CN101790368B - Detergent for the skin and method for cleansing the skin with the same - Google Patents
Detergent for the skin and method for cleansing the skin with the same Download PDFInfo
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- CN101790368B CN101790368B CN2008801052114A CN200880105211A CN101790368B CN 101790368 B CN101790368 B CN 101790368B CN 2008801052114 A CN2008801052114 A CN 2008801052114A CN 200880105211 A CN200880105211 A CN 200880105211A CN 101790368 B CN101790368 B CN 101790368B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
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Abstract
The invention aims at providing an excellent detergent for the skin which can form fine foam and is excellent in the ejection of foam at low temperature when charged into a foamer container and which can suppress dry skin after cleansing and a method for cleansing the skin. The invention relates to a detergent for the skin which contains (A) a betaine amphoteric surfactant, (B) an N-acylmethyltaurine salt and (C) a polyoxyethylene alkylsulfosuccinic acid salt and/or an alkylsulfosuccinic acid salt in such amounts by mass as to satisfy the relationship: (C)/[(A)+(B)]=0.05 to 0.5 and a method for cleansing the skin with the detergent.
Description
Technical field
The present invention relates to skin abluent and the skin cleaning method that uses this skin abluent; More specifically, relate to following skin abluent and utilize the skin cleaning method of said skin abluent, its alveolar substance is fine and smooth; When being filled in the bubbling container (Off オ one マ one container); Foamy discharge property is good during low temperature, further, can suppress to clean back scaly dry skin.
Background technology
In the past, the cleaning main constituent of skin abluent is known to have higher fatty acid salt, polyethylene oxide alkyl ethers sulfate, MAP etc., wherein, saw from the viewpoint of the exquisiteness of usability, alveolar substance, cleaning force etc., and using more is higher fatty acid salt.
Yet, use higher fatty acid salt, the problem points below existing, crystallization takes place to separate out in the insufficient exquisitenesses of alveolar substance etc. easily, and when being filled in the bubbling container, discharge property from container is bad etc., after the cleaning, makes scaly dry skin etc.
In order to eliminate such problem points; Various technology had been reported in the past; For example report has, and contains the cleansing composition (patent documentation 1) of N-acylamino acid series anion surfactant, anion surfactant in addition, any one chemical compound at least that is selected from amphoteric surfactant and semi-polarity surfactant and polyhydric alcohol; Contain laruate, the myristate of extra fine quality ratio, the cleansing composition (patent documentation 2) of palmitate; The cleansing composition (patent documentation 3) that contains anionic surfactant and/or amphoteric surfactant, water-insoluble particle and nonionic surfactant; Contain lauric acid alkaline amino acid salt, the myristic acid alkaline amino acid salt of extra fine quality ratio and contain the cleansing composition (patent documentation 4) of higher fatty acids; The cleansing composition (patent documentation 5) that contains sulfosuccinic dialkylaminobenzoic acid salt and/or 2-Sulfosuccinic acid PEO alkyl salt, betaine type amphoteric surfac-tant, acrylic acid alkyl methacrylate copolymer, higher fatty acid salt and powder body; Contain sulfosuccinic acid type anionic surfactant, N-acyl acidic amino acid type anionic surfactant and betaine type amphoteric surfac-tant any at least one, the dispersion liquid of fatty acid diol ester, regulate the cleansing composition (patent documentation 6) of composition and water; Contain the specific acyl lactylates of specific mass ratio and the Cleasing compositions (patent documentation 7) of specific auxilliary surfactant; The skin abluent (patent documentation 8) that contains anionic surfactant, amphoteric surfactant, oil and the water of specific mass ratio; Contain specific mass ratio N-carboxylic acyl type surfactant and N-acyl group sulfonic acid type surfactant at least any one, amphoteric surfactant, two surfacant and half-shadow sexual type surfactant at least any one, the cleansing composition (patent documentation 9) of any one and the alkyl diol polyol ethers chemical compound at least of ethanol, glycerol, propylene glycol and dipropylene glycol; Contain specific mass ratio acyl methyl taurine salt type anionic surfactant, alkylamide amino acid salts type amphoteric surfactant and alkyl imino dicarboxylate type amphoteric surfactant at least any one, the cleansing composition (patent documentation 10) of any one and the water soluble dihydric alcohol at least of alkyl betaine-type amphoteric surfactant and alkyl amido betaine type amphoteric surfactant; The cleansing composition (patent documentation 11) that contains anionic surfactant, amphoteric surfactant and the sucrose fatty acid ester of specific mass ratio.
Yet; Even in the technology of above-mentioned that kind, do not find that alveolar substance is fine and smooth, the foamy discharge property when being filled into bubbling container during low temperature and clean the back skin and do not have all good skin abluents of dry sensation, therefore yet; Expect a kind of following good skin abluent; Its alveolar substance is fine and smooth, and the foamy discharge property when being filled into bubbling container during low temperature is good, and can suppress to clean back scaly dry skin.
Patent documentation 1: Japanese Patent Laid is opened the 2006-183039 communique
Patent documentation 2: Japanese Patent Laid is opened the 2005-154651 communique
Patent documentation 3: Japanese Patent Laid is opened the 2005-187411 communique
Patent documentation 4: japanese patent laid-open 1-238521 communique
Patent documentation 5: Japanese Patent Laid is opened the 2006-169453 communique
Patent documentation 6: Japanese Patent Laid is opened the 2005-289823 communique
Patent documentation 7: japanese patent laid-open 6-40850 communique
Patent documentation 8: japanese patent laid-open 7-25726 communique
Patent documentation 9: Japanese Patent Laid is opened the 2005-146016 communique
Patent documentation 10: Japanese Patent Laid is opened the 2006-206720 communique
Patent documentation 11: Japanese Patent Laid is opened the 2007-138023 communique
Summary of the invention
The present invention In view of the foregoing; Purpose is to provide skin abluent and the skin cleaning method that uses this skin abluent, and the alveolar substance of this skin abluent is fine and smooth, when being filled in the bubbling container; Foamy discharge property is good during low temperature, and can suppress to clean back scaly dry skin.
The inventor is in order to reach above-mentioned purpose; Concentrate on studies; The result find through combination (A) betanin be amphoteric surfactant, (B) N-acyl methyl taurine salt and (C) PEO alkyl sulfo succinate and alkyl sulfo succinate at least any one, and the mass ratio of (C)/[(A)+(B)] is set at specific ratios, can obtain the skin abluent of following excellence; Its alveolar substance is fine and smooth; It is good that foam when being filled in the bubbling container during low temperature is discharged property, can suppress to clean back scaly dry skin further, thereby accomplish the present invention.
Therefore, the present invention is,
< 1>a kind of skin abluent; It is characterized in that; Contain (A) betanin and be amphoteric surfactant and, (B) N-acyl methyl taurine salt and (C) PEO alkyl sulfo succinate and alkyl sulfo succinate at least any one; The content of above-mentioned each composition is (C)/[(A)+(B)]=0.05～0.5 than by quality ratio.
< 2>like above-mentioned < 1>described skin abluent, form by being filled into bubbling container.
< 3>a kind of skin method of cleaning is characterized in that, uses any described skin abluent of above-mentioned < 1>to < 2 >.
< 4>like above-mentioned < 3>described skin method of cleaning, the foamed skin abluent that will from bubbling container, discharge with hands is coated on the skin, cleans.
According to the present invention; The skin abluent and the skin cleaning method that uses this skin abluent of following excellence can be provided, and the alveolar substance of this skin abluent is fine and smooth, when being filled in the bubbling container; Foamy discharge property is good during low temperature, and can suppress to clean back scaly dry skin.
The specific embodiment
(skin abluent)
(A) betanin that skin abluent of the present invention contains specific mass ratio be amphoteric surfactant, (B) N-acyl methyl taurine salt with (C) PEO alkyl sulfo succinate and alkyl sulfo succinate at least any one; Further, can contain other any compositions aptly as required and constitute.
(A) composition
Above-mentioned betanin is that amphoteric surfactant ((A) composition) does not have restriction especially; Can carry out suitable choice according to purpose, for example imidazoline type (amino amides type), amidoamino acid salt, carbon betaine type (alkyl betaine, alkyl amido betaine), sulfobetaines type (alkyl sulfobetaines, alkyl hydroxy sulfobetaines) etc. are arranged for example.
Have for example as above-mentioned imidazoline type and for example to be added in the amino amide of stearoyl, cocos nucifera oil alkyl-N-hydroxyethyl imidazoles betanin.Above-mentioned carbon betaine type has for example alkyl betaine for example: lauryl dimethyl glycine betanin, cocos nucifera oil alkyl dimethyl glycine betanin, octadecanoyl dimethylaminoethyl acid betanin etc.; Alkyl amido betaine: fatty acid distribution of coconut oil amido propyl betaine, lauric amide CAB etc.Above-mentioned sulfobetaines type has for example alkyl sulfobetaines for example: fatty acid distribution of coconut oil dimethyl sulfopropyl betaine etc.; Alkyl hydroxy sulfobetaines: fatty acid distribution of coconut oil dimethylamino hydroxyl sulfo betaine, lauryl dimethyl base hydroxy amino sulfobetaines etc.; Also has lauryl hydroxyl sulfo betaine etc.
Wherein, It is amphoteric surfactant that above-mentioned (A) composition it is desirable to the betanin carbon betaine type, that this alkyl chain has a monovalence alkyl of carbon number 12～18; Especially, the betanin that better is has a monovalence alkyl of carbon number 12～16 is an amphoteric surfactant.
In addition, said (A) composition can independent a kind of use, perhaps also can be more than 2 kinds aptly combination use.
Content for above-mentioned (A) composition does not have special restriction, can carry out suitable choice according to purpose, especially, in above-mentioned skin abluent, it is desirable to 2～20 quality %, and that better is 5～15 quality %.The above-mentioned quantity not sufficient 2 quality % that contain, it is insufficient that the sophistication of alveolar substance becomes sometimes, surpasses 20 quality %, after suppressing cleaning, aspect the scaly dry skin, is unfavorable.On the other hand, above-mentioned content aspect the sophistication with more excellent alveolar substance can being provided and cleaning the moist skin abluent of back skin, is favourable in better scope.
(B) composition
As above-mentioned N-acyl methyl taurine salt ((B) composition), there is not restriction especially, can carry out suitable choice according to purpose; But as this acyl group; It is desirable to have the monovalence alkyl of carbon number 5～21, especially, better is has the monovalence alkyl of carbon number 11～15.The carbon number of above-mentioned acyl group in better scope, can provide more excellent when being filled into bubbling container the foam during low temperature discharge aspect the skin abluent of property, be favourable.
Again, as above-mentioned salt, it is desirable to alkali metal salt, alkali earth metal salt, amine salt or amino acid salts, especially better is alkali metal salt, replacement or the non-substituted ammonium salt of sodium, potassium etc.Wherein, it is desirable to sodium salt especially again.Above-mentioned salt is sodium salt, providing aspect the skin abluent with more excellent mildness to skin, is favourable.
As above-mentioned (B) composition; N-lauroyl methyl tauride, N-myristoyl methyl tauride, N-palmityl methyl tauride, N-stearoyl methyl tauride, tallow acid methyl tauride, N-fatty acid distribution of coconut oil methyl tauride, N-capryl methyl tauride etc. are arranged particularly for example; Wherein, it is desirable to N-fatty acid distribution of coconut oil N-methyltaurine sodium especially.
In addition, said (B) composition can independent a kind of use, perhaps also can be more than 2 kinds aptly combination use.
Content for above-mentioned (B) composition does not have special restriction, can carry out suitable choice according to purpose, especially, in above-mentioned skin abluent, it is desirable to 0.5～10 quality %, and that better is 1～5 quality %.The above-mentioned quantity not sufficient 0.5 quality % that contains, the sophistication of alveolar substance becomes insufficient sometimes, surpasses 10 quality %, and the foam when being filled into bubbling container during low temperature is discharged aspect the property, is unfavorable.On the other hand, above-mentioned content is in better scope, and the foam in the time the sophistication with more excellent alveolar substance can being provided and being filled into bubbling container during low temperature is discharged on the skin abluent this point of property, is favourable.
(C) composition
As above-mentioned PEO (below; Sometimes abbreviate POE as) any one ((C) composition) at least of alkyl sulfo succinate and alkyl sulfo succinate, there is not restriction especially, can carry out suitable choice according to purpose; But as this alkyl chain; It is desirable to have the monovalence alkyl of carbon number 12～22, especially, better is has the monovalence alkyl of carbon number 12～14.The carbon number less than 12 of abovementioned alkyl chain, undesirable aspect skin irritation, surpass 22, the foam when being filled into bubbling container during low temperature is discharged aspect the property, is unfavorable.On the other hand, the carbon number of abovementioned alkyl chain in better scope, can provide have more excellent for skin mildness and when being filled into bubbling container the foam during low temperature discharge on the skin abluent this point of property, be favourable.
Again, as above-mentioned salt, it is desirable to alkali metal salt, alkali earth metal salt, amine salt or amino acid salts, especially better is alkali metal salt, replacement or the non-substituted ammonium salt of sodium, potassium etc.Wherein, it is desirable to sodium salt especially again.Above-mentioned salt is sodium salt, providing aspect the skin abluent with more excellent mildness to skin, is favourable.
Again, the ethylene addition molal quantity of above-mentioned PEO alkyl sulfo succinate it is desirable to 1～10, and especially, better is 2～5.Above-mentioned ethylene addition molal quantity less than 1, the foam when being filled into bubbling container during low temperature are discharged the property aspect and are considered, are unfavorable, surpass 10, consider from the sophistication aspect of alveolar substance, and be unfavorable.On the other hand, above-mentioned ethylene addition molal quantity is in better scope, and the foam when more excellent low temperature when being filled into bubbling container can be provided is discharged aspect the skin abluent of sophistication of property and alveolar substance, is favourable.
In addition, as above-mentioned (C) composition, especially, it is desirable to the PEO alkyl sulfo succinate.
As above-mentioned (C) composition; POE (1) alkyl (12～14) sulfosuccinate, POE (2) alkyl (12～14) sulfosuccinate, POE (3) dialkyl group (12～14) sulfosuccinate, POE (5) dialkyl group (12～14) sulfosuccinate, POE (7) dialkyl group (12～14) sulfosuccinate, POE (9) dialkyl group (12～14) sulfosuccinate, POE (2) alkyl (12～15) sulfosuccinate, the single oleyl amidic-salt of 2-Sulfosuccinic acid POE (2), POE (4) fatty acid distribution of coconut oil isopropanol amide sulfosuccinate, 2-Sulfosuccinic acid POE (5) lauroyl glycollyl amine salt, endecatylene acyl group amide ethyl sulfosuccinate, 2-Sulfosuccinic acid diethylhexyl salt, 2-Sulfosuccinic acid Laurel salt, sulfosuccinic dodecyl gallate salt etc. are arranged particularly for example; Wherein, it is desirable to POE (2) alkyl (12～14) disodium sulfosuccinate.
In addition, said (C) composition can independent a kind of use, perhaps also can be more than 2 kinds aptly combination use.
Content for above-mentioned (C) composition does not have special restriction, can carry out suitable choice according to purpose, especially, in above-mentioned skin abluent, it is desirable to 1～7 quality %, and that better is 1.5～6 quality %.The above-mentioned quantity not sufficient 1 quality % that contains, the foam when being filled into bubbling container during low temperature discharge the property aspect and consider, are unfavorable, surpass 7 quality %, and the scaly dry skin aspect after suppressing to clean is considered, is unfavorable.On the other hand, above-mentioned content is in better scope, and the foam when more excellent low temperature when being filled into bubbling container can be provided is discharged property and cleaned the back skin and do not have aspect the exsiccant skin abluent, is favourable.
< content ratio >
The content of each composition of above-mentioned (A)～(C) compares by quality ratio, (C)/[(A)+(B)]=0.05～0.5, it is desirable to 0.1～0.4, better is 0.15～0.4.Above-mentioned mass ratio less than 0.05, the foam when being filled into bubbling container during low temperature are discharged the property aspect and are considered, are inadequate, surpass 0.5, and the scaly dry skin aspect after suppressing to clean is considered, is inadequate.On the other hand, above-mentioned mass ratio is in better scope, and the foam when more excellent low temperature when being filled into bubbling container can be provided is discharged property and cleaned the back skin and do not have aspect the exsiccant skin abluent, is favourable.
< any composition >
Skin abluent of the present invention in the scope of not damaging effect of the present invention, can mix any composition except each composition of above-mentioned (A)～(C).Can in the middle of the material that is generally used for the skin abluent, carry out suitable choice as above-mentioned any composition; Insoluble polymer powder body, propylene glycol, ethanol, glycerol, water etc. that medicament, antibacterial, antiseptic, pH adjustment agent, antioxidant, metal chain stopper, UV absorbent, animals and plants extract or its derivant, pigment, spice, pigment, inorganic particle, clay mineral, nylon, the polyethylene etc. of the alcohols, agnolin derivant, protein derivatives, acrylic resin dispersion liquid, cation property copolymer, anionic property polymer, nonionic polymer, vitamin etc. of the non-ionic surface active agent of the anion surfactant, amine oxide, polyethylene oxide alkyl ethers etc. of the PEO alkane ether sulfate of removing above-mentioned (B), (C) composition etc., the amphoteric surfactant of removing above-mentioned (A) composition, oil content, silicone, rudimentary or higher alcohol etc. for example, are arranged for example.
< manufacturing >
Manufacturing approach as skin abluent of the present invention; Do not have special restriction, can carry out suitable choice according to purpose, for example; Mix above-mentioned (A)～(C) composition, any composition and water (mix remainder and make that whole skin abluent is 100 quality %), can obtain the skin abluent.Again,, do not have restriction especially, can carry out suitable choice, especially it is desirable to possess shearing force and the agitating device that can make whole blended a plurality of stirring vanes (propeller, turbine, disperser etc.) according to purpose as the device of the above-mentioned skin abluent of preparation.In addition, during preparation skin abluent, above-mentioned (A)～(C) composition of independent use and any composition be can distinguish, also can above-mentioned (A)～(C) composition and any composition be used with the state that contains the mixture of ingredients more than 2 kinds.
< container >
Skin abluent of the present invention has suppressed separating out at low temperatures, so suitable the filling as the bubbling container that makes the skin abluent be the blister discharge used the skin abluent.Therefore; As the container of filling skin abluent of the present invention; Do not have special qualification, but it is desirable to bubbling container, again; Above-mentioned skin abluent is suitable to above-mentioned skin abluent is filled into the skin rinse product that forms in the bubbling container, perhaps as by bubbling container be filled into the liquid ceanser product that the skin abluent in the bubbling container constitutes.
Above-mentioned bubbling container has the for example foam amount discharge container of non-pneumatic type for example.Foam amount discharge container as above-mentioned non-pneumatic type; As long as can the skin abluent be mixed with air; Get final product with the foamed state discharge; Do not have special qualification, for example have for example and can discharge foamy extruding bubbling container, can discharge foamy pump bubbling container etc., can carry out suitable choice according to purpose through pushing spray nozzle part through pushing body portion with hands.Such bubbling container for example can use big with system jar (strain) make, the container of (strain) lucky wild industrial manufacturing etc.
The foam amount discharge container of above-mentioned non-pneumatic type has the multiple aperture plasma membrane body (material it is desirable to the plastic material of nylon, polyester, polyene etc.) that the formation foam is used usually, and the skin abluent is through this multiple aperture plasma membrane body, thus the formation foam.As the mesh (mesh) of this multiple aperture plasma membrane body, there is not restriction especially, can carry out suitable choice according to purpose, for example it is desirable to more than 100 orders (eyelet number per square inch), better is 100～400 orders, it is desirable to 200～350 orders especially.Again,, do not have restriction especially, can carry out suitable choice,, it is desirable to 2～4 from improving the viewpoint of foaming properties according to purpose as the number of above-mentioned multiple aperture plasma membrane body.
More specifically, as above-mentioned bubbling container, can use japanese patent laid-open 7-315463 communique, japanese patent laid-open 8-230961 communique and Japanese Patent Laid to open the described bubbling container of 2005-193972 communique etc. aptly.
< character >
As the character of skin abluent of the present invention, it is desirable to is liquid at normal temperatures.
Again, as the viscosity of above-mentioned skin abluent, when using bubbling container; More specifically, for example use when pushing spray nozzle part and can discharge foamy pump bubbling container and 2 200 orders and 305 orders, under the temperature conditions that uses; It is desirable to below the 15mPas, that better is 1～10mPas.In addition, above-mentioned viscosity be through BL type viscometer (banbury roller (ロ one タ one) No.1,60rpm, after 1 minute/Tokyo gauge (strain) makes) value measured.
Again, above-mentioned skin abluent waits in the bathroom when using, and the pump part is sneaked into steam or water sometimes.During the residual skin abluent of pump part, because the skin abluent might be diluted, so consider that from the efficiency of preservation aspect pH of above-mentioned skin abluent (25 ℃) it is desirable to 4～6.
Again; Stating such hand washing after above-mentioned skin abluent is applied to cleans (in addition; In this manual, " hand washing clean " is meant with hands foamed skin abluent to be coated in and cleans skin on the skin) time, the foam of from bubbling container, discharging can at once not disappear (head retention is good); Be coated in easily on the skin, this is necessary.Therefore, at this moment, the viscosity of foamed above-mentioned skin abluent (bubble viscosity) it is desirable to about 2500～3100mPas.When above-mentioned bubble viscosity surpassed 3100mPas, alveolar substance is thick a little, and was undesirable.On the other hand, above-mentioned bubble viscosity is in ideal scope, and foamy persistence is good, with regard to the skin abluent that is suitable for hand-washing cleaning can be provided, is favourable.In addition, above-mentioned bubble viscosity is the value of measuring according to the viscosimetry of Japanese Pharmacopoeia ordinary test method, and use Brookfield viscometer under this is determined at 25 ℃ (NO2, rotating speed 60rpm, after 30 seconds/and Tokyo gauge (strain) manufacturing) carry out.
< purposes >
As the purposes of skin abluent of the present invention, there is not qualification especially, can be applied to for example bath gel, handwashing liquid, cleansing milk etc.Especially, the alveolar substance of skin abluent of the present invention is fine and smooth, and it is excellent to clean the moist aspect of skin, back, even for responsive flesh also gentleness, is suitable as the skin abluent of the human of baby, young woman, old people or responsive skin.
(skin cleaning method)
Skin cleaning method of the present invention is characterised in that, uses the skin abluent of the invention described above.
As above-mentioned skin cleaning method; Do not have special restriction, can carry out suitable choice, have the skin abluent of for example getting above-mentioned liquid state to be placed on the clean apparatus such as sponge, nylon towel for example according to purpose; After foaming on the above-mentioned implement, clean the method for skin; Skin abluent show bubble ground in the bubbling container that is filled into above-mentioned that kind is discharged, above-mentioned discharge foam is coated on the skin method of cleaning etc. with hands or implement.Wherein above-mentioned skin cleaning method it is desirable to the latter, especially it is desirable to above-mentioned discharge foam is coated in the method (hand washing is cleaned) of cleaning on the skin with hands
Again, in above-mentioned skin cleaning method, for the skin part as cleaning object, not having restriction especially, can be cleaning object at interior whole body to comprise face and trick.
Skin cleaning method is in the past generally got the liquid cleaning material of 3g and is placed on sponge or the nylon towel; Clean whole body, there is following problem points in it, aspect usability; The generation of bubble is inconvenient; Perhaps owing to use implement continuously skin is carried out over-drastic friction, clean back scaly dry skin, percutaneous moisture evapotranspiration increases.
Yet skin cleaning method of the present invention it is desirable to above-mentioned skin abluent is filled in the container that pump plays alveolitoid, becomes cystose to discharge, so aspect usability, be easy.And the alveolar substance during discharge is fine and smooth, and foamy persistence is good, discharges foam so for example directly get about 1g (about 1g/l discharges) through (at every turn), is coated on the skin, just can clean whole body with less discharge number of times.When hand washing is cleaned like this,,, can clean skin in milder ground so can suppress to clean back scaly dry skin, the increase of percutaneous moisture evapotranspiration owing to do not use implement again.
Again; The discharge foam of getting above-mentioned skin abluent is placed on easily when cleaning on the implement (for example, sponge, nylon towel etc.) that skin is rubbed, and the alveolar substance when above-mentioned skin abluent is discharged is also fine and smooth; Foamy persistence is also good; So compared to the situation of cleaning, can suppress to clean back scaly dry skin, the increase of percutaneous moisture evapotranspiration, can leniently clean skin with liquid abluent.
Embodiment
Below, through embodiment and comparative example, more be described in detail the present invention, but the present invention is not limited by following embodiment.In addition, do not specify in the following example, " % " expression quality % of composition, ratio is represented mass ratio, the amount of each composition in the table is the amount that is converted into pure article.
[embodiment 1～17 and comparative example 1～6]
Prepare the skin abluent of the composition of table 1～4 demonstrations according to common method; The skin abluent of the liquid state that obtains is adjusted into initial value pH5 (to be measured with the pH meter measuring device; HM-30G/ East Asia electric wave industry (strain) is made), fill the pump receptacle of 400ml to capacity 500ml with allotter (dispenser).Again, the skin abluent of the above-mentioned liquid state of 400ml is filled into the pump bubbling container (using 1 in 1 in 200 orders and 305 orders) of capacity 500ml, obtains non-aerial fog type foam shape skin abluent.In addition, as each composition in table 1～4, the commodity shown in the table of stating after using respectively 8.
Skin abluent to obtaining carries out following evaluation.The result is remembered in the lump in table 1～4.
Foam during-low temperature when being filled into bubbling container discharge property-
Preserve non-aerial fog type foam shape skin 1 week of abluent down at 5 ℃, then, under 5 ℃ condition, carry out 300 times the operation from the discharge of pump bubbling container repeatedly, based on following metewand, the foam when estimating low temperature is discharged property.5 samples are estimated, and the result shows with its meansigma methods.
< metewand >
5: do not mix thick foam, can discharge with the foam of exquisiteness.
4: the foam that partial hybrid is thick, but can discharge with the foam of exquisiteness, no problem on the quality.
3: integral body mixes thick foam, but can discharge with the foam of exquisiteness, and is no problem on the quality.
2: integral body mixes thick foam, can not discharge with the foam of exquisiteness, and problem is arranged on the quality.
1: do not form foam, can not discharge, problem is arranged on the quality with the foam of exquisiteness.
The sophistication of-alveolar substance-
Get the liquid skin abluent of about 3g and be placed on the nylon towel with 40 ℃ tap water moistening, the cleaning arm is estimated the sophistication of its alveolar substance.Estimated by 30 high special testers (paneler) of evaluation precision, according to following reference recording mark, the result shows with meansigma methods.
< metewand >
◎: feel more than 25 that foamy sophistication is good.
Feel that foamy sophistication is good for zero: 20～24.
△: feel that foamy sophistication is good for 15～19.
*: feel below 14 that foamy sophistication is good.
The increase of-percutaneous moisture evapotranspiration-
General using skin abluent is removed the skin care composition superfluously as everybody knows, and percutaneous moisture evapotranspiration increases.The barrier function of skin descends, and percutaneous moisture evapotranspiration is promoted, clean sometimes the burning sense of aftersensation or itch etc. excitement.Therefore; Liquid skin abluent with about 3g; 4 30 years old male testers cleaned the arm medial part 1 minute with hands, under the environment of 20 ℃ of temperature, humidity 40%, after the Hue 30 minutes; With percutaneous moisture evapotranspiration determinator (manufacturing of AS-TW2 ASAHI BIOMED society), the percutaneous moisture evapotranspiration of each arm is measured 5 times.Percutaneous moisture evapotranspiration before cleaning is made as 100,,, calculates the increment rate (%) after the cleaning, estimate the increase (decline of skin barrier function) of percutaneous moisture evapotranspirations by 4 meansigma methodss according to following formula according to 5 times meansigma methods.According to following metewand display result.In addition, we can say with clean before compare percutaneous moisture evapotranspiration the low skin abluent of increment rate be to the gentle abluent of skin.
< formula >
Moisture evapotranspiration (5 meansigma methodss) * 100 before increment rate (%)=[the moisture evapotranspiration (5 meansigma methodss) before the moisture evapotranspiration after the cleaning (5 meansigma methodss)-cleaning]/cleaning
< metewand >
5: increment rate is below 0%
4: increment rate 1～20%
3: increment rate 21～40%
2: increment rate 41～60%
1: increment rate is more than 61%
Skin after the-cleaning is moist-
Get the liquid skin abluent of about 3g and be placed on the nylon towel that has wet with 40 ℃ of tap waters, clean after the arm, estimate the inhibition of scaly dry skin.Estimate by 10 high special testers of evaluation precision, according to following benchmark record mark, with the meansigma methods display result.
< metewand >
◎: answer more than 8 in 10 and can suppress dry.
6～7 answers can suppress dry in zero: 10.
△: 4～5 answers can suppress dry in 10.
*: answer below 3 in 10 and can suppress dry.
[table 1]
[table 2]
[table 3]
[table 4]
See and to know from the result of table 1～4; (A)～(C) composition all contains and the skin abluent of the present invention (embodiment 1～17) within the specific limits of mass ratio (C)/[(A)+(B)] is excellent skin abluent; Its alveolar substance is fine and smooth, and it is good and can suppress to clean back scaly dry skin that the foam when being filled in the bubbling container during low temperature is discharged property.And do not contain (A)～(C) composition any one perhaps the mass ratio of (C)/[(A)+(B)] do not satisfy the alveolar substance sophistication of the skin abluent (comparative example 1～6) of certain limit, the foam when being filled in the bubbling container during low temperature discharge property and clean the back skin moist any at least one bad.
[embodiment 18: the liquid ceanser that mixes anti-inflammatory agent]
The liquid ceanser of the mixing anti-inflammatory agent of forming through the proportioning shown in below the common method preparation.
Quality %
Lauric amide CAB 10.00
Cocos nucifera oil alkyl-N-hydroxyethyl imidazole betanin 0.50
N-fatty acid distribution of coconut oil N-methyltaurine sodium 2.50
POE (2) alkyl (12～14) disodium sulfosuccinate 2.00
2-Sulfosuccinic acid POE (5) lauroyl glycollic amide disodium (Sanyo Chemical Industries, Ltd.) 0.50
Propylene glycol 13.00
Concentrated glycerin 5.00
1,3 butylene glycol 2.00
Poise C-80M (Lion Corporation) 0.05
Glycyrrhizic acid dipotassium 0.10
Spice 0.50
Blue No. 1 0.00015
Yellow No. 4 0.0001
Citric acid is adjusted into the amount of pH5.0
The Purified Water surplus
Add up to 100.00
(C)/[(A)+(B)] ratio=0.19
[embodiment 19: the cystose abluent is used in deodorant and antibacterial]
The cystose abluent is used in deodorant and antibacterial through the proportioning shown in below the common method preparation is formed.
Quality %
Lauric amide CAB 9.00
Fatty acid distribution of coconut oil amido propyl betaine 1.00
Lauryl dimethyl glycine betanin 0.50
N-fatty acid distribution of coconut oil N-methyltaurine sodium 2.50
POE (2) alkyl (12～14) disodium sulfosuccinate 2.50
Propylene glycol 13.00
Dipropylene glycol 0.50
Concentrated glycerin 5.00
1,3 butylene glycol 2.00
Chlorination dimethyldiallylammonium acrylamide copolymer liquid 0.50
(the Na Le コ ジ ヤ パ of Co., Ltd. Application)
Ethanol 3.00
Isopropyl methyl phenol 0.10
Octopirox (ピ ロ Network ト Application オ ラ ミ Application) 0.10
L-menthol 0.30
Spice 0.50
Blue No. 1 0.0001
Yellow No. 4 0.0001
Citric acid is adjusted into the amount of pH5.0
The Purified Water surplus
Add up to 100.00
(C)/[(A)+(B)] ratio=0.19
[embodiment 20: gentle liquid ceanser for baby]
The for baby gentle liquid ceanser of forming through the proportioning shown in below the common method preparation.
Quality %
Lauric amide CAB 5.00
Lauryl dimethyl glycine betanin 0.50
Fatty acid distribution of coconut oil dimethylamino hydroxyl sulfo betaine 0.50
N-fatty acid distribution of coconut oil N-methyltaurine sodium 0.50
2-Sulfosuccinic acid POE (5) lauroyl glycollic amide disodium 1.50
Propylene glycol 10.00
Concentrated glycerin 4.50
1,3 butylene glycol 2.00
Dipropylene glycol 0.50
Herba Rosmarini Officinalis extract 1.00
Jojoba oil 0.50
Poise C-80M (Lion Corporation) 0.05
Glycyrrhizic acid dipotassium 0.10
Spice 0.50
Blue No. 1 0.00015
Yellow No. 4 0.0001
Fructus Citri Limoniae is adjusted into the amount of pH5.0
The Purified Water surplus
Add up to 100.00
(C)/[(A)+(B)] ratio=0.23
Likewise the skin abluent of embodiment 18～20 is carried out each evaluation with above-mentioned.The result is presented in the table 5.The skin abluent of embodiment 18～20 is excellent skin abluent, and its alveolar substance is fine and smooth, and it is good and can suppress to clean back scaly dry skin that the foam when being filled in the bubbling container during low temperature is discharged property.
[table 5]
[embodiment 21: the evaluation of cleaning method]
In order to find the cleaning method that is fit to skin abluent of the present invention, carry out following evaluation.
The difference of the increase of the percutaneous moisture evapotranspiration that the difference of-cleaning method is brought-
The skin abluent of embodiment 1 is filled into pump bubbling container (1 in 1 in 200 orders and 305 orders); Get that about 1g discharges that foam is placed on hands or the nylon towel that wet with 40 ℃ tap water on; 4 30 years old male testers cleaned the upper arm medial part 1 minute with this, every day 1 time, continued 5 days.After cleaning in the 5th day, under the environment of 20 ℃ of temperature, humidity 40%, after the Hue 30 minutes, with percutaneous moisture evapotranspiration determinator (manufacturing of AS-TW2 ASAHI BIOMED society) to the percutaneous moisture evapotranspiration mensuration of each arm 5 times.Percutaneous moisture evapotranspiration before cleaning was made as 100 o'clock,,, calculates the increment rate (%) after the cleaning, estimate the increase (decline of skin barrier function) of percutaneous moisture evapotranspirations by 4 meansigma methodss according to following formula according to 5 times meansigma methods.Result according to following metewand is presented in the table 6.In addition, we can say with clean before compare the increment rate of percutaneous moisture evapotranspiration low (the metewand value is high) the skin cleaning method be to the gentle cleaning method of skin.
< formula >
Moisture evapotranspiration (5 meansigma methodss) * 100 before increment rate (%)=[the moisture evapotranspiration (5 meansigma methodss) before the moisture evapotranspiration after the cleaning (5 meansigma methodss)-cleaning]/cleaning
< metewand >
5: increment rate is below 0%
4: increment rate 1～20%
3: increment rate 21～40%
2: increment rate 41～60%
1: increment rate is more than 61%
The moist difference that the difference of-cleaning method is brought-
The skin abluent of embodiment 1 is filled into pump bubbling container (1 in 1 in 200 orders and 305 orders), get that about 1g discharges that foam is placed on hands or the nylon towel that wet with 40 ℃ tap water on, cleaned upper arm medial part 1 minute with this, every day 1 time, lasting 5 days.After cleaning in the 5th day, estimate the inhibition of scaly dry skin.Estimate by 10 high special testers of evaluation precision,, its meansigma methods as a result of is presented in the table 6 according to following reference recording mark.
< metewand >
◎: answer more than 8 in 10 and can suppress dry.
6～7 answers can suppress dry in zero: 10.
△: 4～5 answers can suppress dry in 10.
*: answer below 3 in 10 and can suppress dry.
[table 6]
| ? | Hand washing is cleaned | Nylon towel ※ cleans |
| Percutaneous moisture evapotranspiration | 5.0 | 4.0 |
| It is moist to clean the back skin | ◎ | ○ |
※ nylon towel: マ one Na manufactured メ レ Application ゲ サ ボ Application towel (softness)
See from the result of table 6; Even skin abluent of the present invention adopts any cleaning method that hand washing is cleaned and the nylon towel cleans; Also obtained good result aspect the increase inhibition of the moist and percutaneous moisture evapotranspiration of the skin after cleaning; Especially, in hand washing was cleaned, its effect was remarkable.Hence one can see that, and skin abluent of the present invention is especially to be fit to the skin abluent that hand washing is cleaned.
[embodiment 22: the evaluation of the quality of bubble viscosity and foamy persistence]
In the time of during the hand washing that the skin abluent is applied to above-mentioned that kind is cleaned, the foam of from bubbling container, discharging does not disappear (the foam persistence is good) at once, is prone to be coated on the skin, and this is necessary.Therefore, like the bubble viscosity of estimating skin abluent of the present invention and the quality of foam persistence followingly.
-bubble viscosity-
The skin abluent and the commercially available skin abluent of above-mentioned each embodiment shown in the table 7 and comparative example are filled in the pump bubbling container (1 in 1 in 200 orders and 305 orders); Viscosimetry according to Japanese Pharmacopoeia ordinary test method; Use Brookfield viscometer (NO2 down at 25 ℃; Rotating speed 60rpm, after 30 seconds/Tokyo gauge (strain) makes) measure the foamy bubble viscosity of discharging.The result is shown in Table 7.In addition, see, can be evaluated as above-mentioned bubble viscosity and it is desirable to about 2500～3100mPas from the viewpoint of the quality of the persistence of the sophistication of alveolar substance and bubble.
The quality of-foamy persistence-
The skin abluent and the commercially available skin abluent of above-mentioned each embodiment shown in the table 7 and comparative example are filled in the pump bubbling container (1 in 1 in 200 orders and 305 orders); Get about 5g discharge bubble and put into SV100 pipe (shape) medicine bottle; Fill equably, carry out the evaluation of foam persistence.Bubble after the discharge at mensuration initial stage is foam-filled is high and the bubble after 30 minutes is high.Bubble height to discharge after foam has just been filled is 100 o'clock, according to 5 times meansigma methods, according to following formula, calculates to discharge and steeps the water holdup (%) of filling after 30 minutes.The formula as a result of the following metewand of foundation is in table 7.In addition, skin abluent that we can say than firm filling the water holdup high (the metewand value is high) after intact is the high abluent of foam persistence.
< formula >
Water holdup (%)=[discharging the bubble height after bubble height/discharge foam after foam-filled 30 minutes has just been filled] * 100
< metewand >
5: water holdup is more than 90%
4: water holdup is 71～89%
3: water holdup is 51～70%
2: water holdup is 31～50%
1: water holdup is below 30%
[table 7]
| ? | Bubble viscosity (mPas) | The quality of foam persistence |
| Embodiment 1 | 2800 | 5 |
| Embodiment 5 | 3060 | 5 |
| Embodiment 8 | 3080 | 5 |
| Embodiment 11 | 2500 | 5 |
| Embodiment 15 | 2660 | 5 |
| Embodiment 16 | 2580 | 5 |
| Comparative example 1 | 1800 | 1 |
| Comparative example 2 | 2420 | 4 |
| Comparative example 3 | 2200 | 4 |
| Comparative example 4 | 2320 | 4 |
| Commercially available article A * | 2200 | 4 |
| Commercially available article B ** | 2200 | 4 |
| Commercially available article C *** | 2000 | 1 |
*The main of commercially available article A formed: alkyl (C12-15) potassium phosphate/lauryl dimethyl hydroxypropyl sulfobetaines/1,3 butylene glycol/propylene glycol/glycerol=10/3/2.5/0.3/2 (quality %)
*The main of commercially available article B formed: cocos nucifera oil acyl glycine potassium/undecyl hydroxyethyl imidazoles betanin sodium/propylene glycol/glycerol=13/4/12/8 (quality %)
* *Commercially available article C: plant story Ha one Block Block レ Application De bubble is washed face (Lion Corporation's manufacturing)
Can know that from the result of table 7 skin abluent of the present invention is compared with the skin abluent of comparative example or commercially available skin abluent, bubble viscosity and foam persistence are excellent.Therefore, can know that skin abluent of the present invention is that the foam of from bubbling container, discharging does not disappear (the foam persistence is good) at once, is prone to be coated on the skin abluent on the skin, promptly is the skin abluent that is suitable for hand-washing cleaning.
In addition, the producer of each composition of above-mentioned each embodiment use is as follows.
[table 8]
Utilizability on the industry
Skin abluent of the present invention can be widely used in for example bath gel, handwashing liquid, cleansing milk etc.Especially, skin abluent of the present invention is fine and smooth in alveolar substance, and it is very excellent to clean moist these aspects of skin, back, even for responsive skin also gentleness, is suitable as the skin abluent of the human of baby, young woman, old people or responsive skin.
Again; Skin cleaning method to using above-mentioned skin abluent does not have special restriction; But the viewpoint of cleaning skin from milder ground sees that preferred following hand washing cleaning method does not use implements such as sponge, nylon towel; Get the blister skin abluent of discharging and be placed on hand, clean skin with this foam from bubbling container.
Claims (3)
1. a skin abluent is characterized in that, contains
(A) betanin be amphoteric surfactant,
(B) the N-acyl methyl taurine salt and
(C) PEO alkyl sulfo succinate and alkyl sulfo succinate at least any one,
The above-mentioned content that is equipped with composition is (C)/[(A)+(B)]=0.15～0.4 than by quality ratio,
Said (B) N-acyl methyl taurine salt is selected from more than N-fatty acid distribution of coconut oil methyl tauride, N-lauroyl methyl tauride and N-myristoyl methyl tauride at least a,
Said (C) PEO alkyl sulfo succinate and alkyl sulfo succinate any one has the monovalence alkyl as the carbon number 12～14 of alkyl at least,
Said skin abluent is filled in the bubbling container and forms.
2. a skin cleaning method is characterized in that, uses following skin abluent, and this skin abluent contains
(A) betanin be amphoteric surfactant,
(B) the N-acyl methyl taurine salt and
(C) PEO alkyl sulfo succinate and alkyl sulfo succinate at least any one,
The content of above-mentioned each composition is (C)/[(A)+(B)]=0.15～0.4 than by quality ratio,
Said (B) N-acyl methyl taurine salt is selected from more than N-fatty acid distribution of coconut oil methyl tauride, N-lauroyl methyl tauride and N-myristoyl methyl tauride at least a,
Said (C) PEO alkyl sulfo succinate and alkyl sulfo succinate any one has the monovalence alkyl as the carbon number 12～14 of alkyl at least,
Said skin abluent is filled in the bubbling container and forms.
3. skin cleaning method as claimed in claim 2, the foamed skin abluent that will from bubbling container, discharge with hands is coated on the skin, cleans.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007223518 | 2007-08-30 | ||
| JP2007-223518 | 2007-08-30 | ||
| PCT/JP2008/064651 WO2009028339A1 (en) | 2007-08-30 | 2008-08-15 | Detergent for the skin and method for cleansing the skin with the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101790368A CN101790368A (en) | 2010-07-28 |
| CN101790368B true CN101790368B (en) | 2012-04-25 |
Family
ID=40387065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801052114A Active CN101790368B (en) | 2007-08-30 | 2008-08-15 | Detergent for the skin and method for cleansing the skin with the same |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP5356234B2 (en) |
| KR (2) | KR101444502B1 (en) |
| CN (1) | CN101790368B (en) |
| HK (1) | HK1142279A1 (en) |
| MY (1) | MY155245A (en) |
| TW (1) | TWI448550B (en) |
| WO (1) | WO2009028339A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5796801B2 (en) * | 2010-12-14 | 2015-10-21 | 中野製薬株式会社 | Dye removal method |
| JP5663290B2 (en) * | 2010-12-14 | 2015-02-04 | 中野製薬株式会社 | Dye removal agent composition and dye removal method |
| JP6190239B2 (en) * | 2013-10-15 | 2017-08-30 | クラシエホームプロダクツ株式会社 | Cleaning composition |
| JP6237173B2 (en) * | 2013-12-04 | 2017-11-29 | 日油株式会社 | Liquid detergent composition |
| JP6183849B2 (en) * | 2013-12-12 | 2017-08-23 | クラシエホームプロダクツ株式会社 | Skin cleanser composition |
| JP6937435B2 (en) * | 2018-05-29 | 2021-09-22 | ライオン株式会社 | Skin cleanser composition |
| JP7466939B2 (en) | 2022-08-31 | 2024-04-15 | 東洋ビューティ株式会社 | O/D Phase Composition and Oil-in-Water Emulsion Composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007009092A (en) * | 2005-06-30 | 2007-01-18 | Toho Chem Ind Co Ltd | Cationically modified gellan gum and cosmetic composition containing the same |
| CN1914229A (en) * | 2004-01-30 | 2007-02-14 | 东邦化学工业株式会社 | Cation-modified purified galactomannan polysaccharide and cosmetic composition containing the substance |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08183729A (en) * | 1994-12-29 | 1996-07-16 | Kao Corp | Article for cleansing skin |
-
2008
- 2008-08-15 WO PCT/JP2008/064651 patent/WO2009028339A1/en active Application Filing
- 2008-08-15 JP JP2009530050A patent/JP5356234B2/en active Active
- 2008-08-15 CN CN2008801052114A patent/CN101790368B/en active Active
- 2008-08-15 MY MYPI2010000825A patent/MY155245A/en unknown
- 2008-08-15 KR KR1020107005395A patent/KR101444502B1/en active IP Right Grant
- 2008-08-15 KR KR1020147019928A patent/KR20140102316A/en not_active Application Discontinuation
- 2008-08-26 TW TW097132570A patent/TWI448550B/en active
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2010
- 2010-09-17 HK HK10108884.0A patent/HK1142279A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1914229A (en) * | 2004-01-30 | 2007-02-14 | 东邦化学工业株式会社 | Cation-modified purified galactomannan polysaccharide and cosmetic composition containing the substance |
| JP2007009092A (en) * | 2005-06-30 | 2007-01-18 | Toho Chem Ind Co Ltd | Cationically modified gellan gum and cosmetic composition containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1142279A1 (en) | 2010-12-03 |
| KR20100061674A (en) | 2010-06-08 |
| CN101790368A (en) | 2010-07-28 |
| TWI448550B (en) | 2014-08-11 |
| JP5356234B2 (en) | 2013-12-04 |
| KR101444502B1 (en) | 2014-09-24 |
| MY155245A (en) | 2015-09-30 |
| KR20140102316A (en) | 2014-08-21 |
| TW200911980A (en) | 2009-03-16 |
| JPWO2009028339A1 (en) | 2010-11-25 |
| WO2009028339A1 (en) | 2009-03-05 |
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