The specific embodiment
The present invention is a kind of anti-dandruff shampoo composition, comprises by weight percentage: surfactant 5.0%~50.0%, unsaturated fatty alcohol (acid) ester 0.01%~10.00%, dandruff removing agent 0.1%~5.0%, aqueous carrier surplus.
Surface active agent composition of the present invention is selected from a kind of in anion surfactant, the amphoteric surfactant or their combination.
The suitable anion surfactant that is used for the present composition comprises known hair-care or other personal care cleansing of can be used for.The anion surfactant component concentrations should be enough to the cleaning and the foaming effect that provide required in the compositions, and mass concentration is generally 5% to about 50%, preferred about 8% to about 30%, and more preferably from about 10% to about 25%, even more preferably from about 12% to about 18%.
Be applicable to that preferred anionic surfactants surfactant of the present invention is alkyl or alkyl ether sulfate.These materials have formula ROSO separately
3M and RO (C
2H
4O)
XSO
3M, wherein R is about 8 alkyl or alkenyls to about 18 carbon atoms, x is that value is 1 to 10 integer, and M is cation, as ammonium, alkanolamine, as triethanolamine, the monovalence metal is as sodium ion and potassium ion.In alkyl and alkyl ether sulfate, R has preferred about 8 to about 18 carbon atoms, and more preferably from about 10 to about 16 carbon atoms, even more preferably from about 12 to about 14 carbon atoms.This alkyl ether sulfate typically can be used as oxirane and has the about 8 condensation product preparations to the monohydric alcohol of about 24 carbon atoms.Monohydric alcohol and 0 to about 10 moles, preferred about 2 to 5 moles, the mixture of the more preferably from about reacting ethylene oxide of 3 mol ratios, and gained molecular species has about 3 moles of ethylene oxide of for example average every mol of alcohol by sulphation and neutralization.
Other suitable anionic detersive surfactant is to meet formula [RSO
3M] the water soluble salt of organic sulfur acid reaction product, wherein R is to have about 8 to about 24 carbon atoms, preferred about 10 straight chain or side chain, radical of saturated aliphatic alkyl to about 18 carbon atoms; And M is a cation mentioned above.
Other anionic detersive surfactant that is suitable for is a succinate, embodiment comprises N one disodium octadecyl sulfosuccinate, lauryl disodium sulfosuccinate, lauryl 2-Sulfosuccinic acid diammonium, N-(1,2 one dicarboxyl ethyl)-N one octadecyl 2-Sulfosuccinic acid four sodium, the diamyl vinegar of sodium sulfosuccinate, the dihexyl vinegar of sulfo group coloured glaze succinum sodium, dioctyl vinegar of 2-Sulfosuccinic acid sodium salt or the like.
The preferred anionic surfactants detersive surfactant that is used for the present composition comprise lauryl sulphate acid by, laureth sulphuric acid is pressed, the lauryl sulfate triethylamine, laureth sulphuric acid triethylamine, triethanolamine lauryl sulfate, laureth sulphuric acid triethanolamine, lauryl sulfate monoethanolamine, laureth sulphuric acid monoethanolamine, lauryl sulfate diethanolamine, laureth sulphuric acid diethanolamine, lauric acid glycerol list vinegar sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, lauryl potassium sulfate, the laureth potassium sulfate, sodium lauryl sarcosinate, Laurel phthalein sodium sarcosinate, month a few propylhomoserin Laurel vinegar, the cocoyl sarcosine, cocoyl sulphuric acid is pressed, dodecane phthalidyl sulphuric acid is pressed, cocoyl sodium sulfate, Laurel phthalidyl sodium sulfate, the cocoyl potassium sulfate, lauryl potassium sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, cocoyl sulphuric acid monoethanolamine, the lauryl sulfate monoethanolamine, the tridecyl benzene sulfonic acid sodium salt, dodecylbenzene sodium sulfonate, one or more combinations in the cocoyl sodium isethionate.
Be suitable for amphoteric surfactant of the present invention and comprise known those of hair-care or other personal care cleansing of being used for.The mass concentration of above-mentioned amphoteric detersive surfactants is preferably about 0.5% to about 20%, preferred about 1% to about 5%.Suitable amphoteric surfactants is described to those surfactants of the derivant of aliphatic secondary amine or tertiary amine, wherein aliphatic group can be a straight or branched, and one of them aliphatic substituent group comprises about 8 to about 18 carbon atoms, and an aliphatic substituent group comprises anionic group, as carboxyl, sulfonate radical, sulfate radical, phosphate radical.Be used for preferred amphoteric surfactant of the present invention and comprise N-cocamidopropyl ethyl-N hydroxyethyl acetate, N-cocamidopropyl ethyl-N hydroxyethyl diacetin, N-lauroyl amido ethyl-N hydroxyethyl acetate, N-lauroyl amido ethyl-N hydroxyethyl diacetin, and their mixture.Zwitterionic compound such as betanin are preferred.
Being suitable for unsaturated fatty acid of the present invention (alcohol) ester is a kind of ester of gained after unsaturated fatty acid (alcohol) and monobasic or polynary organic alcohol (acid) esterification, but do not contain conjugated linoleic acid, only, attach being incorporated in the compositions in addition as the micro constitutent of other solvent or optional components.Unsaturated fatty acid in this compositions (alcohol) ester content is 0.01%-10.00% by weight percentage, preferably at 0.05%-5.00%, more preferably at 0.10%-3.7%, most preferably at 0.12%-2.34%.Unsaturated fatty acid (alcohol) is the straight or branched with 8-40 carbon atom, has more than one unsaturated bond, and for liquid, index of refraction is more than 1.46 in the time of 25 ℃ down for room temperature.Preferably have conjugated unsaturated bonds, index of refraction is more than 1.47; For with anti-dandruff dose of non-hydrophilic particle be the combined system of pyrithione slaine, more preferably have the fatty acid (alcohol) of conjugated unsaturated bonds.Unsaturated fatty acid (alcohol) the ester non-limiting example that is fit to comprises, two oleic acid phosphate esters, oleyl alcohol ether-5 phosphate ester, olein, linoleic acid Malaysia ester, linolenic acid Malaysia ester, arachidic acid glyceride, Oleum Ricini Malaysia ester and all kinds of natural oil olive oil that contains these unsaturated fatty acids alcohol esters, Oleum sesami, safflower oil, American Avocado Tree oil or the like, preferred Oleum Ricini maleate and two oleic acid phosphate esters, oleyl alcohol ether-5 phosphate ester.
Be applicable to that it is 0.1%-5.0% that dandruff removing agent of the present invention accounts for the shampoo composite percentage by weight, is preferably 0.2%-3.5%, more preferably at 0.3%-3.0%.
Be applicable to anti-dandruff dose of at least two kinds of comprising in the following material of the present invention: pyrithione slaine, selenium sulfide, sulfur, coal tar, than Roc ketone ethanolamine salt (Octopirox), iodine propilolic alcohol butyl mephenesin Carbamate (IPBC), climbazole, hexamidine two (hydroxyethylsulfonic acid .) salt, hexamidine two PARABEN salt, hexamidine PARABEN salt.Preferred anti-dandruff dose is that a kind of crystal powder and hexamidine two (hydroxyethylsulfonic acid .) salt in Zinc Pyrithione (ZPT), selenium sulfide, the sulfur gets compositions, and preferred anti-dandruff dose is the two compositions of Zinc Pyrithione (ZPT) and hexamidine two (hydroxyethylsulfonic acid .) salt.ZPT is a crystal powder, and particle diameter is controlled at D10>0.19 micron, D50=0.37-0.53 micron, D90<1 micron, does abundant dissolving and dispersion with aforementioned unsaturated fatty acids alcohol ester before use.Guarantee that Zinc Pyrithione (ZPT) is to be in the state that dissolves saturated and abundant moistening in the unsaturated fatty acids alcohol ester.Zinc Pyrithione (ZPT) and the weight ratio of hexamidine two (hydroxyethylsulfonic acid .) salt in compositions 300: 1 to 1: 10; Preferably at 258: 1 to 1: 8; More preferably at 200: 1 to 1: 5.
The form of the liquid that the present composition (under environmental condition) is dumpable typically.Therefore, said composition will typically comprise aqueous carrier, and its content is about 50% to about 95%, preferred about 60% to about 85%.Aqueous carrier can comprise water or can miscible water and the mixture of organic solvent, but comprises that also all kinds of homogeneous are dispersed or dissolved in polymer in the compositions, non-ionic surface active agent, emulsified silicone oil, amido silicon oil, cation opsonizing agent or the like additive.
Help polymer of the present invention and comprise that hydrolyzed protein mainly contains hydrolyzed silk protein, hydrolyzed wheat protein, hydrolyzed gluten, hydrolyzed soybean protein, hydrolytic collagen, hydrolysis of keratin, elastin hydrolysis, hydrolysis milk proem etc., the molecular weight of described hydrolyzed protein is between 3000D to 5000D, and preferred molecular weight is between 3500D to 4500D; The hydrolyzed protein derivant comprises: Laurel hydroxypropyl hydrolyzed protein alkyl dimethyl ammonium chloride, cocoyl hydroxypropyl hydrolyzed protein alkyl dimethyl ammonium chloride, hydroxypropyl hydrolyzed protein trimethyl ammonium chloride etc.
Help non-ionic surface active agent of the present invention and account for composition weight 0.2% to 5.0%, preferred 0.5% to 2.5%.This non-ionic surface active agent is meant the surfactant with prolongation and stable foam, mainly is selected from fatty acid alkanol amides, preferred coconut oil single ethanol amide.
Being applicable to that emulsified silicone oil of the present invention is a polydimethylsiloxane, is the mixture of nonvolatile silicone rubber resina and polydimethylsiloxane, it comprise viscosity in the time of 25 ℃ more than or equal to 800000mm
2.s
-1With less than 10000mm
2.s
-1The polysiloxane mixtures of material.Its detailed description comprises US 4152416 that authorized people such as Spitzer on May 1st, 1979 and the Chemistry and Technologyof silicones that Noll, Walter are shown, New York:Academic Press 1968. describes General Electric (now renaming Momentive Performance Material company as) SiliconeRubber Product Data Sheets ES30, SE33, SE54 and the SE76 in addition of silicone rubber in addition.The molal weight of typical case's silicone rubber is more than 150000, general between between in 150000 to 900000, instantiation comprises polydimethylsiloxane, poly-(dimethyl siloxane, ethylene methacrylic radical siloxane) copolymer and their mixture.It also is included in the preparation siloxanes process by trifunctional or four functional silane are sneaked into the crosslinked polymer siloxane that obtains in simple function or the two functional silane.Each silicon atom has about 1.1 oxygen atoms at least, preferably between 1.2-1.0.Preferred embodiment comprises the XF49-B8324 of Momentive Performance Material company.
Help amido silicon oil of the present invention and account for compositions 0.01-3%, preferably at 0.03-2%, more preferably it possesses following general formula at 0.05-1%.:
Wherein: n is the integer of 0-1000, and m is the integer of 1-500, and m and n sum are the integers of 1-1000, and R1 and R2 are hydrogen, C
1-C
4Alkyl or alkane hydroxyl.Satisfy in the amino silicones of above-mentioned general formula and contain 0.1% weight or volatile solvent still less or hexamethyl siloxanes, be less than 0.5% weight prestox siloxanes and be less than 1.0% weight decamethyl siloxanes, and the molal weight of described amino silicones is between 2000-600000. the commercially available amino silicones that can be used for inventing includes but not limited to available from Dow Corning company, DowCorning 8566 Amino Fluids; Available from SM 2115 of Momentive Performance Material company etc.
Helping additive of the present invention also comprises: Polyquaternium-10 or Guar Quats or Polyquaternium-7 and their compositions, and the Polyquaternium-10 addition is at 0.01-0.6% when needing; Guar Quats addition is at 0.01-0.5% when needing; The Polyquaternium-7 addition is at 0.01-0.44% and other all kinds of suitable high molecular weight water soluble polymers when needing.Antiseptic: Kazon, p-Hydroxybenzoate, diazolidinyl urea, imidazolidinyl urea, DMDM Hydantoin etc.; Acidity regulator: citric acid, Etidronic Acid, sodium hydroxide etc.; Pigment: FD﹠amp; C or D﹠amp; Dyestuff among the C; Essence; Intercalating agent: Etidronic Acid, EDTA etc.; Pearling agent; Inorganic salt: sodium chloride, ammonium chloride, zinc chloride etc.; Antioxidant; Freshener; Deionized water etc.
The present invention finds under study for action, manage to improve the affinity of anti-dandruff dose of non-hydrophilic particle and scalp sebum, thereby can realize improving anti-dandruff dose of non-hydrophilic particle on scalp retention and the purpose of utilization, again in conjunction with anti-dandruff dose of purpose that just reaches the quantity of instant and long-acting controlling microbial (chlosma yeast) of hydrophilic efficiently.Simultaneously, the unsaturated fatty acids alcohol ester has higher refractive index usually, has outstanding effect to improving the brightness of hair hair, and anti-dandruff dose fabulous affinity and certain dissolubility is arranged with non-hydrophilic particle.With anti-dandruff dose of non-hydrophilic particle by means of having the unsaturated fatty acids alcohol ester of fine intermiscibility to wrap up in band and attached on the scalp with sebum, thereby can bring into play the purpose of the quantity of Sustainable Control microorganism (chlosma yeast).
Embodiment
Following embodiment further describes and the interior embodiment of for example clear scope of the invention.These embodiment that given only are illustrative; unintelligible is limitation of the present invention; because under the situation that does not deviate from the present invention's spirit and protection domain, can carry out many changes; and all by weight percentage; unless explanation is hereinafter arranged in addition, is suitable for composition in addition and is trade name or INCI name.The prescription of embodiment A-K such as following table 1, wherein A-D, G-H are example of the present invention, E-F, I-K are reference examples.
Table 1
The hair gloss testing experiment
Hair gloss test utilizes the measurement of luster instrument of German ERICHSEN TESTING EQUIPMENT company: 20 °/60 °/85 ° of Picogloss, model: Model 503, and test for 60 ° with Picogloss.All tests are to restrain on the topknots by the 0.5ml product being used through 2 after the bleaching, after rubbed three minutes, comb is suitable, use the 50ml flushing with clean water, and after hair dryer dried up, the drying baker of putting constant temperature and humidity into was tested in constant-temperature constant-humidity environment after 2 hours again.And the glossiness of the hair after will bleaching (using the preceding hair of shampoo) is defined as 1.0.The ratio of all the other test values and this test value is as the glossiness after using, and the result represents with the meansigma methods of 5 glossiness test results, sees Table 2.
Table 2
Embodiment |
Float back hair gloss degree |
Use the glossiness after 1 time |
The increment rate of glossiness |
Use the glossiness after 5 times |
The increment rate of glossiness |
A |
1.00 |
?1.25 |
25% |
?1.38 |
38% |
B |
1.0 |
?1.32 |
32% |
?1.45 |
45% |
C |
1.0 |
?1.20 |
20% |
?1.31 |
31% |
D |
1.0 |
?1.20 |
20% |
?1.34 |
34% |
E |
1.0 |
?1.13 |
13% |
?1.15 |
15% |
F |
1.0 |
?1.11 |
11% |
?1.12 |
12% |
G |
1.0 |
?1.21 |
21% |
?1.33 |
33% |
H |
1.0 |
?1.22 |
22% |
?1.32 |
32% |
I |
1.0 |
?1.12 |
12% |
?1.13 |
13% |
J |
1.0 |
?1.21 |
21% |
?1.34 |
34% |
K |
1.0 |
?1.12 |
12% |
?1.21 |
21% |
From the test data of table 2 as can be known the present invention have the characteristics of obvious enhancing hair gloss degree, all add the prescription of unsaturated fatty acid (alcohol) esters, after it uses the glossiness of hair obvious enhancing is all arranged.Such as, the data show of prescription A and prescription E: the shampoo of adding unsaturated fatty acid (alcohol) ester just differs about 12% in the glossiness of using a postocciput to send out with the shampoo of not adding, use five times after glossiness differ about 23%.This has improved the satisfaction behind consumer's use product undoubtedly greatly.
The minimal inhibitory concentration testing experiment
The minimal inhibitory concentration index is one of static attribute method of anti-dandruff efficacy.Usually, the index of compositions is high more, and anti-dandruff efficacy is good more, and this is because dandruff removing agent suppresses the capability increase of growth of microorganism.
1. principle
The mould growth in the flask that contains the mDixon culture medium of chaff shape fish-scale (referring to people such as E.Gueho, Antoinie Leeuwenhoek (1996), No.69,337-55 introduces the present invention as a reference).Diluent adding with dissolved anti-microbial active matter contains in the testing tube of fused mDixon agar then.The mould inoculum of secret bran shape fish-scale joins in the pipe of each fusion agar, will manage rotation, and agar is poured in the sterilization culture dish separately.Behind dull and stereotyped incubation, can observe the mould growth of chaff shape fish-scale.There is not the minimum test diluent of the anti-microbial active matter of growth to be defined as minimum inhibitory concentration (MIC).By relatively the MIC value of anti-microbial active matter and the MIC value of ZPT are calculated the MIC exponential quantity.The MIC exponential quantity is the sign of the potential ability of anti-microbial active matter.
2. equipment/reagent
Microorganism chaff shape fish-scale mould (ATCC 14521) derives from institute of internal medicine of the Chinese Academy of Medical Sciences (Nanjing); Conical flask 250ml; The active substance of agar culture medium 9.5ml mDixon agar/every concentration/whenever will test; Aqueous solvent, dimethyl sulfoxide (DMSO), other is applicable to the solvent that will test active substance; Zinc Pyrithione ZPT, mean diameter is about 0.38 μ m, from Zhejiang regent company; The active substance of 2 pipes of testing tube/every kind anti-microbial active matter/every concentration/whenever will test, sterilization, size=18mm * 150mm; The active substance of 2 wares of culture dish/every kind anti-microbial active matter/every concentration/whenever will test, sterilization, size=15mm * 100mm.
3. experimental procedure
1) makes with the temperature of 320rpm and 30 ℃ that chaff shape fish-scale is mould grows in the 250ml conical flask that contains 100ml mDixo culture medium, until muddiness.
2) adopt the twice dilution series, the selected diluent of preparation anti-microbial active matter in solvent allows the sample active substance to dissolve before adding final test agar.For each concentration of ZPT sample, solvent must be DMSO; For other sample, solvent can be water or DMSO or other suitable solvent.
3) diluent (remaining in 45 ℃ of water-baths) of adding 0.25ml anti-microbial active matter in the testing tube that contains the fused mDixon agar of 9.5ml.
4) in each testing tube of fusion agar, add the mould inoculum of 0.25ml chaff shape fish-scale and (be adjusted to 5 * 10 by direct count
5Cfu/ml).
5) each pipe of vortex is poured material wherein in each culture dish into.
6) after agar solidifies, put upside down flat board and with them 30 ℃ of incubations 5 days.
7) observe the dull and stereotyped mould growth of visible chaff shape fish-scale of.
4. determine exponential quantity
By the MIC value of more every kind of anti-microbial active matter and the MIC value of ZPT, promptly by with the MIC value of ZPT MIC value divided by the anti-microbial active matter of test, and definite MIC exponential quantity.For example, if MIC
ZPTValue is 1.0 μ g/g, MIC
TestValue is 4.0 μ g/g, and the exponential quantity of then testing active substance is 1/4, is equivalent to exponential quantity and equals 0.25.Result's the meansigma methods of getting three groups of parallel tests sees Table 3 as result of the test.
Table 3
Embodiment |
Anti-dandruff active matter |
The minimal inhibitory concentration exponential quantity |
D |
The castor oil-base maleate, 0.5%; ZPT, 0.7%; Hexamidine two (hydroxyethylsulfonic acid .) salt, 0.08%. |
1.03 |
E |
ZPT, 0.7%; Hexamidine two (hydroxyethylsulfonic acid .) salt, 0.08% |
0.92 |
K |
ZPT, 0.7% |
0.85 |
I |
ZPT, 1.0%; |
1.0 |
Table 3 test data shows between Zinc Pyrithione (ZPT), castor oil-base maleate and hexamidine two (hydroxyethylsulfonic acid .) salt the obvious synergistic effect, the minimal inhibitory concentration exponential quantity of embodiment D and I is very approaching, show that indirectly bacteriostasis is approaching, anti-dandruff effect is approaching, and anti-dandruff dose the addition of embodiment D obviously reduces.The possibility of result of embodiment K, E and D shows that the existence of unsaturated fatty alcohol (acid) ester has improved anti-dandruff dose and acted on the mould chance of chaff shape fish-scale.
Anti-dandruff effect hair caring chamber testing experiment
The test of hair caring chamber is to utilize the well-known on the market product W salable of China to compare for the sample among benchmark product and the embodiment. the experimenter is provided the 0-10 branch by double blinding two products on probation to every index, representative in 10 fens is own the most satisfied to this performance, representative in 0 fen is dissatisfied. and experimenter (totally 44 people, 1 group of per 4 people) is the long hair women of dandruff worry.The specialty teacher adopts identical program and time that product is done the half a head test, and the water with identical and capacity rinses out then.The experimenter that participation is estimated fixedly half a head uses the W sample, and another side uses the sample among the embodiment, uses continuously 14 days, follows the tracks of after stopping using 5 days again.By 18 professional teachers every experimenter's dandruff situation is carried out tracking evaluation marking (10 are divided into dandruff seldom, and 0 is divided into the dandruff especially severe) before using every day, average is as the dandruff score value on the same day.The result gathers as table 4.
Table 4
The continuous table of going up:
After stopping using, the prescription trier of containing unsaturated fatty alcohol (acid) ester as can be seen from top data still keep the long period not perplexed by dandruff, and use control sample W and do not contain the trier of the prescription of castor oil-base maleate, very fast dandruff stages a comeback again after inactive.All prescription user that contain the hexamidine derivant use the effect that just shows the better controlled dandruff at the beginning.The data of embodiment D and reference examples E, F show with unsaturated fatty alcohol (acid) ester moiety and replace having anti-dandruff dose of (ZPT) not only anti-dandruff effect of non-hydrophilic particle of injury not descend to environment, and it is also stronger to suppress the ability of dandruff lastingly.Reference examples J, K the 14th day later outstanding unsaturated fatty alcohol (acid) ester that shows of data anti-dandruff dose of (ZPT) lasting anti-dandruff effect of the water-insoluble particles of promotion arranged.