CN101288631A - Skin cleaning agent composite - Google Patents
Skin cleaning agent composite Download PDFInfo
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- CN101288631A CN101288631A CNA2008100908020A CN200810090802A CN101288631A CN 101288631 A CN101288631 A CN 101288631A CN A2008100908020 A CNA2008100908020 A CN A2008100908020A CN 200810090802 A CN200810090802 A CN 200810090802A CN 101288631 A CN101288631 A CN 101288631A
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Abstract
A skin cleansing composition contains the following ingredients (A), (B) and (C): (A) a polyoxyethylene alkylether sulfate, (B) a polyoxyethylene alkylether carboxylate, and (C) a cationic group-containing polymer having a cationic charge density of not less than 4.5 meq/g, and/or polyvinylpyrrolidone. A weight ratio (A):(B) of the ingredient (A) to the ingredient (B) is from 85:15 to 25:75. A total content of the ingredients (A) and (B) based on the whole composition ranges from 5 to 25 wt %. A content of the ingredient (C) ranges from 0.05 to 1 wt %. The skin cleansing composition is excellent in foamability and foam quality, and provides a good stop feeling during rinsing and a refreshed touch feeling after towel blotting.
Description
Technical field
The present invention is relevant skin cleaning agent composite.
Background technology
In the middle of many performances to the skin cleaning agent that is used for cleaning face and whole body, as the sensation during flushing in the use, importantly have frictional resistance sense of touch (sense that pauses, stopfeeling).In when flushing, until feeling that the time till this pauses sense is short, and its intensity can be given salubrious sense, therefore preferably when strong.
In the prior art, the surfactant of extensive use is the skin cleaning agent composite of polyoxyethylene alkyl ether sulfate salt as host in this field, though its foaming characteristic is good, has the problem of residual slimy sensation when flushing.In patent documentation 1 and 2, put down in writing, in the agent compositions of removing ornaments and formal dress as the individual of host with the water soluble surfactant active of polyoxyethylene alkyl ether sulfate salt etc., by adding the water-insoluble oil of polyisobutylene and silicone wet goods, thus the flushing sense when giving the flushing of improvement.; if so the oiliness composition is added in the skin cleaning agent composite; particularly under situation about using in order to clean whole body; pause sensation during flushing just becomes abundant inadequately; after flushing, give the residual sense and the oiliness sense of skin stronger; so have the sense of being clamminess, can not get salubrious sense of touch.
In patent documentation 3 and patent documentation 4, put down in writing and contained the specific surfactant and the cleansing composition of cation property copolymer.Such cation property copolymer is used the comb general character of finger when improving flushing as the adjustment agent that reduces crude sense in hair cleansing.In addition, in skin cleaning agent, also use as the adjustment agent that skin is preserved moisture.But these cleansing compositions are in the purposes that skin is cleaned, and the viewpoint of the pause sense during from flushing can not fully meet the demands.
Patent documentation 1: Japanese Unexamined Patent Application Publication 2001-513539 communique
Patent documentation 2: Japanese Unexamined Patent Application Publication 2001-513538 communique
Patent documentation 3: Japanese kokai publication hei 2-42013 communique
Patent documentation 4: Japanese kokai publication hei 9-165598 communique
Summary of the invention
The present invention provides a kind of skin cleaning agent composite, and it contains following ingredients (A), (B) and (C):
(A) polyoxyethylene alkyl ether sulfate salt
(B) polyoxyethylene alkyl ether carboxylate
(C) cationic charge density is above polymer that contains cation radical and/or a polyvinylpyrrolidone of 4.5meq/g,
Composition (A) and mass ratio (B) they are (A): (B)=85: 15～25: 75, composition (A) and total content (B) in all forming they are 5～25 quality %, the content of composition (C) is 0.05～1 quality %.
Skin cleaning agent composite of the present invention bubbles rapidly, foam volume and alveolar substance brilliance, and the pause sense during flushing is good, and has salubrious sense after doing toweling off.In addition, owing to contain polyvinylpyrrolidone, further improved the pearly-lustre sense.Further, by containing higher fatty acids or higher alcohol, during bath towel after flushing is used and the defoaming in the gutter during flushing become good.
The specific embodiment
The invention relates to a kind of skin cleaning agent composite, the pause sense when it has remarkable foaming characteristic and alveolar substance, flushing is good, towel off and have salubrious sense after doing.
The present inventor finds, by being used in combination polyoxyethylene alkyl ether sulfate salt and polyoxyethylene alkyl ether carboxylate and specific polymer that contains cation radical or polyvinylpyrrolidone, the skin cleaning agent composite of the above-mentioned problem that just can be resolved.
As the polyoxyethylene alkyl ether sulfate salt of employed composition (A) in the present invention, preferably with the represented material of following formula.
R-O(CH
2CH
2O)
n-SO
3X
In the formula, R represents the alkyl or alkenyl of carbon number 10～18; N represents average, is 0.5～5 number; X represents hydrogen atom, alkali metal, alkaline-earth metal, ammonium or organic ammonium.
In the formula, as the alkyl of the preferred carbon number 12～14 of R.In addition, the average addition molal quantity of oxirane is 0.5～5, but is preferably 1～4.
In addition, can enumerate the alkali metal of sodium and potassium etc. as X; The alkaline-earth metal of calcium and magnesium etc.; Ammonium; The ammonium that comes from the alkanolamine of monoethanolamine, di-methylcarbinol amine and triethanolamine etc.; Come from the cation of alkali type amino acids such as arginine and lysine etc.
Composition (A) can use more than a kind, is preferably containing 1～20 quality % in full group, and 3～13 quality % more preferably are because brilliance aspect the pause sense of this moment when lather quickness, foam volume and flushing.
As the polyoxyethylene alkyl ether carboxylate of composition (B), the material that preferably is expressed from the next.
R-O(CH
2CH
2O)
nCH
2-COOX
In the formula, R represents the alkyl or the thiazolinyl of carbon number 10～18; N represents average, is 0.5～10 number; X represents hydrogen atom, alkali metal, alkaline-earth metal, ammonium or organic ammonium.
In the formula, as the R alkyl of carbon number 12～16 more preferably.In addition, the average addition molal quantity of oxirane is 0.5～10, but more preferably 1～6.
In addition, can enumerate the alkali metal of sodium and potassium etc. as X; The alkaline-earth metal of calcium and magnesium etc.; Ammonium; The ammonium that comes from the alkanolamine of monoethanolamine, di-methylcarbinol amine and triethanolamine etc.; Come from the cation of alkali type amino acids such as arginine and lysine etc.
Composition (B) can use more than a kind, is preferably containing 1～20 quality % in full group, and 1.5～10 quality % more preferably are because brilliance aspect the pause sense of this moment when foam volume alveolar substance and flushing.
In the present invention, composition (A) and mass ratio (B) they are (A): (B)=85: 15～25: 75, be preferably 75: 25～35: 65.If in this scope, so brilliance aspect the pause sense when foaming characteristic, foam volume and flushing so is preferred.
In addition, composition (A) and total content (B) in all forming are 5～25 quality %, are preferably 7.5～20 quality %.If in this scope, so brilliance aspect foaming characteristic, foam volume and alveolar substance so is preferred.
In the present invention, use mentioned component (A) and (B) time, also being used in combination composition (C) cationic charge density is above polymer that contains cation radical and/or polyvinylpyrrolidone of 4.5meq/g.
At this, so-called cationic charge density is meant the equivalents (meq/g) of the cationic charge in the monomer unit that constitutes polymer.
The cationic charge density that contains the polymer of cation radical is more than the 4.5meq/g, and is preferred 4.5～7, more preferably 5～7, most preferably 5.5～6.5.If have the material of the high-cation charge density of this scope, the pause sense the during flushing of cleansing composition is good so.Especially preferably the amphiphilic polymers that except containing above-mentioned cation radical, also contains anion base.
Wherein, be the polymer that contains cation radical more than the 4.5meq/g as positive ion density, such as the homopolymer that can enumerate dimethyl diallyl ammonium chloride; The monomeric copolymer of other of dimethyl diallyl ammonium chloride and (methyl) acrylic acid, (methyl) acrylate, (methyl) acrylamide etc.; Polymethyl acyl chlorides oxy-ethyl-trimethyl salmiac etc.
Particularly, can enumerate the homopolymer (Merquat100 of dimethyl diallyl ammonium chloride; Charge density 6.2meq/g), (Merquat 295 for dimethyl diallyl ammonium chloride and acrylic acid copolymer オ Application デ オ Na Le コ society system:; Charge density 5.9meq/g), dimethyl diallyl ammonium chloride and acrylic acid copolymer (Merquat280 オ Application デ オ Na Le コ society system:; Charge density 5.0meq/g), (Kao Corp makes polymethyl acyl chlorides oxy-ethyl-trimethyl salmiac: charge density 4.8meq/g) オ Application デ オ Na Le コ society system:.
Consider from the corrosion resistance aspect of manufacturing equipment, the homopolymer of preferred dimethyl diallyl ammonium chloride, with dimethyl diallyl ammonium chloride and acrylic acid copolymer, especially dimethyl diallyl ammonium chloride and acrylic acid copolymerization ratio be 95: 5 copolymer (above-mentioned Merquat295; オ Application デ オ Na Le コ society makes: the aspect of the pause sense during charge density 5.9meq/g) for flushing and the amount of bubble and preferred.
In addition, in composition (C), as polyvinylpyrrolidone, because the pause sense brilliance in when flushing, so its K value is preferably 10～100, more preferably 15～90.At this, so-called K value is the intrinsic viscosity that derives as the formula of the Fikentscher of the function representation of concentration from the viscosity with polyvinylpyrrolidonesolution solution.The kind of polyvinylpyrrolidone is by this K value representation, and it becomes the supposition of the cardinal principle of molecular weight.
Composition (C) can use more than a kind, and also can be used in combination cationic charge density is above polymer that contains cation radical and polyvinylpyrrolidone of 4.5meq/g.Composition (C) contains 0.05～1 quality % in full the composition, preferably contain 0.075～1 quality %.If in this scope, so brilliance aspect the pause sense in when flushing so is preferred.
As composition (C), be used in combination under the situation that cationic charge density is polymer that contains cation radical more than the 4.5meq/g and polyvinylpyrrolidone, pause sense and the good viewpoint of liquid appearance during from flushing, its mass ratio is preferred, cationic charge density is the above polymer that contains cation radical of 4.5meq/g: polyvinylpyrrolidone=90: 10～20: 80, more preferably 80: 20～25: 75.
Skin cleaning agent composite of the present invention can further contain (D) inorganic salt or the acylate of carbon number below 6.Can enumerate the salt of alkali metal, alkaline-earth metal and halogen, sulphuric acid, sulfurous acid and phosphoric acid etc. as inorganic salt.Particularly, can enumerate sodium chloride, potassium chloride, sodium bromide, magnesium chloride, sodium sulfate, potassium sulfate, sodium dihydrogen phosphate and sodium hydrogen phosphate etc.In addition, as acylate, can also enumerate acetic acid, the salt of the hydroxy acid of lactic acid, malic acid, citric acid, succinic acid etc. and polyprotic acid and alkali metal etc.In the middle of these, be preferably sodium chloride, natrium malicum, sodium lactate, sodium citrate and sodium succinate.
Composition (D) can use more than a kind in the scope of foaming characteristic that does not hinder effect of the present invention and alveolar substance, from by composition (A), (B) and (C) complex of the slightly solubility that forms of 3 compositions of (particularly cationic charge density is the polymer that contains cation radical more than the 4.5meq/g) can be easily dissolved, improve the viewpoint of pausing sense and improving liquid appearance (transparency), the amount of composition (D) in full the composition is preferably 0.5～10 quality %, more preferably 0.5～6 quality %.
In the present invention, composition (A) and mass ratio (B) they are (A): (B)=85: 15～25: 75, the complex that is formed by composition (A), (B) and 3 compositions (C) becomes and dissolves easily in this case, (C)/[(A)+(B)] value is under 0.025～0.08 situation, and complex becomes and is more prone to dissolving.
Also have, by containing (D) inorganic salt or the acylate of carbon number 6 below, the complex that is formed by composition (A), (B) and 3 compositions (C) becomes and is more prone to dissolve.Viewpoint from improving dissolubility, stability and embodying pearly luster etc. easily, be more preferably (D)/value of [(A)+(B)+(C)] is in 0.19～0.34 scope.Skin is separated out and be adsorbed in to dissolved complex in the process of dilution, so the very fast disappearance of clammy sensation, the sense that pauses also further is improved, so preferred.Preferred especially (A), (B) and (C) cationic charge density be above polymer that contains cation radical of 4.5meq/g and (D) combination of inorganic salt.
Skin cleaning agent composite of the present invention can further contain (E) higher fatty acids and/or higher alcohol.At this, higher fatty acids and higher alcohol are preferably the material of the carbon number 10～18 of straight chain, the more preferably material of carbon number 12～15 respectively.
By containing these compositions, usually the amount that can suppress to steep under the situation of the dilution ratio more taller than the dilution ratio of the detergent of clean health all can become good so remain in the foamy froth breaking easiness (the broken bubble) that residues in discharge outlet behind foamy froth breaking easiness (broken bubble) on the bath towel after the use and the flushing health.
In addition, as aftermentioned, skin cleaning agent composite of the present invention preferably shows the pH value of faintly acid～neutral region.In said composition, higher fatty acids is not the fatty acid soaps of the form of salt, but is contained in the compositions with lipid (free fatty) form, usually, in cleaning the dilution ratio zone of health, think that it helps the raising of performance of the bubble of the texture of steeping etc.
Composition (E) can use more than a kind, also can be used in combination higher fatty acids and higher alcohol.Further, from putting forward high foaming performance and having the viewpoint of the effect of good froth breaking simultaneously, preferred compositions is used lauric acid and myristyl alcohol.
Composition (E) preferably contains 0.3～3 quality % in full constituent, more preferably 0.5～2 quality %.
Skin cleaning agent composite of the present invention can further contain composition (F) pearly luster imparting agent.
Can enumerate the fatty acid of carbon number 16～22 and the ester of ethylene glycol (single, two) as the pearly luster imparting agent, the fatty acid of carbon number 16～22 and have the ester etc. of the unitary Polyethylene Glycol of polyoxyethylene (1～7).Also has the glycol ester of the fatty acid of preferred carbon number 16～18 (single, two).
More specifically, can enumerate for example ethylene glycol fatty acid ester of ethylene glycol monostearate and glycol monomethyl behenic acid ester etc.; The ethylene glycol bis fatty acid ester of Ethylene Glycol Distearate and ethylene glycol bis behenic acid ester etc.
The pearly luster imparting agent can use more than a kind, from the good viewpoint of pearly luster sense, preferably contains 1～3 quality % in full constituent, more preferably 1.5～2.5 quality %.
Skin cleaning agent composite of the present invention in the scope that does not hinder effect of the present invention, can also contain other the surfactant that is generally used in the cleansing composition except above-mentioned composition.Particularly can enumerate for example cationic surfactant of alkylbenzenesulfonate, alpha-alkene sulfonate, alkane sulfonate, alpha-sulfo fatty acid ester salt, acylated amino salt, alkylphosphonate, acyl group-L-glutamate, Glu etc.; The non-ionic surface active agent of the two alkanolamides of polyoxyalkylene alkyl, alkyl polyglucoside, fatty acid monoalkylol amide or fatty acid, polyoxyalkylene type block copolymer, fatty acid glyceride, alkyl glycerylether etc.; The cationic surfactant of quaternary ammonium salt etc.; The amphoteric surfactant of carboxybetaine class, sulfobetaines class, imidazolinium betaine class, hydroxyl betaines, fatty acid amide betaines etc.
Skin cleaning agent composite of the present invention further can also contain the various compositions that are generally used in the cleansing composition according to necessity.Particularly, can enumerate for example wetting agent of propylene glycol, dipropylene glycol, glycerol and Sorbitol etc.; The solvent of water and ethanol etc.; The viscosity modifier of methylcellulose etc.; The antibacterial of triclosan, triclocarban etc.; The anti-inflammatory agent of dipotaccium glycyrrhizate and alpha-tocopherol acetate etc.; The antiseptic of methyl parahydroxybenzoate, butyl p-hydroxybenzoate, phenyl phenol and benzoate etc.; Other pigment, spice, UV absorbent and antioxidant etc.
Skin cleaning agent composite of the present invention can be according to usual way, by weighing allotment composition, in any order it is mixed in water or with water as main body and comprise in the aqueous medium of other water-soluble solvents of alcohol etc. and make.Thereby can use as bathing shampoo, wash one's face agent and cleansing product etc.
Skin cleaning agent composite of the present invention preferably is adjusted to faintly acid, and this moment is little to the stimulation of skin, and remarkable cleaning strength can not be suffered damage and the foaming characteristic when clean becomes well, brilliance aspect pause sense when washing and the use feeling.
So-called faintly acid is meant that pH is 4.5～7, is preferably pH4.5～6.5.In the present invention, pH is the value under 25 ℃ of temperature conditions of expression when being diluted to 20 times of quality with ion exchange water.
Embodiment
Embodiment 1～32, comparative example 1～13
Make the skin cleaning agent composite of the composition shown in table 1～table 9, feel when estimating flushing pause speed till the sense, the pause sense when flushing finishes intensity, towel off the salubrious sense after doing and the amount of bubble.In addition, in the embodiment of a part, dried smooth feeling, pearly-lustre sense, broken bubble and liquid appearance have also been done evaluation.At last with the result respectively combined statement be shown in table 1～table 9.
Manufacture method
Composition shown in the weighing table also joins it in ion exchange water, stirs fully under 50 ℃ temperature conditions, thereby obtains skin cleaning agent composite.Add an amount of sodium hydroxide or malic acid, the pH that is adjusted into 20 times diluent becomes faintly acid.At this, pH is diluted to 20 times and obtain after the aqueous solution of 5 quality % with ion exchange water with compositions, uses pH tester (HORIBA makes, model F-22) to measure.
Evaluation methodology
(1) the speed (preceding wrist cleaning evaluation) till the sense of pausing is felt the time in flushing:
Get each cleansing composition 1.0g in one on hand, with the tap water dilution and afterwash two wrists (from the elbow to the front end) that make it to bubble, wash with tap water.At this moment, while the wrists that rub before two wash, measure until feel the sense of pausing being arranged till the time the friction number of times.Standard is carried out classification according to following metewand to measurement result.
5: the friction number of times is less than 3 times.
4: the friction number of times is less than 6 times more than 3 times.
3: the friction number of times is less than 9 times more than 6 times.
2: the friction number of times is less than 12 times more than 9 times.
1: the friction number of times is more than 12 times.
The intensity (whole body cleaning evaluation) of the pause sense when (2) flushing finishes:
Use for 1 day 1 time each cleansing composition to clean whole body by 10 professional estimators.Continuous like this carrying out 3 days estimated the intensity of washing the pause sense when finishing, and represented the result of determination of 3 days overall merit by following benchmark.
◎: have the pause sense when 8 people are above to answer the flushing end strong.
Zero: the pause sense when having 5～7 people to answer the flushing end is strong.
△: the pause sense when having 2～4 people to answer the flushing end is strong.
*: have no talent or to have 1 people to answer the pause sense of flushing when finishing strong.
(3) towel off salubrious sense (whole body cleaning evaluation) after doing:
Use for 1 day 1 time each cleansing composition to clean whole body by 10 professional estimators.Continuous like this carrying out 3 days estimated the salubrious sense that towels off after doing, and represented the result of determination of 3 days sum total evaluation by following benchmark.
◎: there have the above answer of 8 people to towel off dried aftersensation to be salubrious.
Zero: there have 5～7 people's answers to towel off dried aftersensation to be salubrious.
△: there have 2～4 people's answers to towel off dried aftersensation to be salubrious.
*: have no talent or have 1 people to answer to towel off dried aftersensation salubrious.
(4) Pao amount:
To be diluted to 150 times (conditions when being equivalent to clean health) as the sample aqueous solution with 4 degree hard water at each embodiment and the synthetic compositions of comparative example.Band bottle stopper at 50mL also adds sample solution 7.5ml and covers bottle stopper in the graduated glass cylinder pipe, (IWAKI of Co., Ltd. industry is made to use vibrator, model universal shaking machine V-SX), vibrates 30 seconds, read the bubble amount after vibration finishes with the speed of 300 strokes/minute.
(5) dried smooth feeling:
Use for 1 day 1 time each cleansing composition to clean whole body by 10 professional estimators.Continuous like this carrying out 3 days estimated dried smooth feeling, represented the result of determination of 3 days overall merit by following benchmark.
◎: have the dry aftersensation of the above answer of 8 people smooth.
Zero: there have 5～7 people to answer dry aftersensation to be smooth.
△: there have 2～4 people to answer dry aftersensation to be smooth.
*: have no talent or to have 1 people to answer dry aftersensation smooth.
(6) pearly-lustre sense:
Outward appearance when joining cleansing composition in the vial is particularly estimated with visual the pearly-lustre sense.Standard is carried out classification according to following benchmark to evaluation result.
A: the reflecting feel that Margarita is arranged.
B: the reflecting feel of Margarita is more weak.
C: the reflecting feel that does not have Margarita.
(7) broken bubble:
Will be in each embodiment and comparative example synthetic cleansing composition, be diluted to the high magnification (400 times) of the broken bubble after the imagination flushing with 4 degree hard water, as the sample aqueous solution.The sample solution of 7.5mL is joined in 50mL band bottle stopper and the graduated glass cylinder pipe, (IWAKI of Co., Ltd. industry is made to use vibrator, model universal shaking machine V-SX), vibrates 30 seconds, read vibration bubble amount (cm) afterwards with the speed of 300 strokes/minute.
(8) liquid appearance:
Outward appearance when joining cleansing composition in the vial (transparent feel) with visual valuation.Standard is carried out classification according to following benchmark to evaluation result.
A: transparent feel is arranged.
B: transparent feel is more weak.
C: do not have transparent feel.
Embodiment 33
The method identical with embodiment 1～32 made the bathing shampoo of composition shown below.
Table 10
Embodiment 34
The method identical with embodiment 1～32 made the bathing shampoo of composition shown below.
Table 11
Embodiment 35
The method identical with embodiment 1～32 made the bathing shampoo of composition shown below.
Table 12
Embodiment 36
The method identical with embodiment 1～32 made the bathing shampoo of composition shown below.
Table 13
The bathing shampoo that obtains among the embodiment 33～36 all demonstrates good foaming characteristic and alveolar substance, and the pause sense in when flushing and the salubrious sense that towels off after doing are also all good.In addition, the pearly-lustre sense is also good.
Claims (6)
1. skin cleaning agent composite is characterized in that:
Contain following ingredients (A), (B) and (C):
(A) polyoxyethylene alkyl ether sulfate salt
(B) polyoxyethylene alkyl ether carboxylate
(C) cationic charge density is above polymer that contains cation radical and/or a polyvinylpyrrolidone of 4.5meq/g,
Composition (A) and mass ratio (B) they are (A): (B)=85: 15～25: 75, composition (A) and total content (B) in all forming they are 5～25 quality %, the content of composition (C) is 0.05～1 quality %.
2. the skin cleaning agent composite of putting down in writing as claim 1 is characterized in that:
The polymer that contains cation radical of composition (C) is the homopolymer of dimethyl diallyl ammonium chloride, perhaps dimethyl diallyl ammonium chloride and acrylic acid copolymer.
3. as claim 1 or 2 skin cleaning agent composites of being put down in writing, it is characterized in that:
Also contain (D) inorganic salt or the acylate of carbon number below 6.
4. as any skin cleaning agent composite of being put down in writing in the claim 1～3, it is characterized in that:
Also contain (E) higher fatty acids or higher alcohol.
5. as any skin cleaning agent composite of being put down in writing of claim 1～4, it is characterized in that:
Also contain (F) pearly luster imparting agent.
6. as any skin cleaning agent composite of being put down in writing of claim 1～5, it is characterized in that:
PH when being diluted to 20 quality times with ion exchange water is 4.5～7.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007111423 | 2007-04-20 | ||
| JP2007111424 | 2007-04-20 | ||
| JP2007-111424 | 2007-04-20 | ||
| JP2007-111423 | 2007-04-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101288631A true CN101288631A (en) | 2008-10-22 |
| CN101288631B CN101288631B (en) | 2013-01-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810090802 Active CN101288631B (en) | 2007-04-20 | 2008-04-02 | Skin cleaning agent composite |
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| Country | Link |
|---|---|
| JP (1) | JP2008285480A (en) |
| CN (1) | CN101288631B (en) |
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| CN103796629A (en) * | 2011-09-02 | 2014-05-14 | 花王株式会社 | Skin cleanser composition |
| CN103800213A (en) * | 2012-11-08 | 2014-05-21 | 花王株式会社 | Detergent composition |
| CN104159564A (en) * | 2012-03-07 | 2014-11-19 | 花王株式会社 | Skin washing composition |
| CN106473948A (en) * | 2015-09-02 | 2017-03-08 | 花王株式会社 | Cleanser compositions |
| CN106473938A (en) * | 2015-09-02 | 2017-03-08 | 花王株式会社 | Cleanser compositions |
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| JP6538342B2 (en) * | 2014-12-16 | 2019-07-03 | クラシエホームプロダクツ株式会社 | Pearl-like gloss composition |
| JP6538343B2 (en) * | 2014-12-16 | 2019-07-03 | クラシエホームプロダクツ株式会社 | Pearl-like gloss composition |
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| CN106473948B (en) * | 2015-09-02 | 2021-08-27 | 花王株式会社 | Detergent composition |
Also Published As
| Publication number | Publication date |
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| CN101288631B (en) | 2013-01-02 |
| JP2008285480A (en) | 2008-11-27 |
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