inc. is with trade name PRESTIGE
, FLONAC
Those that provide; By EMD Chemicals, Inc. is with trade name TIMIRON
, COLORONA
, DICHRONA
And XIRONA
Those that provide; And by Engelhard Co. with trade name FLAMENCO
, TIMICA
, DUOCHROME
Those that provide.
Polymeric viscosifier
In some embodiments, compositions of the present invention also can comprise one or more polymeric viscosifiers.When existing, the typical case mixes polymeric viscosifier in the present composition, and it is about 10% that its content is no more than by weight of the composition, preferably be no more than about 8%, also more preferably no more than about 7%.When existing, the typical case mixes polymeric viscosifier in the present composition, and its content is at least about 0.01% by weight of the composition, more preferably at least about 0.05%, also more preferably at least about 0.1%.Different polymeric viscosifier blend is together normally useful to produce best stability and rheological behavior.
The non-limiting example that can be used for polymeric viscosifier of the present invention comprises carboxylic acid polyalcohol, such as carbomer (as with trade name CARBOPOL
900 serial cities are sold by those of B.F.Goodrich; Such as CARBOPOL
954) and derive from the Luvigel series of BASF.Other suitable carboxylic acid polymerizer comprises acrylic acid C
10-30The copolymer of Arrcostab and one or more monomers.Described monomer comprises: acrylic acid, methacrylic acid or their short chain (are C
1-4Alcohol) a kind of in the ester, wherein cross-linking agent is the allyl ether of sucrose or tetramethylolmethane.These copolymers are called as acrylate/C
10-30Alkyl acrylate cross-linked polymer, and can trade name CARBOPOL
1342, CARBOPOL
1382, CARBOPOL
Ultrez21, CARBOPOL
Ultrez20, CARBOPOL
Ultrez10, PEMULEN
TR-1 and PEMULEN
The TR-2 city is sold by B.F.Goodrich.
Other limiting examples of polymeric viscosifier comprises crosslinked polyacrylate polymers, comprises cationic polymer and non-ionic polymers.
Other limiting examples of polymeric viscosifier also comprises polyacrylamide polymers, and non-ionic polyacrylamide polymer especially comprises side chain or the unbranched polymer of replacement.The non-ionic polymers of CTFA called after polyacrylamide and isoparaffin and laureth-7 more preferably in these polyacrylamide polymers, with trade name Sepigel305 available from SeppicCorporation (Fairfield, NJ).Can be used for other polyacrylamide polymers of the present invention and comprise the acrylamide of acrylamide and replacement and acrylic acid segmented copolymer of acrylic acid and replacement.The commercially available embodiment of these segmented copolymers comprises and derives from Lipo Chemicals, the HYPAN of Inc. (Patterson, NJ)
SR150H, SS500V, SS500W, SSSA100H.
Another the non-limiting classification that can be used for polymeric viscosifier of the present invention is polysaccharide.The limiting examples of polysaccharide gellant comprises those that are selected from cellulose and cellulose derivative.The material of the CTFA called after cetyl hydroxyethyl-cellulose that preferably gives in alkyl-hydroxyalkylcelluloswith ether, it is the ether of spermol and hydroxyethyl-cellulose, with trade name NATROSEL
CS PLUS is sold by Aqualon Corporation (Wilmington, DE).Other spendable polysaccharide comprises scleroglycan, it comprises the straight chain of the glucose unit of one (1-3) connection, per 3 unit have the glucose that (1-6) connects, and its commercially available embodiment is the CLEAROGEL available from Michel MercierProducts Inc
TMCSll.
Another the non-limiting classification that can be used for polymeric viscosifier of the present invention is natural gum.The limiting examples that can be used for natural gum of the present invention comprises Strese Hofmann's hectorite., Shionox, xanthan gum and their mixture.
Another the non-limiting classification that can be used for polymeric viscosifier of the present invention is modified starch.Can use acrylate modified starch such as the WATERLOCK available from Grain Processing Corporation
With trade name STRUCTURE XL
Be another embodiment of available modified starch available from the hydroxypropyl starch phosphate ester of National Starch, and other available embodiment comprise the ARISTOFLEX available from Clariant
HMB (ammonium acryloyldime-thyltaurate// mountain Yu base polyoxyethylene ether-25 methacrylate cross linked polymer) and cationic polymerization stabilizing agent.
Siloxanes
Siloxanes can be used as the optional member in the present composition such as the polydialkysiloxane with 3 to 9 silicon atoms, poly-diaromatic siloxane, poly-alkaryl siloxanes and Cyclomethicone.These siloxanes comprise volatile material and nonvolatile matter.These siloxanes are disclosed in the United States Patent (USP) of authorizing Orr 5,069,897 of December in 1991 announcement on the 3rd, and it is incorporated herein by reference.Described poly-alkylsiloxane comprises, for example, is about 5E-7m 25 ℃ of viscosity that have
2/ s (0.5 centistoke) is to about 0.6m
2The poly-alkylsiloxane of/s (600,000 centistoke).Selector combination general formula R
3SiO[R
2SiO]
xSiR
3The above-mentioned poly-alkylsiloxane of (wherein R is alkyl (R is preferably methyl or ethyl, more preferably methyl), and x is integer) is to realize required viscosity.Commercially available poly-alkylsiloxane comprises polydimethylsiloxane, and it also is called as dimethicone, and embodiment comprises the VICASIL that is sold by General Electric Company
Series and the Dow Corning that is sold by Dow Corning Corporat ion
200 series.Can be used for the poly-alkylsiloxane of ring-type of the present invention comprises and meets chemical general formula [SiR
2-O]
nThose, wherein R is alkyl (R is preferably methyl or ethyl, more preferably methyl), and n is about 3 to about 9 integer, more preferably n is about 3 to about 7 integer, and most preferably n is about 5 to about 6 integer.When R was methyl, these materials typical case was called as the ring-type polymethyl siloxane.Also spendable material is for example trimethylsiloxy esters of silicon acis, and it is to meet chemical general formula [(CH
2)
3SiO
1/2]
x[SiO
2] polymeric material of y, wherein x is about 1 to about 500 integer, and y is about 1 to about 500 integer.Commercially available trimethylsiloxy esters of silicon acis as with the mixture of polydimethylsiloxane with Dow Corning
593 fluids are sold.Also can be used for of the present invention is dimethiconol, and it is the terminal dimethyl siloxane of hydroxyl that is.These materials can be by chemical general formula R
3SiO[R
2SiO]
xSiR
2OH and HOR
2SiO[R
2SiO]
xSiR
2OH represents that wherein R is alkyl (R is preferably methyl or ethyl, more preferably methyl).Commercially available dimethiconol typical case is to sell (Dow Corning for example with the mixture of polydimethylsiloxane or ring-type polymethyl siloxane
1401,1402 and 1403 fluids).Also can be used for of the present invention is the polyoxyethylene alkyl aryl radical siloxane, is about 1.5E-5m 25 ℃ of viscosity that have preferably
2/ s (15 centistoke) is to about 6.5E-5m
2The PSI of/s (65 centistoke).These materials for example SF1075 aminomethyl phenyl fluid (being sold by General Electric Company) and the poly-trimethicone fluid of 556 cosmetics-stage phenyl (by Dow Corning Corporation sale) are buied.Siloxanes as herein described can with the silicone gum blend to send required sense organ and skin condition beneficial effect.Above-mentioned blend can be available from Dow Corning and GE Silicones.In addition, the commercially available acquisition of the silicone gum of emulsifying and being applicable in the present composition.
When existing, present composition typical case comprises by weight of the composition about 0.1% to about 25%, preferred about 0.5% to about 20%, and 1% to about 10% siloxanes more preferably from about.
Silicone elastomer
Compositions of the present invention also can be chosen wantonly and comprise by weight of the composition about 0.1% to about 30% silicone elastomer component.The preferred content of silicone elastomer is about 0.5% to about 30% by weight of the composition, and more preferably about 1% to about 20%.
Being applicable to silicone elastomer of the present invention can be crosslinked siloxane elastomer emulsifying or non-emulsifying or its mixture.Do not have special restriction for curable organopolysiloxane composition type, it can be used as the elastomeric raw material of cross-lined organic polyorganosiloxane.Embodiment in this respect is, the organopolysiloxane composition that additive reaction is solidified, diorganopolysiloxanecompositions by comprising SiH and have and the organopolysiloxane of the vinyl of silicon bonding between additive reaction, under platinum metal catalyst, described compositions is solidified; Condensation cured organopolysiloxane composition, by hydroxy-end capped diorganopolysiloxanecompositions with comprise dehydrogenation reaction between the diorganopolysiloxanecompositions of SiH, in the presence of organo-tin compound, described compositions is solidified; And condensation cured organopolysiloxane composition, in the presence of organo-tin compound or titanate esters, described compositions is solidified.
Because their very fast solidification rate and good curing uniformity, the organopolysiloxane composition of additive reaction-curing can be preferred.The organopolysiloxane composition of a kind of preferred additive reaction-curing is prepared by following material:
(A) has the organopolysiloxane of at least 2 low-grade alkenyls in each molecule;
(B) have at least 2 organopolysiloxanes that connect the hydrogen atom of silicon in each molecule; With
(C) platinum type catalyst.
Compositions of the present invention can be chosen the cross-lined organic polyorganosiloxane elastomer of the cross-lined organic polyorganosiloxane elastomer that comprises emulsifying, non-emulsifying or their mixture wantonly.Term used herein " non-emulsifying " definition does not contain the cross-lined organic polyorganosiloxane elastomer of polyoxyalkylene unit.The cross-lined organic polyorganosiloxane elastomer of term used herein " emulsifying " refers to have at least one polyoxyalkylene (for example, polyoxyethylene or polyoxypropylene) unit.The elastomer of the preferred emulsifying of this paper comprises the elastomer of polyoxyalkylene modification, and it is by divinyl compound, especially has the siloxane polymer of at least two free vinyl, forms with the reaction of Si-H key on polysiloxane backbone.Preferably, described elastomer is by the crosslinked dimethyl polysiloxane in Si-H site on the spherical MQ resin of molecule.The cross-lined organic polyorganosiloxane elastomer of emulsifying can be selected from U.S.5 especially, and 412,004, U.S.5,837,793 and U.S.5, the cross linked polymer described in 811,487.In addition, by the dimethicone copolyol cross linked polymer (with) emulsifying elastomer that forms of polydimethylsiloxane can trade name KSG-21 available from Shin Etsu.
Advantageously, the elastomer of this non-emulsifying is the Dimethicone/Vinyl Dimethicone cross linked polymer.This class Dimethicone/Vinyl Dimethicone cross linked polymer can be by a lot of suppliers supply, comprise Dow Corning (DC9040 and DC9041), General Electric (SFE839), Shin Etsu (KSG-15,16,18[polydimethylsiloxane/phenyl vinyl polydimethylsiloxane cross linked polymer]) and GrantIndustries (GRANSIL
TMThe series elastomer).Can be used for cross-lined organic polyorganosiloxane elastomer of the present invention and preparation method thereof and also be described in U.S.4, in 970,252, U.S.5,760,116 and U.S.5,654,362.Can be used for other cross-lined organic polyorganosiloxane elastomer of the present invention is disclosed among the Japanese patent application JP61-18708 that transfers Pola Kasei Kogyo KK.
The commercially available silicone elastomer that preferably can be used for this paper is the 9040 silicone elastomer blends of Dow Corning, the KSG-21 of Shin Etsu and their mixture.
Aqueous carrier
The present composition preferably comprises water.The present composition comprises by weight of the composition the typical case at least about 20%, preferably at least about 30%, more preferably at least about 40%, more preferably at least about 50% water.
The present composition also can comprise optional solvent, such as ethanol, isopropyl alcohol and their mixture.In one embodiment, the present composition comprises by weight of the composition less than about 50%, preferably less than about 30%, be more preferably less than about 10% alcoholic solvent, it is selected from by the following group that those form: ethanol, isopropyl alcohol and their mixture.In one embodiment, the present composition comprises by weight of the composition less than about 1%, preferred 0% alcoholic solvent, and it is selected from by the following group that those form: ethanol, isopropyl alcohol and their mixture.
Other optional member
The present composition also can comprise other optional member.Other suitable optional member comprises spice, antiseptic, chelating agen, sensory agent, desquamation active substance, anti-acne active substance, anti-wrinkle/anti-atrophy active substance, antioxidant/free radical scavenger, flavonoid, antiinflammatory, anti-cellulite scorching agent, local anesthetic, tanned active substance, skin lightening agent, skin is consoled and rehabilitation agent, anti-microbial active matter, sunscreen actives, skin appearance reinforcing agent, etc.Above-mentioned optional member is described in the U.S. Provisional Application serial number 60/658,687 (Attorney Docket9933P) of submitting on March 4th, 2005 more imperfectly.
In one embodiment, the present composition is substantially free of or does not contain active component, and such as U.S.5,811,111 the 8th hurdles the 10th walk to those described in the 10th hurdle the 16th row.In one embodiment, the present composition is substantially free of or does not contain salicylic acid.
Compositions of the present invention has about 3 to about 9 with the typical case, and preferred about 4 to about 8, more preferably from about 5 pH to about 7 scopes.
Packing
Compositions of the present invention can be packaged in the multiple suitable container.The non-limiting example of appropriate vessel comprises pipe, bottle, jar, hand pump type container etc.Described container typical case is made by plastic material.The embodiment of suitable plastic material comprises high density polyethylene (HDPE) (" HDPE "), Low Density Polyethylene (" LDPE "), polyethylene terephthalate (" PET "), polypropylene (" PP "), polrvinyl chloride, Merlon, nylon and PEP.Described bottle can make by multiple diverse ways known in the art, such as blowing moulding, injection molding, etc.The preferred bottle of the present invention is made by HDPE or PP via the extrusion blow method, or is made by PET via injection blow molding method.
The method of cleaning skin
The invention still further relates to the method for cleaning skin, wherein said method comprises makes skin contact with compositions of the present invention, and water is its flush away from the skin, or with substrate it is wiped from skin, to remove at least a portion compositions from skin.
In preferred embodiments, compositions of the present invention also can be used for cleaning and/or moisturizing skin, especially can be used for the cleaning of facial and neck area.Typically, the Cleasing compositions of Sq or effective dose can be applied in the zone of to be cleaned and/or moisturizing.Alternatively, can via indirectly being administered on bath towel, sponge, protective pad, cotton balls or other application device, use the Cleasing compositions of Sq.If necessary, the pre-moistening of regional available water to be cleaned.Find that during the cleaning course and from the skin during the flush away, compositions of the present invention can make up with water.Alternatively, described compositions can be used separately, and uses protective pad, cotton balls, thin paper or other similar device or substrate, wipes from skin.Described clean method is typically two-stage process, relates to using of compositions, thereafter or the described product of water flush away, or wipes in the situation that does not make water.Usually, the effective dose of stand-by compositions will depend on a human needs and use habit.
Lipoid modulus method of testing
At first on the TA InstrumentsAR2000 Stress Control flow graph that is equipped with Peltier temperature control sample stage or equivalent, measure the rheological behavior of lipoid.Use is arranged with the parallel-plate in 40mm plate and 1mm gap.With bottom plate heating to 85 ℃, and lipoid and the structural agent (if present) of melting added on the base plate, and make it balance.Then upper plate is reduced to the 1mm gap location, guarantees that simultaneously lipoid fills up the gap fully, the rotation top board also adds more lipoid impelling wicking, and described sample is quickly cooled to 25 ℃, and 25 ℃ of lower balances 5 minutes.Then usually on the device of these types applied stress gradual change program measure viscosity, use the gradual change of logarithm stress to continue 2 minutes from 20Pa to 2500Pa, per ten comprise 60 measurement points.The stress of starting and ending is enough to induce mobile and reaches at least 10s
-1Shear rate.Record viscosity, and use formula 1 that data fitting is become power law model.Only between 0.001s
-1And 40s
-1Between name a person for a particular job and be used in the power law fit.Calculate 1.0s by formula 1
-1The viscosity at place.Should examine sample at test period, stop the method with when ejection under the convenient material slave plate.
Formula 1:
η＝κ·γ(dot)(
n-1)
η=viscosity wherein, κ is denseness, and γ (dot) is shear rate, and n shears index.
The test of lipoid modulus utilizes the data of being collected by the test of lipoid rheological behavior.In this case, data are mapped to the % strain with stress (Pa).The value (if in 200% strain place have data point use range estimation infer) and will be worth divided by 2 (200% strain are 2 strain) of described modulus by record 200% strain place obtains to obtain the lipoid modulus.Usually, test five samples, and discard high value and low value, and three values of centre are averaged, to obtain the lipoid modulus value.
Embodiment
It below is the non-limiting example of the present composition.Described compositions is cleaning cream or cleaning emulsion form, and is suitable for cleaning skin.
| Composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Mixture A | ||||||
| Water | In right amount to 100 | In right amount to 100 | In right amount to 100 | In right amount to 100 | In right amount to 100 | In right amount to 100 |
| Glycerol | 3 | 5 | 5 | 3 | 3 | 3 |
| Decyl glucoside 1 | --- | --- | 1.25 | 2.5 | 2.5 | 2.5 |
| Disodiumedetate | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| Mixture B | ||||||
| Isopropyl palmitate 2 | 15 | 10 | 15 | 15 | 10 | 8 |
| Mineral oil 3 | 1.75 | 1.0 | 1.75 | 1.75 | ||
| Vaseline | 3.25 | 2.0 | 3.25 | 3.25 | 6 | 5 |
| Docosanol | --- | 0.25 | --- | 0.25 | 0.25 | --- |
| Stearyl alcohol | 1.33 | 0.75 | 1.5 | 0.75 | 0.75 | 1.33 |
| Spermol | 1.33 | 2.50 | 1.5 | 2.5 | 2.5 | 1.33 |
| VARISOFT TA100 4 | 1.0 | 1.5 | 1.25 | 1.5 | 1.5 | 1.5 |
| Stearyl polyoxyethylene ether-21 5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Stearyl polyoxyethylene ether-2 6 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
| Mixture C | ||||||
| The polyethylene beads of oxidation 7 | --- | 1.0 | --- | 1.0 | 1.0 | --- |
| Aromatic | 0.2 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| Menthol | --- | 0.05 | --- | --- | --- | --- |
| Mixture D | ||||||
| Cetyl betaine 8 | 2 | 2 | 2 | 2 | 2 | 2 |
| Sodium lauryl sulfate 9 | 1 | 1 | 1 | 1 | 1 | 1 |
| Glydant Plus | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Mixture E | ||||||
| Ring-type polymethyl siloxane D5 | --- | --- | --- | --- | 5 | --- |
| DC 9040 silicone elastomers 10 | --- | --- | --- | --- | 5 | --- |
| Polydimethylsiloxane (30,000cts) | --- | --- | --- | --- | --- | 3 |
1Buy with trade name Plantaren 2000USP (Cognis Corp)
2Buy with trade name Stepan IPP (Stepan)
3Buy with trade name Hydrobright 1000 (Crompton)
4Buy with trade name Arosurf TA-100 (Degussa)
5Buy with trade name Brij 721 (Uniqema)
6Buy with trade name Brij 72 (Uniqema)
7Buy with trade name A-C Oxidized Polyethylene (Honeywell)
8Buy with trade name Lonzaine SP16 (Lonza)
9Buy with trade name Stepanal WAC (Stepan)
10Derive from Dow Corning Corp. with trade name siloxanes elasticity dispersion
Be prepared as follows the compositions among the embodiment 1 to 6.In a suitable container, under agitation mixture A composition is heated to about 75 ℃.In an independent container, under agitation mixture B composition is heated to about 75 ℃.Under agitation mixture B is joined among the mixture A.Mixture C is joined among mixture A and the B.Described mixture is cooled to about 50 ℃, and under agitation as appropriate, adds mixture E, to guarantee emulsifying.Mixture is cooled to about 35 ℃.In the independent container, the mixture D composition is mixed, and under agitation join in the remaining mixture.
| Composition | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| Mixture A | ||||||
| Carbomer 11 | 0.15 | 0.16 | 0.16 | 0.14 | 0.2 | 0.2 |
| Water | 19.85 | 19.8 | 19.85 | 19.86 | 19.85 | 19.85 |
| Mixture B | ||||||
| Pemulen TR1 | 0.1 | 0.12 | 0.11 | 0.1 | 0.15 | 0.15 |
| Water | 14.9 | 14.85 | 14.9 | 14.9 | 14.9 | 14.9 |
| Mixture C | ||||||
| Sodium hydroxide | 0.065 | 0.065 | 0.65 | 0.65 | 0.07 | 0.07 |
| Water | 2.217 | 2.217 | 2.217 | 2.217 | 2.217 | 2.217 |
| Mixture D | ||||||
| Water | In right amount to 100 | In right amount to 100 | In right amount to 100 | In right amount to 100 | In right amount to 100 | In right amount to 100 |
| Disodiumedetate | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Glycerol | 4 | 4 | 6 | 4 | 4 | 4 |
| Mixture E | ||||||
| Isopropyl palmitate 12 | 10 | 7.5 | 10 | 15 | 15 | 15 |
| Mineral oil 13 | 1.75 | 0.875 | 1.75 | 1.75 | --- | --- |
| Vaseline | 3.25 | 1.625 | 3.25 | 3.25 | 7 | 7 |
| Stearyl alcohol | 0.875 | 0.875 | 0.875 | 0.875 | 1 | 1 |
| Spermol | 0.875 | 0.875 | 0.875 | 0.875 | 1 | 1 |
| Stearic acid | 0.11 | 0.11 | 0.11 | 0.11 | 0.2 | 0.2 |
| Stearyl polyoxyethylene ether-21 14 | 0.5 | 0.5 | 0.5 | 0.5 | 0.7 | 0.7 |
| Stearyl polyoxyethylene ether-2 15 | 0.25 | 0.25 | 0.25 | 0.25 | 0.4 | 0.4 |
| Methyl parahydroxybenzoate | 0.2 | 0.2 | 0.2 | 0.2 | --- | --- |
| Propyl p-hydroxybenzoate | 0.15 | 0.15 | 0.15 | 0.15 | --- | --- |
| Polydimethylsiloxane (30,000cts) | --- | --- | --- | --- | --- | 2 |
| DMDM Hydantoin/IPBC 16 | --- | --- | --- | --- | 0.3 | 0.3 |
| Decyl glucoside 17 | 0.48 | 0.48 | 0.48 | 0.48 | --- | --- |
| Aromatic | 0.15 | 0.15 | 0.15 | 0.15 | 0.25 | 0.25 |
11Buy with trade name Carbopol 954 (BF Goodrich).
12Buy with trade name Stepan IPP (Stepan).
13Buy with trade name Hydrobright 1000 (Crompton).
14Buy with trade name Brij 721 (Uniqema).
15Buy with trade name Brij 72 (Uniqema).
16Buy with trade name Glydant Plus (Lonza).
17Buy with trade name Plantaren 2000USP (Cognis Corp).
Be prepared as follows the compositions among the embodiment 7 to 12.Stir the mixture A, B and C are until they are distributed in the water.In a suitable container, after polymer and sodium hydroxide are distributed in the water, mixture A, B and C are joined in the mixture D.When stirring with paddle, with this mixture heated to 70 ℃ to 75 ℃.Oil-phase component is joined in the suitable container together, and when stirring with paddle, with this mixture heated to 75 ℃ to 80 ℃.Remove thermal source, and pre-composition is joined in the oil phase, and stir oil phase with paddle simultaneously, until it is even.Continue to stir, until temperature is down to 45 ℃ to 50 ℃, add aromatic, GlydantPlus and decyl glucoside, and continue to stir with paddle.When stirring with paddle, this batch materials is cooled to 35 ℃ to-40 ℃, guarantee that this batch materials is consistent and even.This batch materials is transferred to container in order to storing.
| Composition | Embodiment 13 | Embodiment 14 | Embodiment 15 |
| Isopropyl palmitate 18 | 15 | 15 | 15 |
| Mineral oil 19 | 1.75 | 1.75 | 1.75 |
| Vaseline 20 | 3.25 | 3.25 | 3.25 |
| INCROQUAT TMC-80 ECONOL TM22 21 | 2.25 | --- | 2.25 |
| Isopropyl alcohol | 0.598 | --- | 0.598 |
| The amino diemethylamine of stearoyl 22 | --- | 2 | --- |
| Pidolidone 23 | --- | 0.64 | --- |
| Spermol 24 | 1.86 | 2 | 1.86 |
| Stearyl alcohol 25 | 4.64 | 4.5 | 4.64 |
| Benzylalcohol 26 | 0.4 | 0.4 | 0.4 |
| Methylchloroisothiazandnone/Methylisothiazolinone 27 | 0.0005 | 0.0005 | 0.0005 |
| Spice | 0.5 | 0.25 | 0.5 |
| NaOH | 0.014 | --- | 0.014 |
| Pantothenylol 28 | 0.05 | 0.05 | 0.05 |
| Panthenyl ethyl ether 29 | 0.05 | 0.05 | 0.05 |
| Disodiumedetate 30 | 0.127 | --- | 0.127 |
| Ethylenediaminetetraacetic acid 31 | --- | 0.1 | --- |
| Polyoxyethylene (12) tridecyl ether 32 | --- | --- | 0.1 |
| Deionized water | In right amount to 100% |
[0154] 18Kessco IPP is available from Stepan Chemicals.
19Hydrobrite 1000 PO are available from Crompton Corporation.
20Super White Protopet is available from Witco Chemicals.
21Genamin KDMP is available from Clariant.
22Lexamine S-13 is available from Inolex.
23Available from Ajinmoto.
24CO-1695F is available from P﹠amp; G Chemicals.
25CO-1897F is available from P﹠amp; G Chemicals.
26Available from Charkit Chemicals.
27Kathon CG is available from Rohm﹠amp; Haas.
28Available from Roche.
29Available from Roche.
30Dissolvine NA2-S is available from Akzo Nobel.
31Dissolvine Z is available from Akzo Nobel.
32Renex 30, available from Uniquema Americas.
Be prepared as follows the compositions among the embodiment 13 to 15.Deionized water is heated to 85 ℃.Cationic surfactant and hard fat compounds of group are blended in the water.Add isopropyl palmitate, mineral oil and vaseline.Make water be maintained at about 85 ℃ temperature, until described component homogenize and do not observe solid.Described mixture is cooled to about 55 ℃ and remain under this temperature, to form gel-type vehicle.Continue to stir during this period of time in, make described gel-type vehicle be maintained at about 50 ℃, to guarantee homogenize.When comprising, also can add at this moment other annexing ingredient, such as spice, rheology modifier and antiseptic.After the homogenize, be cooled to room temperature.
When any implication of term in any implication of term in this written document record or definition and the document that is incorporated herein by reference or define when conflicting, will be as the criterion with implication or the definition of giving term in this written document record.
Should be appreciated that each higher limit that provides in this manual will comprise each lower limit, namely as this lower limit clear and definite expression is arranged all also in the present note.Each lower limit that provides in this specification will comprise each higher limit, at this paper clear and definite expression be arranged all also as this higher limit.Each numerical range that provides in this specification will comprise all narrower numerical rangies that are contained in this broader numerical, at this paper clear and definite expression be arranged also as this narrower numerical range.
Although illustrated and described the present invention with specific embodiments, it will be apparent to those skilled in the art that many other variations and modifications may be made in the case of without departing from the spirit and scope of protection of the present invention.Therefore, in additional claims, comprise all such changes and modifications that belong in the scope of the invention consciously.
Claims (7)
1. Cleasing compositions, described compositions comprises based on composition weight:
(a) the high-modulus lipoid of 1-10wt%, this high-modulus lipoid are the vaseline with lipoid modulus value of at least 50;
(b) aliphatic ester of 8-40wt%, this aliphatic ester are selected from isopropyl palmitate, IPIS, Dermol DIPS and their mixture;
(c) water of 20wt% at least; And
(d) non-ionic surface active agent, this non-ionic surface active agent have 8 to 20 average HLB;
(e) less than the solvent that is selected from the group that is formed by following material of 50wt%: ethanol, isopropyl alcohol and their mixture.
2. Cleasing compositions as claimed in claim 1, wherein said compositions also comprises hydrophobic structure reagent.
3. Cleasing compositions as claimed in claim 2, wherein said hydrophobic structure reagent is selected from the group that is comprised of following material: spermol, stearyl alcohol, docosanol and their mixture.
4. Cleasing compositions as claimed in claim 1, wherein said non-ionic surface active agent have 10 to 16 average HLB and the alkyl chain length of 8 to 14 carbon atoms.
5. Cleasing compositions as claimed in claim 1, wherein said compositions also comprises cationic surfactant.
6. Cleasing compositions as claimed in claim 5, wherein said cationic surfactant is selected from the group that is comprised of following material: VARISOFT TA100, INCROQUAT TMC-80 ECONOL TM22, the amino diemethylamine of stearoyl and their mixture.
7. the method for a cleaning skin said method comprising the steps of:
(a) skin is contacted with each compositions among the claim 1-6; With
(b) water washes described skin or with the described skin of substrate wiping.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US65868705P | 2005-03-04 | 2005-03-04 | |
| US60/658,687 | 2005-03-04 | ||
| US70096005P | 2005-07-20 | 2005-07-20 | |
| US60/700,960 | 2005-07-20 | ||
| PCT/US2006/008006 WO2006096677A2 (en) | 2005-03-04 | 2006-03-03 | Rinse-off or wipe-off skin cleansing compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101132834A CN101132834A (en) | 2008-02-27 |
| CN101132834B true CN101132834B (en) | 2013-03-13 |
Family
ID=38943728
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200680001463 Pending CN101090752A (en) | 2005-03-04 | 2006-03-03 | Rinse-off or wipe-off skin cleansing compositions |
| CN200680007132.0A Active CN101132834B (en) | 2005-03-04 | 2006-03-03 | Rinse-off or wipe-off skin cleansing compositions |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200680001463 Pending CN101090752A (en) | 2005-03-04 | 2006-03-03 | Rinse-off or wipe-off skin cleansing compositions |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN101090752A (en) |
| ES (1) | ES2358920T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4916568B2 (en) * | 2010-08-13 | 2012-04-11 | 株式会社黒龍堂 | Mascara remover |
| CN102008418B (en) * | 2010-12-10 | 2012-01-11 | 中国人民武装警察部队后勤学院 | Skin cleaning solution |
| DE102011085509A1 (en) * | 2011-10-31 | 2013-05-02 | Beiersdorf Ag | Fixation of perfume on wet skin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004065536A1 (en) * | 2003-01-17 | 2004-08-05 | Basf Aktiengesellschaft | Cosmetic compositions comprising alkyl glycol alkoxylates or diglycol alkoxylates |
-
2006
- 2006-03-03 ES ES06737209T patent/ES2358920T3/en active Active
- 2006-03-03 CN CN 200680001463 patent/CN101090752A/en active Pending
- 2006-03-03 CN CN200680007132.0A patent/CN101132834B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004065536A1 (en) * | 2003-01-17 | 2004-08-05 | Basf Aktiengesellschaft | Cosmetic compositions comprising alkyl glycol alkoxylates or diglycol alkoxylates |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2358920T3 (en) | 2011-05-16 |
| CN101090752A (en) | 2007-12-19 |
| CN101132834A (en) | 2008-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8563491B2 (en) | Methods of cleansing skin and rinse-off or wipe-off compositions therefor | |
| CN102088949B (en) | Ester compounds for use in personal care products | |
| KR101830943B1 (en) | Water-releasing cosmetic composition | |
| CN103200926B (en) | Acrylate copolymer thickener | |
| US6287580B1 (en) | Cosmetic compositions with self-warming component | |
| CN101048200B (en) | Personal care compositions with silicones and dihydroxypropyl trialkyl ammonium salts | |
| US7704517B2 (en) | Topical cosmetic composition containing hybrid silicone composite powder | |
| CN101132756B (en) | Personal care composition containing hydrophobically modified polymers | |
| US6503517B1 (en) | Cosmetic compositions with menthol | |
| US20070189989A1 (en) | Cosmetic compositions and methods of making and using the compositions | |
| Azeem et al. | Emerging role of microemulsions in cosmetics | |
| CN104736131A (en) | Cosmetic composition comprising bi-modal emulsion | |
| US20080102050A1 (en) | Water-based skin care composition with polyalkylsilsesquioxane powder emulsion and method for making the same | |
| MX2007004063A (en) | Method of providing lubricious surfaces. | |
| CN101217929A (en) | Rheology improvement for a personal care composition | |
| CA2524322A1 (en) | Wet skin treatment compositions comprising gel-networks | |
| CN102083409B (en) | Personal care compositions having improved compatibility and providing improved sun protection | |
| KR101137241B1 (en) | Clear oil-in-water emulsions | |
| CN103260594A (en) | Leave-on nonsolid skin conditioning compositions containing 12-ydroxystearic acid | |
| CN102946850A (en) | Skin improving dermo-cosmetics | |
| US20040234478A1 (en) | Personal care compositions containing a silicone elastomer | |
| CN101132834B (en) | Rinse-off or wipe-off skin cleansing compositions | |
| JP2003520205A (en) | Cosmetic composition | |
| AU2004238310A1 (en) | Personal care compositions containing a silicone elastomer and a dispersed oil phase | |
| CN101511332A (en) | Cosmetic compositions with ethylene brassylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1116117 Country of ref document: HK |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1116117 Country of ref document: HK |