CN1870970A - Hair care composition - Google Patents
Hair care composition Download PDFInfo
- Publication number
- CN1870970A CN1870970A CNA2004800313674A CN200480031367A CN1870970A CN 1870970 A CN1870970 A CN 1870970A CN A2004800313674 A CNA2004800313674 A CN A2004800313674A CN 200480031367 A CN200480031367 A CN 200480031367A CN 1870970 A CN1870970 A CN 1870970A
- Authority
- CN
- China
- Prior art keywords
- compositions
- weight
- hair
- composition
- alkyl
- 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.)
- Granted
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/927—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of insects, e.g. shellac
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/006—Antidandruff preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
Abstract
Aqueous hair conditioning and cleansing compositions comprising both beeswax and a silicone polymer to provide improved straightness and manageability for hair from compositions which have improved stability to phase separation of ingredients.
Description
Invention field
The present invention relates to the improvement of Wo 2008069000.This compositions can be improved and sends out or do the situation of sending out wet, and this also is a purpose of this compositions, and this improvement refers to such as the easy combing of hair, do not tangle, level and smooth and submissive performance.Except that the main purpose (for example being used for shampoo, approved product or hair dyeing system) of compositions, opsonic action also is useful, perhaps it can be used as the main purpose of compositions, and the conditioner that need rinse well after for example being used for maybe can be stayed conditioner and the mousse on the hair.The present invention be more particularly directed to conditioner shampoo or shower gels, be used for hair washing, degrease and decontamination, the present invention also provides the hair conditioning benefit.
Background technology
There is different hobbies in the consumer of different background, culture and ethnic derivation for hair conditioning.Hair style and fashion consider also can to cause the change of the hair condition expected.One class consumer wishes hair easier combing of direct sum after processing: this just means, and hair volume reduces, still less fluffy and arrangement mutually better.
One of approach that realizes this point is the viscosity conditioning materials of smearing on hair such as the heavy polymer of for example siloxanes (polydialkysiloxane) or hydrocarbon ils or wax.Although in compositions, exist this material can obtain that hair volume reduces, the feature of expectation still less fluffy and that arrange mutually better, also can bring sensorial negative issue, it can make hair feel that coating, greasy and be clamminess is arranged.
In addition, the water-insoluble conditioning materials generally can be suspended in compositions less than granule or the drop of 50 μ m usually as diameter, especially in the shampoo composite.This is for conditioning granule or drop are deposited on the hair, and guarantees to keep relative stability during the product stock, and component separating can not take place.In order to obtain the conditioning materials suspension, sometimes shampoo is designed to have the shear thinning viscosity profile, make their thickness under low shearing rate, thereby conditioning materials is suspended, but not too sticking under the higher shear rate, shampoo can be poured out from bottle.The compositions desired viscosity profile can realize by using such as the viscosity modifier of polymer, but also can realize by the micellar phase structure of regulating shampoo with electrolyte.Can be during long term storage interact such as some viscosity conditioning materials of mineral oil and wax and ester oil, cause the structural stability forfeiture, and finally cause the physical separation of each composition with the phase structure of shampoo.
Have now found that,, can obtain stretching and conditioning effect navigability, reduce problem negative, that apply sensation and toughness simultaneously by in the aqueous hair-treatment composition, being used in combination high-viscosity silicone polymer and Cera Flava.Find in addition, Cera Flava and siloxane polymer in conjunction with reduced compositions, particularly shampoo that surfactant constitutes and with after composition isolating problem between the storage life in the conditioner composition that need rinse well.
Summary of the invention
First aspect the invention provides the aqueous Wo 2008069000, and it comprises:
A) account for the Cera Flava of total composition 0.1-8 weight %;
B) account for the siloxane polymer of total composition 0.01-10 weight %, the viscosity of this polymer under 0.01Hz and 25 ℃ is at least 80,000mm
2/ s.
Second aspect the present invention relates to the preparation method of Haircare composition discussed above, is included in the step of first emulsified beeswax before joining in the compositions.
The 3rd aspect the present invention relates to the purposes that compositions discussed above is used for conditioning hair.
The present invention describes in detail
" water-insoluble " refers to that the dissolubility of this material in 25 ℃ of water is 0.1 weight % or littler of water." fixedness " refers to that the vapour pressure of this material under 25 ℃ is lower than 1000Pa.
Viscosity unless otherwise indicated all refers to dynamic viscosity.Available cone and plate rheometer is at 25 ℃ and 0.01s
-1Shear rate is measured down.
Alleged granule is generalized granule in this description, refers to that this material exists with unpack format.If material is a liquid, then granule is exactly the drop form.
Particle size is fit to use such as Malvern
TMThe instrument of Mastersizer is measured by laser scattering method.Particle diameter intermediate value particle diameter (D
50) express.
Waterborne compositions
Compositions according to the present invention comprises water.Suitable compositions comprises 60% or more according to the present invention, and preferred 65% or more, more preferably 70 weight % or more water.
Cera Flava
Cera Flava is by the glandular secretion of Apis under its abdominal part.Apis makes up Nidus Vespae with it.Wax can be used as the Mel results and purified commercial side-product obtains.Cera Flava is in the present invention preferably as intermediate value (D
50) particle diameter is 50 μ m or littler, preferred 20 μ m or littler, more preferably 10 μ m or littler, even more preferably 1 μ m or littler granule use with particulate form.
Mellisic content is the 0.1-8 weight % of total composition, preferred 0.2-5 weight %, more preferably 0.4-3 weight %, most preferably 0.6-2 weight %.
Cera Flava can be pre-formed emulsion or dispersion before adding remaining compositions.Preferably Cera Flava is pre-formed emulsion.
The method for optimizing that Cera Flava is mixed in the compositions comprises that step (i) will not contain mellisic compositions and be heated to 65 ℃ or higher, preferred 75 ℃ or higher temperature, (ii) melt Cera Flava, (iii) Cera Flava being combined stirring simultaneously with all the other compositionss and (iv) composition cools is arrived room temperature, generally is 25 ℃.
It is shocking that if then carry out this method, but Cera Flava need not just self emulsifying of vigorous stirring.
Mixing mellisic method for optimizing as selection in compositions may further comprise the steps:
I) at 65 ℃ or higher, preferred 70 ℃ or higher, the more preferably aqueous solution or the dispersion of preparation emulsifying agent under 80 ℃ or the higher temperature;
Ii) at 65 ℃ or higher, preferred 70 ℃ or higher, more preferably 80 ℃ or higher temperature preparation fusion Cera Flava down;
Iii) with step (i) and liquid mixing (ii) and homogenize;
Iv) with dispersions obtained cool to room temperature while gentle agitation;
V) in basic components, add the gained emulsion.
Emulsifying agent can be any suitable surfactant, but the admixture of preferred cationic surfactant and aliphatic alcohol, it is 1 that its content should make emulsifying agent and mellisic weight ratio: 100-1: 10, preferred 1: 50-1: 20.The preferred solvent system is that weight ratio is 1: 5-5: 1 cetyl trimethyl ammonium chloride and 16/octadecanol.
The weight ratio of Cera Flava and siloxane polymer preferred 4 in the compositions: 1-1: 2, more preferably 2: 1-1: 1.
Siloxane polymer
The suitable siloxane polymer viscosity under 25 ℃ that measure under the shear rate of 0.01Hz at least is 80 in the present composition, 000mm
2/ s, preferably at least 1,000,000mm
2/ s, more preferably at least 10,000,000mm
2/ s, even more preferably greater than 100,000,000mm
2/ s.
Siloxane polymer can be based on any suitable poly-diakyl or poly-diaromatic siloxane, but is preferably based on polydimethylsiloxane.Siloxane polymer is preferably water-insoluble and fixedness.
Suitable is that siloxane polymer is as median diameter (D
50) be 50 μ m or littler, preferred 20 μ m or littler, more preferably 10 μ m or littler, even more preferably 1 μ m or littler discrete particle are present in the compositions of the present invention.
In the embodiment of the present invention as selection, siloxane polymer can be the microemulsion form of granule median diameter less than 0.15 μ m.
Preferably siloxane polymer can be used as in the preform emulsion adding remaining set compound.So just need not the compositions high shear mixing, so that in compositions, form the silicone polymer particles of suitable dimension.
It is most preferred that siloxane polymer is to have the divinyl dimethicone of following structure and the copolymer of dimethicone:
Wherein x, y and z are the integers greater than 1.Particularly preferably be this copolymer at 0.01s
-1Has greater than 100,000 000mm under shear rate and 25 ℃
2The viscosity of/s.Suitable commercial material as the water-based emulsion supply is Dow Corning HMW 2220.
The content that siloxane polymer is suitable is the 0.01-10 weight % of compositions, preferred 0.1-5 weight %, more preferably 0.5-4 weight %.
The aqueous Wo 2008069000
The suitable groups compound that is used for the present invention's application comprises mousse, washing liquid and emulsifiable paste.The hair conditioner that need rinse well after preferably using.Particularly preferred compositions is to clean shampoo or shower gels.
Shampoo
One concrete aspect, compositions of the present invention is cleaning shampoo or the shower gels that further contains one or more clean surface activating agents of the acceptable and suitable partial smearing hair of cosmetics.
The clean surface activating agent
Suitable clean surface activating agent (they can use separately or be used in combination) is selected from anion, nonionic, both sexes and zwitterionic surfactant and composition thereof.The mixture of preferred anionic surfactant and amphoteric surfactant.
Anion clean surface activating agent
Shampoo composite of the present invention generally comprises one or more anion clean surface activating agents of the acceptable and suitable partial smearing hair of cosmetics.
The example of suitable anion clean surface activating agent be alkyl sulfate, alkyl ether sulfate, alkylaryl sulfonate, alkanoyl isethionate, alkyl succinate, alkyl sulfo succinate, N-alkyl sarcosine salt, alkylphosphonic, alkyl ether phosphate, alkyl ether carboxy acid salt and alpha-alkene sulfonate, particularly their sodium, magnesium, ammonium and-, two-and three-ethanolamine salt.Alkyl and acyl group have 8-18 carbon atom usually, and can be undersaturated.But alkylether sulfonate, alkyl ether phosphate and alkyl ether carboxy acid salt's per molecule contain 1-10 oxirane or propylene oxide unit.
The typical anion clean surface activating agent that is used for shampoo composite of the present invention comprises oleoyl sodium succinate, lauryl sulfo-ammonium succinate, ammonium lauryl sulfate, dodecylbenzene sodium sulfonate, triethanolamine dodecyl benzene sulfonate, cocoyl hydroxyethyl sulfonate, lauryl hydroxyethyl sulfonate and N-sodium lauryl sarcosinate.Most preferred anion surfactant is sodium lauryl sulfate, sodium laureth sulfate (n) EO (wherein n is 1-3), ammonium lauryl sulfate and Zetesol AP (n) EO (wherein n is 1-3).
The mixture of any above-mentioned anion clean surface activating agent also is suitable.
The total amount of anion clean surface activating agent is generally the 0.5-45% of compositions in the shampoo composite of the present invention, preferred 1.5-35%, more preferably 5-20 weight %.
Cosurfactant
Said composition can comprise cosurfactant, to give compositions aesthetics, physics or cleaning performance.
Preferred examples is both sexes or zwitterionic surfactant, and its content can be the about 8 weight % of 0-, preferred 1-4 weight %.
The example of both sexes and zwitterionic surfactant comprises alkyl amine oxide, alkyl betaine, alkylamide propyl-betaine, alkyl sulfobetaines (sulfobetaines), alkyl glycinate, alkyl carboxyl glycinate, alkyl both sexes propionate, alkyl both sexes glycinate, alkylamide propyl hydroxyl sulfo betaine, acyl taurine salt and acyl glutamate, and wherein alkyl and acyl group have 8-19 carbon atom.The typical both sexes and the zwitterionic surfactant that are used for shampoo of the present invention comprise lauryl amine oxide, coco dimethyl sulfo-CAB, preferably lauryl betaine, cocamido propyl betaine and cocos nucifera oil both sexes sodium propionate.
Another preferred examples is a non-ionic surface active agent, and its content can be the 0-8 weight % of compositions, preferred 2-5 weight %.
For example, can be included in the condensation product that representative ionic surfactant pack in the shampoo composite of the present invention is drawn together aliphatic series (C8-C18) uncle or secondary straight or branched alcohol or phenol and is generally the alkylene oxide of oxirane, and have 6-30 ethylene oxide group usually.
Other representative ionic surfactant pack draw together one-or two-alkyl chain triacontanol amide.The example comprises cocos nucifera oil one-or two-glycollic amide and cocos nucifera oil one isopropanol amide.
Other non-ionic surface active agents that can be included in the shampoo composite of the present invention are alkyl polyglycoside (APGs).Generally speaking, APG is the APG that comprises the alkyl that (not necessarily passing through abutment) be connected with the block of one or several glycosyl.Preferred APGs is defined by following general formula:
RO-(G)
n
Wherein R is saturated or undersaturated branched-chain or straight-chain alkyl, and G is a glycosyl.R can represent the mean alkyl chain length from about C5 to about C20.The about C8 of preferred R representative is to the mean alkyl chain length of about C12.Most preferred R value is between about 9.5 to about 10.5.G can be selected from C5 or C6 monosaccharide residue, preferably glycosides.The group of the optional self-contained glucose of G, xylose, lactose, fructose, mannose and derivant thereof.Preferred G is a glucose.
Polymerization degree n can have about 1 to about 10 or bigger value.Preferred n value is between about 1.1 to about 2.Most preferred n value about 1.3 to about 1.5 scopes.
It is commercially available being used for suitable alkyl polyglycoside of the present invention, for example comprises being labeled as: available from the Oramix NS10 of Seppic, available from the Plantaren 1200 of Henkel and the material of Plantaren2000.
The sugared deutero-ionic surfactant pack of other that can comprise in the present composition is drawn together C10-C18 N-alkyl (C1-C6) the poly-hydroxy fatty acid amide of describing among for example WO 9206154 and US 5194639 such as C12-C18 N-methyl glucose amide, and such as the N-alkoxyl poly-hydroxy fatty acid amide of C10-C18N-(3-methoxy-propyl) glucamide.
Compositions of the present invention also can not necessarily comprise one or more cation cosurfactants, and its content is the 0.01-10 weight % of compositions, more preferably 0.05-5 weight %, most preferably 0.05-2 weight %.
The total amount of clean surface activating agent in the present composition (comprising any cosurfactant and/or any emulsifying agent) is generally the 1-25 weight % of compositions, preferred 2-20 weight %, more preferably 5-17 weight %.
Preferred clean surface activating agent admixture is the combination of Zetesol AP, ammonium lauryl sulfate, PEG 5 coconut oleoyl amines and coconut oleoyl amine MEA (CTFA title).
The cationic deposition polymer
If the median particle diameter of Cera Flava or siloxane polymer is 10 μ m or littler, cationic polymer is a preferred composition in the shampoo composite of the present invention, is used to strengthen the conditioning performance of shampoo.
Cationic polymer can be homopolymer or be formed by the monomer of two or more types.The molecular weight of polymer is generally 5,000-10, and 000,000 dalton, generally at least 10,000, preferred 100,000-2,000,000.This polymer will have the cation nitrogen-containing group such as quaternary ammonium or protonated amino or their mixture.
The cationic nitrogenous group is present on the total monomer units part of cationic polymer as substituent group usually.Therefore when this polymer was not homopolymer, it can contain basic non-cationic monomeric unit at interval.This polymer is described in CTFA Cosmetic IngredientDirectory, in the 3rd edition.Cation should make the cationic charge density of polymer in claimed range with the selection of the ratio of non-cationic monomeric unit.
Suitable cationic conditioning polymer comprise the vinyl monomer that for example has cationic amine or quaternary ammonium degree of functionality with such as the water solublity of (methyl) acrylamide, alkyl and dialkyl group (methyl) acrylamide, (methyl) alkyl acrylate, vinyl caprolactone and ethenyl pyrrolidone basic monomeric copolymer at interval.The monomer that alkyl and dialkyl group replace preferably has the C1-C7 alkyl, more preferably the C1-C3 alkyl.Other suitable interval bases comprise vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol.
Cationic amine can be primary amine, secondary amine or tertiary amine, depends on the concrete kind and the pH value of compositions.Usually preferred secondary amine and tertiary amine, particularly tertiary amine.
Vinyl monomer that amine replaces and amine can amine the form polymerization, then by the quaternized ammonium that changes into.
Cationic conditioning polymer can comprise derived from amine-and/or the monomer of quaternary ammonium-substituted and/or mixture of the monomeric monomeric unit of compatible spacer base.
Suitable cationic conditioning polymer for example comprises:
The copolymer of-1-vinyl-2-pyrrolidine and 1-vinyl-3-methyl-imidazolium salts (for example chloride salt), industrial by Cosmetic, Toiletry, and FragranceAssociation (CTFA) is called Polyquaternium-16.(Parsippany, NJ USA) are purchased with LUVIQUAT trade mark (for example LUVIQUAT FC 370) this material from BASFWyandotte Corp.;
The copolymer of-1-vinyl-2-pyrrolidine and dimethylaminoethyl acrylate methyl base aminoethyl ester, industrial (CTFA) is called Polyquaternium-11.(Wayne, NJ USA) are purchased with GAFQUAT trade mark (for example GAFQUAT 755N) this material from Gaf Corporation;
The polymer of-cation diallyl quaternary ammonium, comprise for example copolymer of dimethyl diallyl ammonium chloride homopolymer and acrylamide and dimethyl diallyl ammonium chloride, industrial (CTFA) is called Polyquaternium 6 and Polyquaternium 7;
-have an inorganic acid salt (seeing the description among the US 4009256) of the amino-Arrcostab of the homopolymer of unsaturated carboxylic acid of 3-5 carbon atom and copolymer;
-PAMC (seeing the description among the WO 95/22311).
Adoptable other cationic conditioning polymers comprise the cationic polysaccharide polymer such as cationic cellulose derivative, cationic starch derivative and cation guar gum derivant.Suitable is that this cationic polysaccharide polymer has the charge density of 0.1-4meq/g.
Be suitable for cationic polysaccharide polymer in the present composition and comprise those of following general formula:
A-O-[R-N
+(R
1)(R
2)(R
3)X
-]
Wherein: A is the anhydrous grape saccharide residue such as starch or cellulose anhydrous grape saccharide residue.R is alkylidene, oxyalkylene, polyoxy alkylidene or hydroxy alkylidene, or their combination.R
1, R
2And R
3Represent alkyl, aryl, alkaryl, aralkyl, alkoxyalkyl or alkoxy aryl independently, each base contains about 18 carbon atoms at most.The total carbon atom number of each cationic moiety (is R
1, R
2And R
3In the carbon atom sum) preferred about 20 or still less, and X is an anionic counter-ion.
Cationic cellulose can be from Amerchol Corp. (Edison, NJ, USA) conduct obtains with the salt of the epoxide reactive hydroxyethyl-cellulose of trimethyl ammonium replacement in PolymerJR (trade mark) and LR (trade mark) series of polymers, and industrial (CTFA) is called Polyquaternium10.Another kind of cationic cellulose comprises the polymeric quaternary ammonium salts of the epoxide reactive hydroxyethyl-cellulose that replaces with the lauryl dimethyl ammonium, and industrial (CTFA) is called Polyquaternium24.(Edison, NJ USA) obtain with trade mark PolymerLM-200 these materials from Amerchol Corp..
Other suitable cationic polysaccharide polymer comprise the cellulose ether (for example describing among the US3962418) that contains quaternary nitrogen, and the copolymer of etherified cellulose and starch (for example describing among the US 3958581).
Available specially suitable cationic polysaccharide polymer type is the cation guar gum derivant such as Rhaball Gum CG-M 8M (being purchased its JAGUAR trade mark series from Rhone-Poulenc).
Example be have low cation group substitution value and full-bodied JAGUAR C13S, have medium substitution value and low viscous JAGUAR C15, JAGUAR C17 (high substituted degree, high viscosity), as the JAGUAR C16 that contains the hydroxypropylation cation guar gum derivant of low content substituent group and cationic quaternary ammonium base, and as the JAGUAR 162 of the high grade of transparency, moderately viscous low degree of substitution guar gum.
The preferred cation conditioning polymer is selected from cationic cellulose and cation guar gum derivant.Particularly preferred cationic polymer is JAGUAR C13S, JAGUAR C15, JAGUARC17, JAGUAR C16 and JAGUAR C162.
The content of cationic conditioning polymer is generally the 0.01-5 weight % of compositions in the present composition, preferred 0.02-1 weight %, more preferably 0.04-0.5 weight %.
With after the conditioner composition that need rinse well
The present invention is maybe can stay care composition on the hair as what need rinse well after the usefulness as the embodiment of selecting.
Contain preferably according to the conditioner composition on the hair maybe can stayed that need rinse well after the usefulness of the present invention that cosmetics can be accepted and one or more conditioning surfactants of suitable partial smearing hair.
Conditioning surfactant
Suitable conditioning surfactant is selected from cationic surfactant, can use separately or use as mixture.Positively charged amino or quaternary ammonium hydrophilic segment when can be used for cationic surfactant in the present composition and containing in being dissolved in waterborne compositions of the present invention.
The example of suitable cationic surfactants is those of following general formula correspondence:
[N(R
1)(R
2)(R
3)(R
4)]
+(X)
-
R wherein
1, R
2, R
3And R
4Be independently selected from (a) 1-22 carbon atom aliphatic group, or (b) aromatic group, alkoxyl, polyoxy alkylidene, alkyl amido, hydroxyalkyl, alkanoyl alkyl (alkoylalkyl), aryl or the alkaryl of maximum 22 carbon atoms; X is such as the salifiable anion of shape that is selected from halogen (for example chloride, bromide), acetate, citrate, lactate, glycol hydrochlorate, phosphate, nitrate, sulfate and alkylsurfuric acid alkali.
Aliphatic group de-carbon and hydrogen atom also can contain ehter bond outward and such as other groups of amine groups.Than the aliphatic group of long-chain, for example about twelve carbon atom or higher group can be saturated or undersaturated.
The preferred cationic surfactant that is used for conditioner composition of the present invention is R wherein
1Have C16-C22 alkyl chain length and R
2, R
3And R
4Have 2 or what is called one alkyl quaternary ammonium compound of carbon atom still less.
Other preferred cationic surfactants are R wherein
1And R
2Have C16-C22 alkyl chain length and R independently
3And R
4Have 2 or the so-called dialkyl quats chemical compound of carbon atom still less.
The example of suitable cationic surfactants comprises quaternary ammonium compound, particularly the QAE chemical compound.
Preferred quaternary ammonium compound comprises cetyl trimethyl ammonium chloride Shan Yu base trimethyl ammonium chloride (BTAC); cetyl pyridinium chloride ; tetramethyl ammonium chloride; tetraethylammonium chloride; the octyl group trimethyl ammonium chloride; Dodecyl trimethyl ammonium chloride; hexadecyltrimethylammonium chloride; the octyldimethyl benzyl ammonium chloride; the decyl dimethyl benzyl ammonium chloride; the stearyl dimethyl benzyl ammonium chloride; the docosyl alkyl dimethyl ammonium chloride; the octacosyl alkyl dimethyl ammonium chloride; the Adeps Bovis seu Bubali trimethyl ammonium chloride; the cocos nucifera oil trimethyl ammonium chloride; PEG-2 oleoyl ammonium chloride and their salt, wherein chloride is by halogen (for example bromide); acetate; citrate; lactate; the glycol hydrochlorate; phosphate; nitrate; sulfate or alkyl sulfate replace.Other suitable cationic surfactants comprise that the CTFA name is called the material of Quaternium-5, Quaternium-31 and Quaternium-18.The mixture of any above-mentioned material also is suitable for.The cetyl trimethyl ammonium chloride that the Arquad16/29 that can be used for useful especially quaternary ammonium cation surfactant in the hair conditioner of the present invention and be for example to provide with GENAMIN CTAC and Akzo Nobel available from Hoechst Celanese is purchased, and the Genamin KDM-P De Shan Yu base trimethyl ammonium chloride (BTAC) that provides such as Clariant.
Another kind of suitable cationic conditioning surfactant is two alkanoyl alkyl dimethyl ammonium halides.This examples for compounds is CTFA title two palmityl ethyl alkyl dimethyl ammonium chlorides.
Other suitable cationic systems be used in combination with acid with provide cation type primary, the second month in a season and uncle's fatty amine.The alkyl of this amine preferably has 12-22 carbon atom, and can be substituted or not be substituted.
Useful especially is uncle's fatty amine that acylamino-replaces, and particularly has the tertiary amine of a C12-C22 alkyl or alkenyl chain.Here this amine of Cai Yonging comprises octadecannamide propyl group dimethylamine, octadecannamide propyl group diethylamine, octadecannamide ethyl diethylamine, octadecannamide ethyl dimethylamine, palmityl aminopropyl dimethylamine, palmityl aminopropyl diethylamine, palmityl aminoethyl diethylamine, palmityl aminoethyl dimethylamine Shan Yu acyl aminopropyl dimethylamine Shan Yu acyl aminopropyl diethylamine Shan Yu acyl aminoethyl diethylamine Shan Yu acyl aminoethyl dimethylamine, Semen arachidis hypogaeae acyl aminopropyl dimethylamine, Semen arachidis hypogaeae acyl aminopropyl diethylamine, Semen arachidis hypogaeae acyl aminoethyl diethylamine, Semen arachidis hypogaeae acyl aminoethyl dimethylamine, the diethyl aminoethyl stearmide.
Also available dimethyl stearylamine, dimethyl Semen sojae atricolor amine, Semen sojae atricolor amine, Semen Myristicae amine, tridecyl amine, ethyl stearmide, N-Adeps Bovis seu Bubali propanediamine, ethoxylation (using 5mol oxirane) stearmide, dihydroxy ethyl stearmide and Semen arachidis hypogaeae Ji Shan Yu amine.
As mentioned above, these amine are used in combination with acid usually, so that cation type to be provided.Here the preferred acid of adopting comprises L-glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, tartaric acid, citric acid, L-glutamic acid hydrochloride, and their mixture; More preferably L-glutamic acid, lactic acid, citric acid.Wherein can be used among the US 4275055 that cationic amine surfactant of the present invention is disclosed in Nachtigal of issuing on June 23rd, 1981 etc.
But protonated amines with from the H of acid
+Mol ratio be preferably about 1: 0.3-1: 1.2, more preferably from about 1: about 1: 1.1 of 0.5-.
In conditioner of the present invention, the content of cationic surfactant is preferably the 0.01-10 weight % of total composition, more preferably 0.05-5 weight %, most preferably 0.1-4 weight %.
Fat material
Conditioner composition of the present invention preferably also contains fat material.Believe in care composition, fat material is used in combination with cationic surfactant useful especially because will form so wherein disperseed cationic surfactant layer structure mutually or liquid crystalline phase.
" fat material " refers to aliphatic alcohol, alkoxy fatty alcohols, fatty acid or their mixture.Preferably the alkyl chain of fat material is complete saturated.
Representative fat material comprises 8-22, more preferably 16-22 carbon atom.The example of suitable aliphatic alcohol comprises spermol, octadecanol and their mixture.The use of these materials also is useful giving on the overall conditioning performance of the present composition.
Oxyalkylated (for example ethoxylation or the propenoxylated) aliphatic alcohol that has about 18 carbon atoms of about 12-in the available alkyl chain replaces aliphatic alcohol itself, or also adopts these alkoxy fatty alcohols except that aliphatic alcohol itself.Suitable example comprises ethylene glycol cetyl ether, polyoxyethylene (2) stearoyl ether, polyoxyethylene (4) cetyl ether, and their mixture.
The appropriate level of fat material is the 0.01-15 weight % of total composition in the conditioner of the present invention, preferred 0.1-10 weight %, more preferably 0.5-4 weight %.Cationic surfactant is 10 with the approrpiate wts ratio of aliphatic alcohol: 1-1: 10, preferred 4: 1-1: 8, preferably 1: 1-1: 7, and for example 1: 3.
Suspending agent
The present composition can not necessarily further comprise 0.1-10 weight %, the suspending agent of preferred 0.6-6 weight %.Suitable suspending agent is selected from cross-linked copolymer, heteropolysaccharide natural gum and the crystallization long acyl derivant of the copolymer of polyacrylic acid, acrylic acid cross linked polymer, acrylic acid and hydrophobic monomer, the copolymer that contains carboxylic acid monomer and acrylate, acrylic acid and acrylate.The long acyl derivant is preferably selected from glycol stearate, have the alkanolamide of fatty acid of 16-22 carbon atom and their mixture.Diglycol stearate and polyglycol distearate are preferred long acyl derivants.Polyacrylic acid can be used as Carbopol 420, Carbopol 488 or Carbopol 493 is purchased.Also can adopt with multifunctional dose of crosslinked polymerizing acrylic acid thing, they can be used as Carbopol 910, Carbopol 934, Carbopol940, Carbopol 941 and Carbopol 980 and are purchased.The example that contains the suitable copolymerizable thing of monomeric carboxylic acid and acrylate is Carbopol 1342.All Carbopol (trade mark) material all obtains from Goodrich.
The suitable cross linked polymer of acrylic acid and acrylate is Pemulen TR1 or PemulenTR2.Suitable heteropolysaccharide natural gum is for example to can be used as the HANSHENGJIAO (xanthan gum) that Kelzan mu obtains.
Yet, if the median particle diameter of mellisic median particle diameter and siloxane polymer less than 10 μ m, compositions suspending agent-containing not preferably, compositions of the present invention in other words contains the suspending agent of less than 0.01 weight %.This is because suspending agent can be deposited on the hair, the sensation that causes the certain user to produce smearing.
Other compositions
Compositions of the present invention also can contain other compositions that are suitable for hair cleaning and care composition.Also can contain other hydrophobic water-insoluble conditioning oil in the present composition.
The present composition also can contain the auxiliary agent that is fit to hair nursing.Every kind content reaches 2 weight % of total composition usually at most in these compositions.
Wherein suitable hair nursing auxiliary agent is the natural root of hair nutrient such as aminoacid and sugar.Suitable amino acid whose example comprises arginine, cysteine, glutamine, glutamic acid, isoleucine, leucine, methionine, serine and valine, and/or their precursor and derivant.Aminoacid can add separately, add as mixture, or with peptide, for example the form of dipeptides and tripeptides adds.Aminoacid also can add such as the protein hydrolysate form of keratin or collagen hydrolysate.Suitable sugar is glucose, dextrose and fructose.They can add separately or add with for example fruit extract form.The combination of the particularly preferred natural root of hair nutrient that can comprise in the present composition is isoleucine and glucose.Particularly preferred amino acid nutrient element is an arginine.Another kind of proper auxiliary agent is a glycolic.
The use pattern
The present composition is mainly used in the partial smearing of human hair and/or the scalp that maybe can stay the compositions on the hair that need rinse well after use is used.Said composition is used for providing hair style stretching, that volume reduces and/or that loft reduces after hair becomes dry.In order to realize this purpose, needn't be with hot blasting device dry hair, and preferably towel off with combing after make the hair natural drying.
The present invention will be by following indefiniteness embodiment explanation.The embodiment of the invention is by the numeral explanation, and comparative example is by the letter explanation.
Embodiment
The average radial measurement of spacing
Average radial spaces and measures relevantly with hair volume, relates to the manageability of hair.Therefore harmonious mean diameter is sent out to the measurement finger that spaces and is easy to management.
Shampoo is handled
With 2g/10 " topknot fastens rope and washes under faucet.The each processing restrainted hair with 4-5.Smear the 0.2ml shampoo along the topknot length direction, and crumpled 30 seconds, washed then 30 seconds.Smear the 0.2ml shampoo along the topknot length direction again, and crumpled 30 seconds, washed then 1 minute.Topknot is dangled and combing from support, with the water bottle flushing, all fibres is held together together then, one night of natural drying.
Laser measurement
Every bundle hair is dangled from support, with the helium-neon laser vertical irradiation of 2mW, λ=632.8nm on the topknot of former state, apart from topknot bottom about 2 ", will shine image recording on CD with the 35mm photographing unit.
Set the identification grade (generation is stored in the threshold value of the picture rich in detail of the some sequence number on the CD) of each image with macro-instruction.With X, the Y coordinate of each point on macro-instruction " lcalc " computed image, and convert this document to the machine readable text presents.Another macro-instruction among the Excel is carried out mathematic(al) manipulation to all coordinates, and coordinate is changed into physical location on topknot from its apparent location with respect to photographing unit.These actual coordinates are used to calculate the average radial distribution of all coordinate distance computer centers, thereby the indicator of topknot volume is provided.This number is more little, and volume is more little.
The result depends on measuring condition and hair type.Therefore every group of contrast test carried out simultaneously with the hair of same type.
Table 1
Weight % in the table 1 refers to the substantial activity chemical substance in the compositions, rather than the raw material of dilution.
| Chemical name | Trade (brand) name | Supplier | Weight % | |||
| A | B | C | 1 | |||
| Lauryl ether (Laureth) is sodium sulfate (2EO) | Empicol ESB70 | Albright & Wilson | 14 | 14 | 14 | 14 |
| Cocamido propyl betaine | Tegobetaine CK | Goldschmidt | 2 | 2 | 2 | 2 |
| Rhaball Gum CG-M 8M | Jaguar C13S | Rhone Poulenc | 0.2 | 0.2 | 0.2 | 0.2 |
| Polydimethylsiloxane 1 | DC1785 | Dow Corning | 2.0 | - | 3.5 | - |
| Divinyl dimethicone/dimethyl silicone copolymer 1 | HMW2220 | Dow Corning | - | - | - | 2.0 |
| Cera Flava phEUR | Koster Keunen | - | 1.5 | - | 1.5 | |
| Diglycol stearate | PK3000AM | COGNIS | 1 | 1 | 1 | 1 |
| Formaldehyde | Formalin | Mallinkropt | 0.1 | 0.1 | 0.1 | 0.1 |
| Water | - | - | Add to 100 | Add to 100 | Add to 100 | Add to 100 |
Clean 18 group members' hair by the skilled hairdresser of beauty parlor, carry out the test of following salon: wash hair wet and separate from the centre.On the hair on every limit, smear the 3g shampoo, under about 40 ℃ of temperature, wash hair in a usual manner with about 12 rench Hard water.The rinsing hair also repeats this process.Towel one's hair dry by the group member then and dry up.After the flushing process neutralization washes, estimate the various features of hair by the hairdresser.
Embodiment A compares with Embodiment B in a test, compares with embodiment 1 in second test.
The test of comparative example B since dislike coating that this product brings, oily sensation and not finishing.Product 1 compares with product A, and the arrangement of product 1, few fluffy, easy processing, submissive and slick feature are preferred under 90% significant level.The greasy feeling of product A and product 1 is suitable.
Therefore product of the present invention shows improved manageability.
The average radial of embodiment 1 and Embodiment C (mm) measurement result of spacing is as follows:
Embodiment 1 Embodiment C
Average radial spaces, and mm 13.79 11.22
The average radial of embodiment 1 spaces and significantly is lower than Embodiment C, so hair volume reduces.
Embodiment C and the test of embodiment 1 on sensor board obtain following result:
| Fineness | Be easy to combing | Clean sensation | |
| Embodiment C | 51.4 | 33.3 | 44.4 |
| Embodiment 1 | 48.6 | 66.7 | 55.6 |
The last table explanation embodiment of the invention has obtained good conditioning, hair is not totally felt to bring any adverse effect.
| Chemical name | Trade (brand) name | Supplier | Weight % | ||||
| 1 | C | 3 | 5 | 6 | |||
| Lauryl ether (Laureth) is sodium sulfate (2EO) | Empicol ESB70 | Albright & Wilson | 14 | 14 | 14 | 14 | 14 |
| Cocamido propyl betaine | Tegobetaine CK | Goldschmidt | 2 | 2 | 2 | 2 | 2 |
| Rhaball Gum CG-M 8M | Jaguar C13S | Rhone Poulenc | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Polydimethylsiloxane 1 | DC1668 | Dow Corning | 2.0 | ||||
| Polydimethylsiloxane 2 | DC1785 | Dow Corning | 2.0 | ||||
| Divinyl dimethicone/dimethyl silicone copolymer 3 | HMW2220 | Dow Corning | 2.0 | 2.0 | 2.0 | ||
| Cera Flava phEUR | Koster Keunen | 1.5 | 1.5 | 1.5 | 0.5 | 3.0 | |
| Diglycol stearate | PK3000AM | COGNIS | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Formaldehyde | Formalin | Mallinkropt | 0.1 | 0.1 | 0.1 | 0.1 | |
| Water | - | Add to 100 | Add to 100 | Add to 100 | Add to 100 | ||
The viscosity of DC1668 under 25 ℃ is 60,000mm
2/ s.
The viscosity of DC1785 under 25 ℃ is 1,000,000mm
2/ s.
The viscosity of HMW2220 under 25 ℃ is 120,000,000mm
2/ s.
Embodiment 1,5 and 6 average radial space as follows:
| Embodiment | 1 | 5 | 6 | C | 3 |
| Average radial spaces, mm | 15.2 | 16.3 | 17.3 | 17.0 | 16.3 |
Therefore containing the mellisic prescription of 1.5 weight % is better than containing 0.5 weight % and the mellisic prescription of 3% (weight).
The prescription that contains high-viscosity silicone is better than containing the Embodiment C than low viscosity silicone.
Claims (11)
1, aqueous Haircare composition comprises:
A) Cera Flava of the 0.1-8 weight % of total composition;
B) viscosity under 0.01Hz and 25 ℃ of the 0.01-10 weight % of total composition is at least 80,000mm
2The siloxane polymer of/s.
2, the aqueous Haircare composition of claim 1, wherein the viscosity of siloxanes under 0.01Hz and 25 ℃ is at least 1,000,000mm
2/ s.
3, the aqueous Haircare composition of claim 1 or claim 2, wherein the viscosity of siloxanes under 0.01Hz and 25 ℃ is at least 100,000,000mm
2/ s.
4, the aqueous Haircare composition of any aforementioned claim, wherein content of siloxane is the 0.5-4 weight % of total composition.
5, the aqueous Haircare composition of any aforementioned claim, wherein Cera Flava content is the 0.2-5 weight % of total composition.
6, the compositions of any aforementioned claim, wherein Cera Flava and siloxane polymer are with median particle diameter (D
50) be that 50 μ m or littler particle form exist.
7, the compositions of any aforementioned claim, wherein compositions is the cleaning combination that further comprises 1-25 weight % clean surface activating agent.
8, the compositions of any aforementioned claim, wherein the clean surface activating agent is selected from anion surfactant, amphoteric surfactant, zwitterionic surfactant, non-ionic surface active agent and their mixture.
9, aforesaid right requires the preparation method of the Haircare composition of any one, is included in the step of first emulsified beeswax before joining in the compositions.
10, the method for claim 9, wherein Cera Flava cationic surfactant emulsifying.
11, the purposes of the conditioning hair of the compositions of arbitrary aforementioned claim.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03256770.3 | 2003-10-27 | ||
| EP03256770 | 2003-10-27 | ||
| GB0402270.3 | 2004-02-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1870970A true CN1870970A (en) | 2006-11-29 |
| CN100502832C CN100502832C (en) | 2009-06-24 |
Family
ID=34585912
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800313674A Expired - Fee Related CN100502832C (en) | 2003-10-27 | 2004-09-16 | Hair care composition |
| CNA2004800316013A Pending CN1870973A (en) | 2003-10-27 | 2004-10-01 | Antidandruff shampoo composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800316013A Pending CN1870973A (en) | 2003-10-27 | 2004-10-01 | Antidandruff shampoo composition |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1677750A1 (en) |
| JP (1) | JP2007509183A (en) |
| CN (2) | CN100502832C (en) |
| AR (1) | AR046203A1 (en) |
| BR (1) | BRPI0415163A (en) |
| MX (1) | MXPA06004594A (en) |
| TW (1) | TW200518778A (en) |
| WO (1) | WO2005046629A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8263053B2 (en) * | 2005-11-22 | 2012-09-11 | Access Business Group International | Hair treatment compositions |
| JP2007277227A (en) * | 2006-03-14 | 2007-10-25 | Mochida Pharmaceut Co Ltd | Azole-based antifungal agent-formulated cleaning composition |
| BRPI1006678B1 (en) * | 2009-04-23 | 2017-02-21 | Unilever Nv | "hair treatment composition" |
| CN103068445A (en) * | 2010-08-18 | 2013-04-24 | 荷兰联合利华有限公司 | Anti-dandruff shampoo |
| JP6134265B2 (en) * | 2010-08-18 | 2017-05-24 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Anti-dandruff shampoo |
| FR2987259B1 (en) * | 2012-02-29 | 2014-02-21 | Oreal | USE AS ANTIPELLICULAR AGENT OF CATALYTIC COMPOUNDS OF OXIDATION SELECTED AMONG PORPHYRINS, PHTHALOCYANINS AND PORPHYRAZINES |
| MX2016013894A (en) * | 2014-04-24 | 2017-02-02 | Procter & Gamble | Scalp care composition. |
| CN106924074A (en) * | 2017-05-08 | 2017-07-07 | 福建华夏蓝新材料科技有限公司 | A kind of colorful washing product and preparation method thereof |
| CN107334653A (en) * | 2017-07-12 | 2017-11-10 | 南雄鼎成新材料科技有限公司 | A kind of antibacterial anti-dandruff and itching-relieving shampoo with treatment containing organosilicon quaternary ammonium salt |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4002734A (en) * | 1973-10-29 | 1977-01-11 | Pickford Melcina H | Hair grooming composition |
| US4843097A (en) * | 1984-06-13 | 1989-06-27 | Groupement D'interet Economique Dit: Centre International De Recherches Dermatologiques C.I.R.D. | 10-aryl-1,8-dihydroxy-9-anthrones and their esters, process for preparing same, and use of same in human and veterinary medicine and in cosmetics |
| US4867971A (en) * | 1988-04-22 | 1989-09-19 | Colgate-Palmolive Company | Low pH shampoo containing climbazole |
| US5213716A (en) * | 1989-06-21 | 1993-05-25 | Colgate-Palmolive Company | Hair conditioning shampoo containing long chain alcohol component |
| US5348736A (en) * | 1989-06-21 | 1994-09-20 | Colgate-Palmolive Company | Stabilized hair-treating compositions |
| US6635702B1 (en) * | 2000-04-11 | 2003-10-21 | Noveon Ip Holdings Corp. | Stable aqueous surfactant compositions |
-
2004
- 2004-09-16 CN CNB2004800313674A patent/CN100502832C/en not_active Expired - Fee Related
- 2004-10-01 JP JP2006537098A patent/JP2007509183A/en not_active Withdrawn
- 2004-10-01 CN CNA2004800316013A patent/CN1870973A/en active Pending
- 2004-10-01 EP EP04790116A patent/EP1677750A1/en not_active Withdrawn
- 2004-10-01 MX MXPA06004594A patent/MXPA06004594A/en not_active Application Discontinuation
- 2004-10-01 BR BRPI0415163-1A patent/BRPI0415163A/en not_active Application Discontinuation
- 2004-10-01 WO PCT/EP2004/011083 patent/WO2005046629A1/en not_active Application Discontinuation
- 2004-10-19 TW TW093131611A patent/TW200518778A/en unknown
- 2004-10-27 AR ARP040103901 patent/AR046203A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AR046203A1 (en) | 2005-11-30 |
| WO2005046629A1 (en) | 2005-05-26 |
| BRPI0415163A (en) | 2006-11-28 |
| TW200518778A (en) | 2005-06-16 |
| CN100502832C (en) | 2009-06-24 |
| MXPA06004594A (en) | 2006-06-27 |
| CN1870973A (en) | 2006-11-29 |
| JP2007509183A (en) | 2007-04-12 |
| EP1677750A1 (en) | 2006-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1104881C (en) | Conditioning shampoo compositions containing select hair conditioning osters | |
| CN1146392C (en) | Shampoo compositions | |
| CN1181812C (en) | Mousse-forming shampoo compsns. | |
| CN1142769C (en) | Personal cleansing compositions | |
| CN1142763C (en) | Shampoo compositions containing silicone | |
| CN1191819C (en) | Mousse-forming shampoo compositions | |
| CN1191048C (en) | Shampoo compositions | |
| CN1120702C (en) | Conditioning shampoo compositions containing polyalphaolefin conditioner | |
| CN1142768C (en) | Personal cleansing compositions | |
| CN101039655A (en) | Hair care compositions | |
| CN1665471A (en) | Conditioning shampoo composition | |
| CN1202800C (en) | Cosmetic composition contg. vinyl polydimethyl siloxanes/polydimethyl copolymer and conditioner and its use | |
| CN1929814A (en) | Hair treatment composition comprising sugar lactone | |
| CN1203840C (en) | Cleaning compositions | |
| JPWO2014148245A1 (en) | Shampoo composition | |
| CN1325675A (en) | Vinyl polydimethyl siloxanes/polydimethy siloxanes copolymer and thickening agent cosmetic compositions and use thereof | |
| CN1217643C (en) | Hair treatment composition | |
| CN101040825A (en) | Hair cleansing composition | |
| CN1304302A (en) | Hair treatment compositions | |
| CN1744878A (en) | Shampoo compositions | |
| CN1259042A (en) | Styling shampoo compositions containing an odor masking base | |
| CN1665470A (en) | Hair conditioning compositions | |
| CN100335031C (en) | Hair conditioning compositions | |
| CN1870970A (en) | Hair care composition | |
| CN1411366A (en) | Hair treatment composition comprising cationic surfactants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210823 Address after: Rotterdam Patentee after: Unilever Intellectual Property Holdings Ltd. Address before: Rotterdam Patentee before: Unilever Nederland B.V. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090624 |