CN101785745B - Shampoo containing chlorine dioxide - Google Patents
Shampoo containing chlorine dioxide Download PDFInfo
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- CN101785745B CN101785745B CN2010101297854A CN201010129785A CN101785745B CN 101785745 B CN101785745 B CN 101785745B CN 2010101297854 A CN2010101297854 A CN 2010101297854A CN 201010129785 A CN201010129785 A CN 201010129785A CN 101785745 B CN101785745 B CN 101785745B
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Abstract
The invention provides shampoo containing chlorine dioxide, which is prepared from surfactant, chelant, humectant, conditioner, thickening agent, chlorine dioxide or chlorine dioxide precursor, pH regulator and deionized water at a certain weight ratio. The invention successfully introduces internationally accepted safest, most effective and environmentally-friendly A1-grade green disinfectant-chlorine dioxide into a shampoo system. The shampoo has moderate quality, is safe and protects environment; after being washed, hair is wet, soft and glossy. The shampoo overcomes the defects of the existing anti-dandruff shampoo and truly realizes that the processes of washing hair, caring hair and removing dandruff can be achieved in one step, people feel that scalp is relaxed after washing hair, and dandruff does not relapse. The shampoo is suitable for people who suffer from dandruff and has favorable curative effect on dandruff and tinea capitis due to seborrheic dermatitis, so that people can trustingly use the shampoo for a long term.
Description
Technical field
The present invention relates to a kind of shampoo, specifically, relate to a kind of shampoo that contains chlorine dioxide.
Background technology
The dandruff is attached on people's the scalp top layer and hair usually, and greatly affect people's is attractive in appearance and healthy.In China, the dandruff problem is more more general than American-European countries, and the adult more than 50% receives the puzzlement of dandruff, head pruritus, alopecia to some extent.When the dandruff occurred, usually with symptoms such as scalp inflammation and scalp itch, if do not take appropriate methods to treat targetedly, this disease may be periodically, the generation of recurrent or persistence, can cause the scalp hair follicles damage when serious, forms permanent alopecia.
The dandruff medically is being called capitis pityriasis, is a kind of dermatosis that is caused by chlosma (being called as pityrosporum furfur in the past, is a kind of in the fungus).The cuticular hyperplasia of the chlosma a large amount of breedings on scalp causing scalp, thus impel corneocyte to come off unusually with the form of white or Lycoperdon polymorphum Vitt squama, and this squama that comes off is the dandruff.
Popular in the market many kinds of dandruff removing shampoos like the Head&Shoulders of P&G, the Chhnang that chases after wind, Uniliver of overlord company, also have that the health king's ketone health dandruff removing lotion sold in pharmacy and Xi'an Yang Sen's adopt happy dandruff removing lotion etc.
The used dandruff removing agent of above-mentioned dandruff removing shampoo is summarized and is mainly contained following several kinds: ZPT (ZPT), climbazole, Octopirox (pyridone ethanolamine); Overlord company is the dandruff removing main component with Chinese medicine, and the pretty good dandruff removing composition of a kind of in addition effect is a ketoconazole.
Domestic patent about Chinese medicine dandruff removing shampoo is CN1513436 such as publication number, and open day is the patent on July 21st, 2004, disclose a kind of by ginger oil resin as effective Chinese medicine ingredients, prepared the dandruff eliminating ginger shampoo; Publication number is CN1344537A; Open day is the patent on April 17th, 2002, discloses a kind of dandruff-removing itching-relieve shampoo of being made up of Fructus Sapindi Mukouossi sarcocarp extracting solution, surfactant, conditioner, thickening agent, pearling agent, antioxidant, chelating agen, pH regulator agent, essence, antiseptic; Publication number is CN1939256A; Open day is the patent on April 4th, 2007; Disclose a kind of extracting solution by Herba Agrimoniae, Cortex Dictamni, the Fructus Kochiae, Pericarpium Granati as the dandruff removing composition, added the draft shampoo that alkyl-glucoside, bioactive peptide conditioner, tea saponin, silk peptide, Aloe extraction solution, silicone oil, polyquaternium etc. have been mixed with dandruff-removing itching-relieve, hair care anticreep.
But, because above-mentioned dandruff removing shampoo can only take stopgap measures, can not effect a permanent cure, these drawbacks limit they promotion and application in actual production.For example:
ZPT is a kind of white powder, and is water insoluble, only is dissolved in ethanol; It is a kind of antifungal agent; Has antibacterial activity simultaneously, because it is unique by the not only safety of the dandruff of FDA approval, but also effective material composition, so it has become the gold raw material of dandruff at present; But it has two shortcomings: the one, certain zest is arranged, and the 2nd, it occurs the problem separated out easily in surfactant system in use; Octopirox has compared a significant advantage with ZPT; Be that it dissolves in the aqueous solution that contains surfactant, and compatibility is good, can be composite with the kinds of surface activating agent; But its shortcoming is to run into metals such as copper, iron ion can present yellow, can affect to the outward appearance of product; Climbazole is a kind of antifungal drug that Bayer A.G develops, and its activity is stronger than Octopirox, is dissolved in ethanol; Be slightly soluble in water, there is not the problem of separating out in it in surfactant system, so should use more more convenient than ZPT; But experiment proof; Its antifungal required time is longer, and effect slowly is difficult to guarantee in those short a few minutes of having one's hair wash, remember good effect; Ketoconazole is that a kind of white is last, water insoluble to filbert crystalline substance, is soluble in dichloromethane; Be dissolved in methanol or chloroform; Its mechanism of action is through suppressing the biosynthesis of fungal cell membrane ergosterol, influences the permeability of cell and suppresses its growth, and it is poor that it exists with surfactant compound property equally; The problem of long action time, and it has certain side effect to human body.
Four kinds of above-mentioned chemical dandruff removing agent, though certain dandruff-removing itching-relieve effect is all arranged, their drawback is, in case life-time service, fungus can produce toleration to it.Want to suppress the dandruff, must often use shampoo instead.
Chinese medicine extraction liquid is safe as the dandruff-removing itching-relieve composition, with the surfactant system compatibility, but needs higher concentration effectively to play a role, and the herb liquid consumption is quite big, and complex manufacturing and cost are higher, are inappropriate for suitability for industrialized production.
The present invention selects for use the best disinfectant-chlorine dioxide of generally acknowledging in the world at present as core dandruff-removing itching-relieve composition; Chlorine dioxide can be killed all microorganisms; Comprise bacterial propagule, bacterial spore, fungus, mycobacteria and virus etc.; Up to now, do not find to have the pathogenic microorganism that to resist chlorine dioxide and not be killed as yet.And these antibacterials, virus can not develop immunity to drugs to it; Chlorine dioxide does not have teratogenesis, carcinogenic, mutagenicity effect to organism, is classified as the agent of AI level efficiently and safely disinfecting by The World Health Organization (WHO), has wide spectrum, quick-acting, characteristics such as consumption is few, drug effect is long.
Summary of the invention
The objective of the invention is to overcome the shortcoming of existing dandruff removing shampoo; A kind of novel, safe and reliable, multi-functional shampoo that contains chlorine dioxide of integrating hair washing, hair care, dandruff-removing itching-relieve is provided, realizes that really hair washing, hair care, dandruff-removing itching-relieve accomplish synchronously.
In order to realize the object of the invention; A kind of shampoo that contains chlorine dioxide of the present invention; Process by following components in weight percentage: surfactant 10-60, wetting agent 1-20, chelating agen 0.01-0.5, conditioner 1-15, thickening agent 1-20 and chlorine dioxide or chlorine dioxide precursor 0.001-5; Add an amount of pH regulator agent and regulate pH value, complement to 100 with deionized water to 5.5-7.5.
Preferably; Aforesaid shampoo; Process by following components in weight percentage: surfactant 15-55, wetting agent 3-15, chelating agen 0.02-0.4, conditioner 2-15, thickening agent 2-15 and chlorine dioxide or chlorine dioxide precursor 0.002-4; Add an amount of pH regulator agent and regulate pH value, complement to 100 with deionized water to 5.5-7.5.
More preferably; Aforesaid shampoo; Process by following components in weight percentage: surfactant 20-50, wetting agent 5-10, chelating agen 0.05-0.3, conditioner 5-10, thickening agent 5-10 and chlorine dioxide or chlorine dioxide precursor 0.004-3; Add an amount of pH regulator agent and regulate pH value, complement to 100 with deionized water to 5.5-7.5.
Aforesaid shampoo, wherein surfactant is one or more in sodium lauryl sulphate, ammonium lauryl sulfate, dodecyl alcohol ether sodium sulfate, dodecyl alcohol ether ammonium sulfate, fatty alcohol-polyoxyethylene ether, N-lauroyl musculamine acid sodium, cocos nucifera oil acyl methyl taurine sodium, cocos nucifera oil both sexes sodium acetate, 1-isobutyl-3,5-dimethylhexylphosphoric acid, 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium salt, fatty alcohol-polyoxyethylene ether monomester succinate disodium, SAS, cocos nucifera oil sodium isethionate, lauryl alcohol carboxylic acid sodium, alkyl polyglucoside, empgen BB, dodecyl CAB, cocos nucifera oil acyl aminopropyl betanin, cocamidopropyl propyl amide hydroxyl sulphonic acid betaine, dimethyl dodecyl amine oxide, cocamidopropyl propyl amide amine oxide, the cocos nucifera oil acyl glutamic acid triethanolamine.
Aforesaid shampoo, wherein wetting agent is one or more in glycerol, propylene glycol, 1,3-butylene glycol, sorbitol, pyrrolidone sodium carboxylate, hyaluronic acid, methyl glucosamine polyoxyethylene ether, lactic acid, sodium lactate, ceramide, water solublity Jojoba oil, water solublity VE, polyoxyethylene-75-lanoline, the Polyethylene Glycol-75-lanoline.
Aforesaid shampoo, wherein chelating agen is ethylenediaminetetraacetic acid, disodiumedetate or tetrasodium ethylenediamine tetraacetate.
Aforesaid shampoo, wherein conditioner is hexadecyltrimethylammonium chloride, OTAC, INCROQUAT TMC-80 ECONOL TM22, Arquad 316, cationic cellulose polymer class (for example JR400), guar gum class, polyquaternary amine salt, cationic conditioning high polymer class (for example Salcare 96, Salcare 60 etc.), polyoxyethylene ether polymer, water-soluble silicon oil and emulsified silicone oil class, vitamin B5, vitamin B6, plants in triol, Aloe extraction solution, Silk Amino Acids, Semen Sesami Nigrum extracting solution, chitosan, quaternized albumen, the high fatty alcohol one or more
Aforesaid shampoo, wherein thickening agent be the two stearates of hydroxyethyl-cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, acrylic copolymer class, acrylate copolymer, PEG-150 distearate, polyethylene glycol 6000, PEG-120 methyl glucosamine, xanthan gum, alginate jelly, card ripple, sodium chloride, Acusol772 Acusol771, methyl vinyl ether, fatty acid distribution of coconut oil single ethanol amide, fatty acid distribution of coconut oil diglycollic amide, day over execute in ADM, the acrylic ester/neodecanoic acid hexenoic acid cross-linked copolymer one or more.
Aforesaid sterilization shampoo, wherein chlorine dioxide precursor is sodium chlorite, potassium chlorite, lithium chlorite, magnesium chlorite or barium chlorite.
Aforesaid sterilization shampoo, wherein the pH regulator agent is one or more in citric acid, sodium citrate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, boric acid, the Borax.
The aforementioned method for preparing that contains the shampoo of chlorine dioxide is specially: measure deionized water in proportion, add chelating agen, wetting agent, stir and make its dissolving; Add the Surfactant component then, be heated to 60-75 ℃, stir and make its whole dissolvings, add the conditioner component then; The restir dissolving adds thickener component, stirs and makes its dissolving, is cooled to 30 ℃ or following then; Feed chlorine dioxide or add chlorine dioxide precursor, stir the back and use pH regulator agent adjust pH to be 5.5-7.5, promptly get.
The present invention is through being incorporated into chlorine dioxide in the shampoo system, and the package action of surfactant system capable of using is introduced directly into chlorine dioxide and forms slow-releasing system in the shampoo on the one hand; On the other hand, also can chlorine dioxide precursor be joined in the shampoo system and form slow-releasing system.When hair washing, shampoo is met water and can system be activated, and discharges chlorine dioxide very soon, reaches the effect of dandruff removing.
The method for using of product of the present invention is: earlier with warm water moistening hair; get these article in right amount (because of personal considerations, hair length different) in the centre of the palm; a little evenly coats on the hair after rubbing out foam to add water; particularly root of hair, scalp position, uses light finger forlement scalp 3-5mins then, totally gets final product with flushing with clean water at last.
By technique scheme, the present invention has advantage and beneficial effect at least:
(1) the present invention is applied to safety, the efficient sterilizing characteristic of chlorine dioxide in the shampoo system, realizes that really hair washing, hair care, dandruff-removing itching-relieve accomplish synchronously;
(2) dandruff-removing itching-relieve shampoo of the present invention is fit to the squarrose crowd of all kinds, no matter be the dandruff that causes of seborrheic dermatitis or because the dandruff that tinea capitis causes is used individual monthly healing of these article 1-2;
(3) not only character is gentle, detergency is good, it is moist, submissive glossy to wash the back hair for dandruff-removing itching-relieve shampoo of the present invention, and the ability antipruritic effect is fine; Remove the dandruff and do, not only can thoroughly treat the dandruff, and can not produce toleration from root; Instant coming into force do not recurred;
(4) these article are nontoxic, harmless to environment, safety and environmental protection, and people are this product of life-time service relievedly.
The specific embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
Embodiment the present invention contains the chlorine dioxide shampoo of different component
Its component formula is shown in table 1-table 6:
Table 1
| Component | Consumption (wt%) |
| Sodium lauryl sulphate | 4 |
| Ammonium lauryl sulfate | 6 |
| Cocos nucifera oil both sexes sodium acetate | 5 |
| The cocamidopropyl propyl amide amine oxide | 5 |
| Glycerol | 4 |
| Pyrrolidone sodium carboxylate | 1 |
| Ethylenediaminetetraacetic acid | 0.05 |
| INCROQUAT TMC-80 ECONOL TM22 | 1.5 |
| The Semen Sesami Nigrum extracting solution | 2.5 |
| Silk Amino Acids | 1 |
| Chlorine dioxide | 0.002 |
| Methyl vinyl ether | 5 |
| The PEG-150 distearate | 5 |
| The pH regulator agent | In right amount |
| Deionized water | Complement to 100 |
Table 2
| Component | Consumption (wt%) |
| Dodecyl alcohol ether sodium sulfate | 10 |
| Fatty alcohol-polyoxyethylene ether | 10 |
| Cocamido propyl betaine | 7.5 |
| Dimethyl dodecyl amine oxide | 7.5 |
| Sorbitol | 5 |
| Sodium lactate | 3 |
| The water solublity Jojoba oil | 2 |
| Disodiumedetate | 0.18 |
| Cation guar gum | 2 |
| Emulsified silicone oil | 2 |
| Vitamin B6 | 1.5 |
| Aloe extraction solution | 2 |
| Chlorine dioxide | 0.01 |
| The pH regulator agent | In right amount |
| Deionized water | Complement to 100 |
Table 3
| Component | Consumption (wt%) |
| 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium | 10 |
| SAS | 10 |
| The N-sodium lauroyl sarcosine | 10 |
| Empgen BB | 10 |
| Alkyl-glucoside | 10 |
| D-panthenol | 3 |
| Hyaluronic acid | 0.2 |
| Water solublity VE | 0.5 |
| Polyethylene Glycol-75-lanoline | 3 |
| Disodiumedetate | 0.3 |
| Polyquaternary ammonium salt-47 | 2 |
| The cationic conditioning high polymer | 2 |
| Hexadecyltrimethylammonium chloride | 2 |
| Plant triol | 4 |
| Alginate jelly | 1 |
| The fatty acid distribution of coconut oil diglycollic amide | 3 |
| Chlorine dioxide | 0.02 |
| The pH regulator agent | In right amount |
| Deionized water | Complement to 100 |
Table 4
| Component | Consumption (wt%) |
| Sodium lauryl sulphate | 4 |
| Ammonium lauryl sulfate | 6 |
| Cocos nucifera oil both sexes sodium acetate | 5 |
| The cocamidopropyl propyl amide amine oxide | 5 |
| Glycerol | 4 |
| Pyrrolidone sodium carboxylate | 1 |
| Ethylenediaminetetraacetic acid | 0.05 |
| INCROQUAT TMC-80 ECONOL TM22 | 1.5 |
| The Semen Sesami Nigrum extracting solution | 2.5 |
| Silk Amino Acids | 1 |
| Sodium chlorite | 0.2 |
| Methyl vinyl ether | 5 |
| The PEG-150 distearate | 5 |
| The pH regulator agent | In right amount |
| Deionized water | Complement to 100 |
Table 5
| Component | Consumption (wt%) |
| Dodecyl alcohol ether sodium sulfate | 10 |
| Fatty alcohol-polyoxyethylene ether | 10 |
| Cocamido propyl betaine | 7.5 |
| Dimethyl dodecyl amine oxide | 7.5 |
| Sorbitol | 5 |
| Sodium lactate | 3 |
| The water solublity Jojoba oil | 2 |
| Disodiumedetate | 0.18 |
| OTAC | 2 |
| Emulsified silicone oil | 2 |
| Vitamin B6 | 1.5 |
| Aloe extraction solution | 2 |
| Sodium chlorite | 1.5 |
| The pH regulator agent | In right amount |
| Deionized water | Complement to 100 |
Table 6
| Component | Consumption (wt%) |
| 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium | 10 |
| SAS | 10 |
| The N-sodium lauroyl sarcosine | 10 |
| Empgen BB | 10 |
| Alkyl-glucoside | 10 |
| D-panthenol | 3 |
| Hyaluronic acid | 0.2 |
| Water solublity VE | 0.5 |
| Polyethylene Glycol-75-lanoline | 3 |
| Disodiumedetate | 0.3 |
| Polyquaternary ammonium salt-47 | 2 |
| The cationic conditioning high polymer | 2 |
| Hexadecyltrimethylammonium chloride | 2 |
| Plant triol | 4 |
| Alginate jelly | 1 |
| The fatty acid distribution of coconut oil diglycollic amide | 3 |
| Sodium chlorite | 1.5 |
| Potassium chlorite | 1.5 |
| The pH regulator agent | In right amount |
| Deionized water | Complement to 100 |
The above-mentioned method for preparing that contains the dandruff-removing itching-relieve shampoo of different component is: remove ionized water by above-mentioned weight percent amount, add chelating agen, wetting agent, stir and make its dissolving; Add the Surfactant component then, be heated to 60-75 ℃, stir and make its whole dissolvings; Add the conditioner component then, the restir dissolving adds thickener component; Stirring makes its dissolving, is cooled to 30 ℃ or following then, feeds chlorine dioxide or adds chlorine dioxide precursor; Stir the back and use pH regulator agent adjust pH to be 5.5-7.5, promptly get.
The present invention contains the bactericidal effect of the dandruff-removing itching-relieve shampoo of chlorine dioxide:
(1) chlosma that produces the dandruff is had good killing action, use these article 5mins action time, sterilization rate is more than 99%;
(2) pityrosporum furfur, antibacterial, the yeast that causes seborrheic dermatitis had good killing action, use these article 5mins action time, sterilization rate is more than 99%.
Though, the present invention has been done detailed description in the preceding text with general explanation and specific embodiments, on basis of the present invention, can to some modifications of do or improvement, this will be apparent to those skilled in the art.Therefore, these modifications or the improvement on the basis of not departing from spirit of the present invention, made all belong to the scope that requirement of the present invention is protected.
Claims (5)
1. shampoo that contains chlorine dioxide; Process by following components in weight percentage: surfactant 10-60, wetting agent 1-20, chelating agen 0.01-0.5, chlorine dioxide or chlorine dioxide precursor 0.001-5, conditioner 1-15 and thickening agent 1-20; Add an amount of pH regulator agent and regulate pH value, complement to 100 with deionized water to 5.5-7.5;
Wherein, said surfactant is one or more in sodium lauryl sulphate, ammonium lauryl sulfate, dodecyl alcohol ether sodium sulfate, dodecyl alcohol ether ammonium sulfate, fatty alcohol-polyoxyethylene ether, N-lauroyl musculamine acid sodium, cocos nucifera oil acyl methyl taurine sodium, cocos nucifera oil both sexes sodium acetate, 1-isobutyl-3,5-dimethylhexylphosphoric acid, 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium salt, fatty alcohol-polyoxyethylene ether monomester succinate disodium, SAS, cocos nucifera oil sodium isethionate, lauryl alcohol carboxylic acid sodium, alkyl polyglucoside, empgen BB, dodecyl CAB, cocos nucifera oil acyl aminopropyl betanin, cocamidopropyl propyl amide hydroxyl sulphonic acid betaine, dimethyl dodecyl amine oxide, cocamidopropyl propyl amide amine oxide and the cocos nucifera oil acyl glutamic acid triethanolamine; Said wetting agent is one or more in glycerol, propylene glycol, 1,3-butylene glycol, sorbitol, pyrrolidone sodium carboxylate, hyaluronic acid, methyl glucosamine polyoxyethylene ether, lactic acid, sodium lactate, ceramide, water solublity Jojoba oil, water solublity VE, polyoxyethylene-75-lanoline and the Polyethylene Glycol-75-lanoline; Said chelating agen is ethylenediaminetetraacetic acid, disodiumedetate or tetrasodium ethylenediamine tetraacetate; Said chlorine dioxide precursor is sodium chlorite, potassium chlorite, lithium chlorite, magnesium chlorite or barium chlorite; Said conditioner is a hexadecyltrimethylammonium chloride; OTAC; INCROQUAT TMC-80 ECONOL TM22; Arquad 316; Cationic cellulose polymer; Cation guar gum; Polyquaternary ammonium salt; Salcare 96; Salcare 60; The polyoxyethylene ether polymer; Water-soluble silicon oil and emulsified silicone oil; Vitamin B5; Vitamin B6; Plant triol; Aloe extraction solution; Silk Amino Acids; The Semen Sesami Nigrum extracting solution; Chitosan; In quaternized albumen or the high fatty alcohol one or more; Said thickening agent is a hydroxyethyl-cellulose; Carboxymethyl cellulose; Polyvinylpyrrolidone; Acrylic copolymer; Acrylate copolymer; The PEG-150 distearate; The two stearates of polyethylene glycol 6000; The PEG-120 methyl glucosamine; Xanthan gum; Alginate jelly; The card ripple; Sodium chloride; Acusol772 Acusol771; Methyl vinyl ether; The fatty acid distribution of coconut oil single ethanol amide; The fatty acid distribution of coconut oil diglycollic amide; Execute in ADM and acrylic ester/neodecanoic acid hexenoic acid cross-linked copolymer one or more over it.
2. shampoo according to claim 1; Process by following components in weight percentage: surfactant 15-55, wetting agent 3-15, chelating agen 0.02-0.4, chlorine dioxide or chlorine dioxide precursor 0.002-4, conditioner 2-15 and thickening agent 2-15; Add an amount of pH regulator agent and regulate pH value, complement to 100 with deionized water to 5.5-7.5.
3. shampoo according to claim 2; Process by following components in weight percentage: surfactant 20-50, wetting agent 5-10, chelating agen 0.05-0.3, chlorine dioxide or chlorine dioxide precursor 0.004-3, conditioner 5-10 and thickening agent 5-10; Add an amount of pH regulator agent and regulate pH value, complement to 100 with deionized water to 5.5-7.5.
4. according to any described sterilization shampoo of claim 1-3, wherein the pH regulator agent is one or more in citric acid, sodium citrate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, boric acid and the Borax.
5. any said method that contains the shampoo of chlorine dioxide of preparation claim 1-4 is specially: measure deionized water in proportion, add chelating agen, wetting agent; Stirring makes its dissolving, adds the Surfactant component then, is heated to 60-75 ℃; Stirring makes its whole dissolvings, adds the conditioner component then, the restir dissolving; Add thickener component, stir and make its dissolving, be cooled to 30 ℃ or following then; Feed chlorine dioxide or add chlorine dioxide precursor, stir the back and use pH regulator agent adjust pH to be 5.5-7.5, promptly get.
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| CN1231826A (en) * | 1998-06-16 | 1999-10-20 | 徐忠奎 | Sterilizing agent for person and its preparing method |
| CN1565421A (en) * | 2003-06-12 | 2005-01-19 | 朱芳海 | A set of externally used products capable of killing multiple pathogenic microorganism |
| CN1537605A (en) * | 2003-07-05 | 2004-10-20 | 周恒德 | Herbal medicine for eliminating dandruff |
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| CN101785745A (en) | 2010-07-28 |
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