CN114601741B - Selenium sulfide shampoo composition - Google Patents
Selenium sulfide shampoo composition Download PDFInfo
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- CN114601741B CN114601741B CN202210399632.4A CN202210399632A CN114601741B CN 114601741 B CN114601741 B CN 114601741B CN 202210399632 A CN202210399632 A CN 202210399632A CN 114601741 B CN114601741 B CN 114601741B
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- selenium
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- 229960005265 selenium sulfide Drugs 0.000 title claims abstract description 91
- 239000002453 shampoo Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 title claims abstract 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000004005 microsphere Substances 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 9
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003014 ion exchange membrane Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- IOKBJSAKTZEMBR-UHFFFAOYSA-N 2-chloro-4-fluoro-3-methylbenzonitrile Chemical compound CC1=C(F)C=CC(C#N)=C1Cl IOKBJSAKTZEMBR-UHFFFAOYSA-N 0.000 claims description 7
- VFKZECOCJCGZQK-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCO VFKZECOCJCGZQK-UHFFFAOYSA-M 0.000 claims description 7
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229940104256 sodium taurate Drugs 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000001284 azanium sulfanide Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003011 anion exchange membrane Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 210000004761 scalp Anatomy 0.000 abstract description 25
- 208000001840 Dandruff Diseases 0.000 abstract description 11
- 239000008139 complexing agent Substances 0.000 abstract description 4
- JNMWHTHYDQTDQZ-UHFFFAOYSA-N selenium sulfide Chemical compound S=[Se]=S JNMWHTHYDQTDQZ-UHFFFAOYSA-N 0.000 description 75
- 239000000243 solution Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- 230000028327 secretion Effects 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 229910000338 selenium disulfide Inorganic materials 0.000 description 5
- 229940091258 selenium supplement Drugs 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229940121375 antifungal agent Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 210000002510 keratinocyte Anatomy 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 210000002374 sebum Anatomy 0.000 description 4
- 229940000207 selenious acid Drugs 0.000 description 4
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 4
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 4
- 210000000434 stratum corneum Anatomy 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000555676 Malassezia Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 230000035755 proliferation Effects 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- 208000003251 Pruritus Diseases 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 230000007803 itching Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- OWEGWHBOCFMBLP-UHFFFAOYSA-N 1-(4-chlorophenoxy)-1-(1H-imidazol-1-yl)-3,3-dimethylbutan-2-one Chemical compound C1=CN=CN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 OWEGWHBOCFMBLP-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000101040 Pityriasis Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000003908 antipruritic agent Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229960003344 climbazole Drugs 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000006694 eating habits Nutrition 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000003410 keratolytic agent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000006996 mental state Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- BTSZTGGZJQFALU-UHFFFAOYSA-N piroctone olamine Chemical compound NCCO.CC(C)(C)CC(C)CC1=CC(C)=CC(=O)N1O BTSZTGGZJQFALU-UHFFFAOYSA-N 0.000 description 1
- 229940081510 piroctone olamine Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 230000008591 skin barrier function Effects 0.000 description 1
- -1 smaller than 1 mu m) Chemical compound 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- RIUORJCWAHCMSA-UHFFFAOYSA-L zinc;4-aminobenzenesulfonate Chemical compound [Zn+2].NC1=CC=C(S([O-])(=O)=O)C=C1.NC1=CC=C(S([O-])(=O)=O)C=C1 RIUORJCWAHCMSA-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/23—Sulfur; Selenium; Tellurium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/006—Antidandruff preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
-
- 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
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
-
- 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
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
Abstract
The invention provides a selenium sulfide shampoo composition, which reasonably controls the balance moving direction of electrolyte through adding pH value and complexing agent, uniformly deposits nano selenium sulfide particles on the surface of carbon microsphere intermittently contacted with cathode, wherein the nano selenium sulfide has nano size, but is adhered on the surface of carbon microsphere in micrometer range, so that the nano selenium sulfide does not harm scalp due to undersize, and the preparation process is simple and easy to obtain on the premise of maintaining high purity and high anti-dandruff, and the yield and the efficiency are far higher than those of similar products.
Description
Technical Field
The invention belongs to the field of daily chemicals, relates to a preparation method of a shampoo composition, and particularly relates to a selenium sulfide shampoo composition.
Background
The shampoo is a product which is mainly compounded by taking a surfactant as a main body, has the functions of cleaning scalp and hair of people and keeping the beauty of the scalp and hair
The product is a daily chemical product with great daily living usage of people. The shampoo comprises the components of a cleaning agent, a hair care component, hair-moistening grease, a conditioning agent, an anti-dandruff antipruritic agent, a preservative, a thickening agent, a chelating agent, a thickening agent, an ultraviolet absorber, nutrient elements and the like, wherein the main effective matters of the shampoo are generally anionic surfactants, and the proper surfactant can achieve the effects of rich foam, low irritation, high cleanliness and weak degreasing capability.
The shampoo is used for cleaning hair, and with the improvement of living standard, people are required to have multiple functions, such as
Removing dandruff, softening hair, and no greasy feeling. The anti-dandruff shampoo is a product added with anti-dandruff components such as climbazole, piroctone olamine, zinc pyrithione and the like, and has a great specific weight in the whole shampoo market because a great number of people have dandruff.
The so-called dandruff is the scale of our scalp area, and the scientific name is "pityriasis". Under normal conditions, keratinocytes on the scalp gradually differentiate and grow from the bottom of the epidermis layer, gradually move to the surface layer of the scalp, gradually differentiate to form horny layers on the scalp, and finally fall off under the influence of relevant body metabolic enzymes to form a fine particle which cannot be seen by naked eyes. However, if the keratinocytes at the scalp are abnormally increased, dandruff is increased, and when more keratinocytes fall off and adhere together, flaky scales which are visible to the naked eye are formed.
The causes of abnormal proliferation of scalp keratinocytes generally have three causes:
1. the microbial balance of the scalp is disrupted by the presence of many microorganisms at our scalp, one of which is known as malassezia, and if this fungus is too much proliferated, it will cause the hyper-proliferation of our horny layer, which forms flaky scales. This is why there are many shampoos on the market which contain antifungal agents, chosen according to their own practice.
2. Sebum secretion excessive sebum secretion is also a major cause of abnormal proliferation of malassezia, but if sebum secretion is too low, scalp lacks protective components, and has insufficient water locking function, which is liable to cause dryness and itching of scalp, and serious scalp inflammation or scalp function barrier weakening is caused. Meanwhile, daily life work and rest, mental state and eating habit are clean and sanitary, and the secretion of scalp sebum can be influenced.
3. The function of the stratum corneum barrier of the scalp is that the stratum corneum of the scalp protects the scalp against the outside, has a water locking function, and prevents the scalp from being dehydrated to cause dryness and itching, so that the importance of protecting the health of the scalp is obvious, and once the stratum corneum barrier function is damaged, external harmful substances easily invade to cause local scalp inflammation or promote abnormal proliferation of scalp stratum corneum cells to form more flaky scales.
The therapeutic agent for dandruff mainly comprises topical keratolytic agent such as sulfur and salicylic acid, and broad-spectrum antifungal agent such as ketone Kang Wa, selenium disulfide, zinc sulfanilate and rimexoolamine, wherein the antifungal agent has good clinical application effect, and is often made into shampoo for convenient use. The curative effects of the above medicines are different, and here we mainly describe selenium sulfide antifungal shampoo.
The prior art prepares selenium sulfide by reacting selenious acid with hydrogen sulfide, and the method comprises the steps of introducing hydrogen sulfide gas into selenious acid solution to generate selenium disulfide, filtering, drying and crushing to obtain the product selenium disulfide, wherein the method has low utilization rate of hydrogen sulfide, and the hydrogen sulfide is easy to pollute the environment, such as CN102060277A, and the method comprises the following steps: preparing a selenium dioxide aqueous solution in a stirring state according to the concentration of 100-200 g/L, filtering, preparing a filtered sodium sulfide aqueous solution in a concentration of 150-350 g/L, simultaneously dripping sodium sulfide solution glacial acetic acid into the stirring selenium dioxide aqueous solution, continuously stirring to promote the reaction, putting the reacted solution into a centrifugal machine for centrifugal separation to obtain a selenium disulfide product, washing the product to be neutral, and drying to obtain the selenium disulfide product, wherein the yield and the purity are obviously improved.
The preparation method of the high-purity selenium sulfide is disclosed in CN109650353A, and is characterized by comprising the following steps: A. dissolving raw material selenium in nitric acid solution; B. crystallizing and separating out the selenious acid after the reaction in the solution; C. dissolving selenious acid crystal in water and filtering to obtain saturated solution; D. stirring the saturated solution, and adding an ammonium sulfide solution and a glacial acetic acid solution or an ammonium bisulfide solution and a glacial acetic acid solution into the saturated solution; E. adding absolute ethyl alcohol or absolute methyl alcohol into the mixed solution obtained in the step D, and continuously stirring; stirring, standing and aging; F. filtering, and washing the filtered matter for several times by using alcohol; and drying after washing. The purity of the selenium sulfide finally prepared by the process is up to 99.99 percent, which is enough to meet the requirement of high purity. Although the purity is high, the obvious preparation process and the complexity thereof have the defects of high purity and insufficient yield.
In addition, regarding electrochemical synthesis of selenium sulfide, the prior art is not available, but a preparation method for synthesizing selenium simple substance by electrochemical synthesis is disclosed in CN202110797078, for example, the selenium sulfide is uniformly dispersed on the surfaces of nano microspheres in a nano form, and can be directly mixed with a shampoo composition for use, sedimentation separation is not easy to occur in the composition, and mixing of selenium sulfide and shampoo is not required during use, so that the method is simple and convenient, carbon sphere particles can be used as an active carbon shampoo additive, can reduce dandruff generation, reduce grease secretion, have obvious inhibition effect on malassezia, and the electrochemical deposition principle is 6H + +SeO 3 2- +4e - →3H 2 O+Se, then preparing selenium sulfide through sulfuration, and then removing redundant sulfur through sublimed sulfur to obtain high-purity selenium sulfide, but in the process of separating sublimed sulfur and selenium sulfide, which is known in the art, partial selenium sulfide loss can be caused, and the whole preparation process is that selenium is obtained first and then selenium sulfide is obtained, and the process is obviously not one-step synthesis.
Disclosure of Invention
Based on the technical problems of complex preparation process, low purity and low yield of selenium sulfide in the prior art, the invention provides a selenium sulfide shampoo composition, wherein the selenium sulfide is prepared by an electrochemical method, the balance moving direction of electrolyte is reasonably controlled by adding a pH value and a complexing agent, nano selenium sulfide particles are uniformly deposited on the surface of carbon microspheres intermittently contacted with a cathode, and the selenium sulfide has nano size but is not excessively small in size and poisons scalp due to being attached to the surface of the carbon spheres in a micrometer range, so that the preparation process is simple and easy to obtain on the premise of maintaining high purity and high scrap removal, and the yield and the efficiency are far higher than those of similar products.
Specifically: the selenium sulfide shampoo composition consists of nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl sodium taurate, essence and water, wherein the mass ratio of the nano selenium sulfide/porous micron carbon spheres to the polyethylene glycol to the glycerol is (2-2.5): (0.8-1.2): (1-1.5): (1.7-2.2): (0.3-0.5): (1.2-1.5): (0.1-0.2): (5-7);
the preparation process of the nano selenium sulfide/porous micro carbon spheres comprises the following steps:
(1) Pretreating porous micron carbon spheres: adding a proper amount of porous carbon microspheres into a multi-neck flask, then adding 200-300ml of 1-2M sodium hydroxide aqueous solution, heating to 97-100 ℃ under stirring, cooling, condensing and refluxing for 40-60min, naturally cooling, washing with a large amount of deionized water, filtering to pH 7.5+/-0.3, and preparing into 10-12g/L hydroxylated porous carbon microsphere suspension;
(2) The preparation process of the nano selenium sulfide/porous micron carbon sphere by electrochemical synthesis is as follows:
(a) 30-40 mM sodium selenate decahydrate and 90-120 mM ammonium hydrosulfide are dissolved in deionized water, 0.03-0.05g of diethylenetriamine pentacarboxylate is added, and hydrochloric acid is used for regulating the pH value to 8-9.
(b) Inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into a catholyte and an anolyte by using an ion exchange membrane, then introducing the hydroxylated porous carbon microsphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5+/-0.3, switching on a power supply under stirring and adjusting, implementing cathode electrolytic reduction, wherein the electrolytic voltage is 3-5V, the time is 15-20min, the stirring speed is 300-500rpm, the pH concentration of the catholyte is monitored in real time during the electrolysis, and sulfuric acid is added for proper time to maintain the pH value to be constant at 7.5+/-0.3;
(c) Stopping the power supply and leading out the catholyte.
(3) And filtering, washing and drying the catholyte to obtain the nano selenium sulfide/porous micro carbon spheres.
Further, the purity of the nano selenium sulfide is more than 99.99%, and the particle size of the nano selenium sulfide is 20-200nm.
Further, the loading of the selenium sulfide in the nano selenium sulfide/porous micro carbon spheres is 4-6wt%.
Further, the porous carbon microspheres have a particle size distribution with a D90 of 7-12 μm.
Further, the ion exchange membrane is an anion exchange membrane.
Further, the drying is vacuum freeze drying, the freezing time is 12-16h, the temperature is less than-35 ℃, and the vacuum degree is 10-12Pa.
Furthermore, the selenium sulfide shampoo composition is matched with shampoo of other brands to be used, and the weight percentage of the selenium sulfide in the shampoo composition is not more than 1.0%.
Electrochemical preparation of nano selenium sulfide/porous micron carbon sphere principle:
firstly, regarding porous carbon microsphere suspension, wherein the porous carbon microsphere is purchased in the market, the porous carbon microsphere has particle size distribution with D90 of 7-12 mu M, but a large amount of grease and amorphous carbon sheets or other impurities are arranged on the surface, and the porous carbon microsphere suspension is hydrophobic, so that surface pretreatment is necessary, the pretreatment mode is that a proper amount of porous carbon microsphere is added into a multi-neck flask, then 200-300ml of 1-2M sodium hydroxide aqueous solution is added, the mixture is heated to 97-100 ℃ under stirring condition, cooled water is cooled and refluxed for 40-60min, naturally cooled, and a large amount of deionized water is washed and filtered to pH of 7.5+/-0.3, so that 10-12g/L of hydroxylated porous carbon microsphere suspension is configured; the existence of the hydroxyl effectively improves the suspension effect of the carbon spheres in the subsequent catholyte, and avoids agglomeration and suspension on the surface of the catholyte, as shown in figure 1.
The main components of the electrolyte of the invention are sodium selenate decahydrate, ammonium hydrosulfide and diethylenetriamine pentacarboxylate, namely Na exists in water + 、NH 4+ 、SeO 4 2- And HS (high speed) - The whole electrolysis is alkaline, and acid such as sulfuric acid or hydrochloric acid is added to adjust pH to 8-9 to ionize and move the solution, with the following reaction formula SeO 4 2- + 4HS - + 4H + ⇌ SeS 4 2- + 4H 2 O, i.e. the equilibrium in which ionization occurs during lowering of the pH of the solution shifts to the right, and in addition the complexing agent pair diethylenetriamine pentacarboxylate pair SeS 4 2- Is significantly greater than SeO 4 2- Further, itIncreasing the balance to shift right, forming more SeS 4 2- 。
Then, a voltage is applied to the electrolyte, and the following reaction [ SeS ] occurs 4 ] 2- + 2e - + 2H 2 O → SeS 2 +2HS - +2OH - I.e. SeS is formed on the cathode surface 2 Particles, seS with the occurrence of electrolysis 2 Forming a film of particles, covering the surface of the cathode, said SeS 2 The film has strong binding force on the surface of the cathode and cannot be effectively stripped, and particularly for the porous inert titanium plate cathode, seS deposited on the surface of the cathode 2 Difficult to recycle and can affect the conductivity of the cathode.
For this purpose, the above-prepared hydroxylated porous carbon microspheres are introduced into the cathode, and are conductive microspheres, and under the condition of stirring speed of 300-500rpm, the microspheres continuously strike the cathode, and electrolytic reduction [ SeS ] is carried out in the process of contacting with the surface of the cathode 4 ] 2- + 2e - + 2H 2 O → SeS 2 +2HS - +2OH - As described above, a local alkaline environment is formed on the surface of the carbon spheres contacted with the cathode, so that the pH of the cathode solution is reduced, the deposition of selenium sulfide on the cathode is facilitated, the pH concentration of the cathode solution is monitored in real time in the electrolysis process, sulfuric acid is added at a proper time to maintain the pH value constant at 7.5+/-0.3, the concentration is consistent with the concentration of the hydroxylated porous micro-carbon spheres, and the concentration range of the pH is the optimal microsphere deposition SeS 2 The range is as the necessary condition, and the anti-dandruff component on the surface of the finally obtained nano selenium sulfide/porous micro carbon sphere is shown in figure 2.
The beneficial technical effects are as follows:
(1) Selenium sulfide is prepared by an electrochemical method, the balance moving direction of electrolyte is reasonably controlled by adding a pH value and a diethylenetriamine pentacarboxylate complexing agent, nano selenium sulfide particles are uniformly deposited on the surface of carbon microspheres intermittently contacted with a cathode, the preparation process is simple and easy to obtain, and the yield and the efficiency are far higher than those of similar products through one-step synthesis.
(2) The relative sizes of the selenium sulfide and the carbon spheres are reasonably controlled, and the nano active components and the micron macroscopic carrier are cooperated, so that the unstable phenomenon that the selenium sulfide lotion is easy to delaminate and the like caused by overlarge particle size of the selenium sulfide (such as larger than 50 mu m) in the selenium sulfide lotion is effectively overcome, or the probability of passing through skin barriers is increased due to overlarge particle size of the selenium sulfide (such as smaller than 1 mu m), and the risk of toxic and side effects of the selenium sulfide lotion on skin is effectively avoided.
(3) Although the selenium sulfide has nano size, the selenium sulfide is adhered to the surface of the carbon sphere in the micrometer range, so that the selenium sulfide cannot be undersized to poison the scalp, the preparation process is simple and easy to obtain on the premise of maintaining high purity and removing scraps, and the yield and the efficiency are far higher than those of similar products.
Drawings
FIG. 1 SEM image of hydroxylated porous carbon microspheres obtained by pretreatment according to the invention.
FIG. 2 is a TEM image of the nano-selenium sulfide/porous micro-carbon spheres prepared in example 2 of the present invention.
Detailed Description
Example 1
The selenium sulfide shampoo composition consists of nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl sodium taurate, essence and water, wherein the mass ratio of the nano selenium sulfide/porous micron carbon spheres to the polyethylene glycol to the glycerol to the bentonite, the hydroxypropyl trimethyl ammonium chloride to the N-oleoyl-N-methyl sodium taurate is (2): (0.8): (1): (1.7): (0.3): (1.2): (0.1): (5).
The preparation process of the nano selenium sulfide/porous carbon microsphere deionized water comprises the following steps:
(1) Pretreating porous micron carbon spheres: adding a proper amount of porous carbon microspheres into a multi-neck flask, then adding 200ml of 1M sodium hydroxide aqueous solution, heating to 97 ℃ under stirring, cooling, condensing and refluxing for 40min, naturally cooling, washing with a large amount of deionized water, filtering to pH 7.5+/-0.3, and preparing into 10g/L hydroxylated porous carbon microsphere suspension.
(2) The preparation process of the nano selenium sulfide/porous micron carbon sphere by electrochemical synthesis is as follows:
(a) 30mM sodium selenate decahydrate and 90mM ammonium hydrosulfide are dissolved in deionized water, 0.03g of diethylenetriamine pentacarboxylate is added, the mixture is stirred uniformly, and the pH value is regulated to 8 by using hydrochloric acid, so that an electrolyte is obtained.
(b) And (3) inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into a catholyte and an anolyte by using an ion exchange membrane, then introducing the hydroxylated porous carbon microsphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5+/-0.3, switching on a power supply under stirring and adjusting, implementing cathode electrolytic reduction, and monitoring the pH concentration of the catholyte in real time at the stirring speed of 300rpm for 15min at the electrolytic voltage of 3V, and adding sulfuric acid for the proper time to maintain the pH value constant at 7.5+/-0.3.
(c) Stopping the power supply and leading out the catholyte.
(3) Filtering, washing, air-cooling and freeze-drying the catholyte for 12 hours at the temperature of less than-35 ℃ and the vacuum degree of 10-12Pa, thus obtaining the nano selenium sulfide/porous micro carbon spheres.
Example 2
The selenium sulfide shampoo composition consists of nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl sodium taurate, essence and water, wherein the mass ratio of the nano selenium sulfide/porous micron carbon spheres to the polyethylene glycol to the glycerol is (2-2.5): (0.8-1.2): (1-1.5): (1.7-2.2): (0.3-0.5): (1.2-1.5): (0.1-0.2): (5-7).
The preparation process of the nano selenium sulfide/porous carbon microsphere deionized water comprises the following steps:
(1) Pretreating porous micron carbon spheres: adding a proper amount of porous carbon microspheres into a multi-neck flask, then adding 250ml of 1.5M sodium hydroxide aqueous solution, heating to 98.5 ℃ under stirring, cooling, condensing and refluxing for 50min, naturally cooling, washing with a large amount of deionized water, filtering to pH 7.5+/-0.3, and preparing into 11g/L hydroxylated porous carbon microsphere suspension.
(2) The preparation process of the nano selenium sulfide/porous micron carbon sphere by electrochemical synthesis is as follows:
(a) 35 mM sodium selenate decahydrate and 105 mM ammonium bisulfide are dissolved in deionized water, 0.04g of diethylenetriamine pentacarboxylate is added, the mixture is stirred uniformly, and hydrochloric acid is used for regulating the pH value to 8.5, so that an electrolyte is obtained.
(b) And (3) inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into a catholyte and an anolyte by using an ion exchange membrane, then introducing the hydroxylated porous carbon microsphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5+/-0.3, switching on a power supply under stirring and adjusting, implementing cathode electrolytic reduction, and monitoring the pH concentration of the catholyte in real time at a stirring speed of 400rpm for 17.5min, wherein sulfuric acid is added for a proper time to maintain the pH constant to 7.5+/-0.3.
(c) Stopping the power supply and leading out the catholyte.
(3) Filtering, washing, air-cooling and freeze-drying the catholyte for 14h at the temperature of less than-35 ℃ and the vacuum degree of 10-12Pa, thus obtaining the nano selenium sulfide/porous micro carbon spheres.
Example 3
The preparation process of the nano selenium sulfide/porous carbon microsphere deionized water comprises the following steps:
(1) Pretreating porous micron carbon spheres: adding a proper amount of porous carbon microspheres into a multi-neck flask, then adding 300ml of 2M sodium hydroxide aqueous solution, heating to 100 ℃ under stirring, cooling, condensing and refluxing for 60min, naturally cooling, washing with a large amount of deionized water, filtering to pH 7.5+/-0.3, and preparing into 12g/L hydroxylated porous carbon microsphere suspension.
(2) The preparation process of the nano selenium sulfide/porous micron carbon sphere by electrochemical synthesis is as follows:
(a) Dissolving 40 mM sodium selenate decahydrate and 120 mM ammonium bisulfide in deionized water, adding 0.05g of diethylenetriamine pentacarboxylate, stirring uniformly, and regulating the pH value to 9 by using hydrochloric acid to obtain an electrolyte.
(b) And (3) inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into a catholyte and an anolyte by using an ion exchange membrane, then introducing the hydroxylated porous carbon microsphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5+/-0.3, switching on a power supply under stirring and adjusting, implementing cathode electrolytic reduction, and monitoring the pH concentration of the catholyte in real time at the stirring speed of 500rpm for 20min at the electrolysis voltage of 5V, and adding sulfuric acid for the proper time to maintain the pH constant to 7.5+/-0.3.
(c) Stopping the power supply and leading out the catholyte.
(3) Filtering, washing, air-cooling and freeze-drying the catholyte for 16h at the temperature of less than-35 ℃ and the vacuum degree of 10-12Pa, thus obtaining the nano selenium sulfide/porous micro carbon spheres.
Comparative example 1
The selenium sulfide shampoo composition consists of nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl sodium taurate, essence and water, wherein the mass ratio of the nano selenium sulfide/porous micron carbon spheres to the polyethylene glycol to the glycerol is (2-2.5): (0.8-1.2): (1-1.5): (1.7-2.2): (0.3-0.5): (1.2-1.5): (0.1-0.2): (5-7).
The preparation process of the nano selenium sulfide/porous carbon microsphere deionized water comprises the following steps:
(1) Pretreating porous micron carbon spheres: adding a proper amount of porous carbon microspheres into a multi-neck flask, then adding 250ml of 1.5M sodium hydroxide aqueous solution, heating to 98.5 ℃ under stirring, cooling, condensing and refluxing for 50min, naturally cooling, washing with a large amount of deionized water, filtering to pH 7.5+/-0.3, and preparing into 11g/L hydroxylated porous carbon microsphere suspension.
(2) The preparation process of the nano selenium sulfide/porous micron carbon sphere by electrochemical synthesis is as follows:
(a) And dissolving 35 mM sodium selenate decahydrate and 105 mM ammonium bisulfide in deionized water, and uniformly stirring to obtain an electrolyte.
(b) And (3) inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into a catholyte and an anolyte by using an ion exchange membrane, then introducing the hydroxylated porous carbon microsphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5+/-0.3, switching on a power supply under stirring and adjusting, implementing cathode electrolytic reduction, and monitoring the pH concentration of the catholyte in real time at a stirring speed of 400rpm for 17.5min, wherein sulfuric acid is added for a proper time to maintain the pH constant to 7.5+/-0.3.
(c) Stopping the power supply and leading out the catholyte.
(3) Filtering, washing, air-cooling and freeze-drying the catholyte for 14h at the temperature of less than-35 ℃ and the vacuum degree of 10-12Pa, thus obtaining the nano selenium sulfide/porous micro carbon spheres.
By examining the selenium sulfide content and size tests in example 2 and comparative example 1 micrometer, wherein the selenium sulfide content and size in the nano-selenium/porous micro-carbon spheres in example 2 is 5.13wt.%, the nano-size is concentrated and distributed near 120nm, the size is uniform, and in comparative example 1, diethylenetriamine pentacarboxylate is not added, and the pH of the mixed solution is not regulated, the balance movement is hindered, the yield is lower, the selenium sulfide content in the nano-selenium/porous micro-carbon spheres is 0.782wt.%, the nano-size is concentrated and distributed at 20-500nm, the particle size is larger, the distribution is nonuniform, and the obvious agglomeration phenomenon exists in the process of preparing the selenium sulfide by electrochemical reduction.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. The selenium sulfide shampoo composition is characterized by comprising nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl sodium taurate, essence and water, wherein the mass ratio of the nano selenium sulfide/porous micron carbon spheres to the polyethylene glycol, the glycerol, the bentonite, the hydroxypropyl trimethyl ammonium chloride, the N-oleoyl-N-methyl sodium taurate to the essence is (2-2.5): (0.8-1.2): (1-1.5): (1.7-2.2): (0.3-0.5): (1.2-1.5): (0.1-0.2): (5-7);
the preparation process of the nano selenium sulfide/porous micro carbon spheres comprises the following steps:
(1) Pretreating porous micron carbon spheres: adding a proper amount of porous carbon microspheres into a multi-neck flask, then adding 200-300mL of 1-2M sodium hydroxide aqueous solution, heating to 97-100 ℃ under stirring, cooling, condensing and refluxing for 40-60min, naturally cooling, washing with a large amount of deionized water, filtering to pH 7.5+/-0.3, and preparing into 10-12g/L hydroxylated porous carbon microsphere suspension;
(2) The preparation process of the nano selenium sulfide/porous micron carbon sphere by electrochemical synthesis is as follows:
(a) Dissolving 30-40 mM sodium selenate decahydrate and 90-120 mM ammonium bisulfide in deionized water, adding 0.03-0.05g of diethylenetriamine pentacarboxylate, uniformly stirring, and regulating the pH value to 8-9 by using hydrochloric acid to obtain electrolyte;
(b) Inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into a catholyte and an anolyte by using an ion exchange membrane, then introducing the hydroxylated porous carbon microsphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5+/-0.3, switching on a power supply under stirring and adjusting, implementing cathode electrolytic reduction, wherein the electrolytic voltage is 3-5V, the time is 15-20min, the stirring speed is 300-500rpm, the pH concentration of the catholyte is monitored in real time during the electrolysis, and sulfuric acid is added for proper time to maintain the pH value to be constant at 7.5+/-0.3;
(c) Stopping the power supply and leading out cathode liquid;
(3) Filtering, washing and drying the catholyte to obtain nano selenium sulfide/porous micro carbon spheres;
the selenium sulfide shampoo composition is matched with shampoo of other brands to be used, and the weight percentage of the selenium sulfide in the shampoo composition is not more than 1.0%;
the purity of the nano selenium sulfide is more than 99.99 percent, and the particle size of the nano selenium sulfide is 20-200nm.
2. A selenium sulphide shampoo composition according to claim 1, characterized in that the loading of selenium sulphide in the nano-selenium sulphide/porous micro-carbon spheres is between 4 and 6wt.%.
3. A selenium sulphide shampoo composition according to claim 1 wherein the porous carbon microspheres have D 90 A particle size distribution of 7-12 μm.
4. A selenium sulphide shampoo composition according to claim 1 wherein the cathode is a titanium electrode and the ion exchange membrane is an anion exchange membrane.
5. A selenium sulphide shampoo composition according to claim 1 wherein the drying in step (3) is vacuum freeze drying for a period of time of 12-16 hours at a temperature of less than-35 ℃ and a vacuum of 10-12Pa.
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| CN113633576A (en) * | 2021-07-14 | 2021-11-12 | 郑小青 | Dandruff-removing itching-relieving hair washing composition |
| CN113633559A (en) * | 2021-07-14 | 2021-11-12 | 郑小青 | Preparation method of dandruff-removing and itching-relieving shampoo |
| CN114010514A (en) * | 2021-10-08 | 2022-02-08 | 大有药业扬州有限公司 | Micronized selenium disulfide active antifungal lotion |
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| CN113633576A (en) * | 2021-07-14 | 2021-11-12 | 郑小青 | Dandruff-removing itching-relieving hair washing composition |
| CN113633559A (en) * | 2021-07-14 | 2021-11-12 | 郑小青 | Preparation method of dandruff-removing and itching-relieving shampoo |
| CN114010514A (en) * | 2021-10-08 | 2022-02-08 | 大有药业扬州有限公司 | Micronized selenium disulfide active antifungal lotion |
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