WO2019029630A1 - 一种含纳米硫组合物及其应用 - Google Patents

一种含纳米硫组合物及其应用 Download PDF

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Publication number
WO2019029630A1
WO2019029630A1 PCT/CN2018/099661 CN2018099661W WO2019029630A1 WO 2019029630 A1 WO2019029630 A1 WO 2019029630A1 CN 2018099661 W CN2018099661 W CN 2018099661W WO 2019029630 A1 WO2019029630 A1 WO 2019029630A1
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Prior art keywords
sulfur
nano
containing composition
acid
sodium
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PCT/CN2018/099661
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English (en)
French (fr)
Inventor
夏魁
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苏州魁星新材料科技有限公司
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Priority to CA3068675A priority Critical patent/CA3068675C/en
Priority to CN202110254298.9A priority patent/CN112999099B/zh
Priority to CN201880042530.9A priority patent/CN110997558B/zh
Priority to JP2019572818A priority patent/JP2020529971A/ja
Priority to US16/627,842 priority patent/US20200156942A1/en
Priority to EP18845221.3A priority patent/EP3666729B1/en
Priority to AU2018315192A priority patent/AU2018315192B2/en
Publication of WO2019029630A1 publication Critical patent/WO2019029630A1/zh
Priority to US17/533,772 priority patent/US11919770B2/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/23—Sulfur; Selenium; Tellurium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/10—Finely divided sulfur, e.g. sublimed sulfur, flowers of sulfur
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/0243—Other after-treatment of sulfur
    • C01B17/0248—Other after-treatment of sulfur of particulate sulfur
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/14—Boron; Compounds thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/157—Inorganic compounds
    • A—HUMAN NECESSITIES
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    • A—HUMAN NECESSITIES
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    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K45/00—Medicinal preparations containing active ingredients not provided for in groups A61K31/00 - A61K41/00
    • A61K45/06—Mixtures of active ingredients without chemical characterisation, e.g. antiphlogistics and cardiaca
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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    • 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
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    • A—HUMAN NECESSITIES
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    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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    • A—HUMAN NECESSITIES
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    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/10—Antimycotics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61P35/00—Antineoplastic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to a nano-containing sulfur composition and uses thereof.
  • Sulfur is a very active non-metallic element that is used in a wide range of applications such as sulfuric acid, pesticides, chemical fibers, rubber, dyes, paper, pharmaceuticals, explosives, matches, and more. Sulfur plays an important role in our daily lives, such as sulfuric acid used for disinfection, sulfur ointment used to treat skin diseases, and so on. Sulfur in nature is also closely related to our health. For example, sulfur hot spring is called “skin soup”, which has the effect of softening the stratum corneum of the skin, and has the effect of relieving itching, detoxification and detoxification.
  • the improvement of inflammation, dermatitis and neuralgia is particularly useful, mainly because the sulfur is disinfected and sterilized; the body is supplemented with polysulfide-rich foods such as garlic, onions, leeks, cabbages, broccoli, etc. It is good for health, mainly because some of the sulfur compounds are at work.
  • sulfur Although sulfur is widely used, its specific application is greatly limited. For example, commercially available sulfur preparations such as sulphur ointments or sulphur creams, although indicated in their instructions for use, can treat many skin diseases, but in practical clinical applications, the effects are not good and are almost eliminated by the market.
  • CN105708770A discloses a acne toner comprising a mixture of a carrier and an active ingredient in a percentage by weight, including: carrier: propylene glycol 3-15%, 1,3-butanediol 6-10%, sorbitol 5-8%, deionized water 64.9-85.2%; efficacy components: nano-sulfur 0.5-1.3%; other functional ingredients 0.3-0.8%.
  • the description of the nanosulfur in this patent is limited to the nanometer sulfur particle size of 50 nm and it can be obtained by processing elemental sulfur using nanotechnology (see paragraphs [0006] and [0031] of the specification), ie the patent does not specifically describe how Characterization data of nano-sulfur powder and nano-sulfur powder with a particle size of about 50 nm were obtained.
  • the preparation process of nano-sulfur powder is usually very complicated, resulting in high cost; in addition, although the particle size of the nano-sulfur powder as a raw material is small, once added After the entire acne toner system or other application system, the nano-sulfur powder will be significantly agglomerated, forming a larger particle size of sulfur particles, so that it is difficult to effectively act on bacteria or bacteria in the skin surface or pores. Similarly, it is also difficult to effectively sterilize other substrates with bacteria or bacteria.
  • One of the objects of the present invention is to provide a nano-sulfur-containing composition which can be used in various sulfur-containing products instead of the existing nano-sulfur or micro-sulfur, so that the action of the sulfur active component can be more fully exerted.
  • Another object of the present invention is to provide a preparation method of a nano-sulfur-containing composition which is simple in process and which can obtain a small particle size for a long time in the obtained composition.
  • a third object of the present invention is to provide a sulfur-containing product in which the action of the sulfur active component can be more fully exerted and has a better application effect.
  • the present invention provides a nano-sulfur-containing composition comprising nano-sulfur and an anti-agglomerating agent for preventing or retarding the nano-sulfur agglomeration. .
  • the anti-agglomerating agent is selected from the group consisting of a thickener, a suspending agent, a dispersing agent, an emulsion, a binder, a deflocculating agent, a coupling agent, an antistatic agent, a surfactant, A combination of one or more of the colloids.
  • the thickener is a combination of any one or more selected from the group consisting of a natural thickener and a chemically synthesized thickener, wherein the natural thickener comprises starch, dextrin, and arabic.
  • the chemically synthesized thickeners include sodium carboxymethyl starch, hydroxypropyl starch ether, sodium starch phosphate, acetyl disodium phosphate, phosphorylated distarch phosphate, and hydroxypropyl distarch phosphate.
  • the suspending agent is selected from the group consisting of glycerin, syrup, gum suspension, plant polysaccharide suspension, cellulosic suspension, carbopol, povidone a combination of one or more of dextran, silicon bentonite, and thixotrope.
  • the dispersing agent is selected from the group consisting of water glass, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, sodium lauryl sulfate, methylpentanol A combination of one or more of a cellulose derivative, a polyacrylamide, a guar gum, a polyethylene glycol, a fatty acid polyethylene glycol ester.
  • the surfactant is a combination of one or more selected from the group consisting of a double-chain ionic surfactant, an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
  • a double-chain ionic surfactant such as sodium dioctyl sulfonate (AOT); an anionic surfactant such as sodium dodecyl sulfate (SDS), Sodium dodecylbenzene sulfonate (DBS); cationic surfactants such as cetyltrimethylammonium bromide (CTAB); nonionic surfactants such as TritonX series (polyoxyethylene ethers).
  • the colloid is a combination of one or more selected from the group consisting of colloidal silica, starch colloid, protein colloid, soy milk, and colloidal silica.
  • the anti-agglomerating agent is a food additive and/or a pharmaceutical excipient.
  • the anti-agglomerating agent is selected from the group consisting of starch, dextrin, gum arabic, carrageenan, pectin, agar, alginic acid, sodium alginate, glycol alginate, tamarind gum , chitin, geranium gum, linseed gum, tianjing gum, guar gum, locust bean gum, xanthan gum, sodium carboxymethyl starch, hydroxypropyl starch ether, sodium starch phosphate, acetyl diamyl phosphate , phosphorylated distarch phosphate, hydroxypropyl distarch phosphate, glycerin, syrup, carbopol, povidone, dextran, bentonite, thixotrope, water glass, sodium tripolyphosphate, six Sodium metaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, sodium lauryl sulfate,
  • the anti-agglomerating agent of the present invention may be any substance which can prevent or delay the agglomeration of nano-sulfur, and may be any anti-agglomerating substance or multiple anti-agglomerates.
  • the combination of the agglomerated substances is not particularly limited.
  • the mass ratio of the nanosulfur to the anti-agglomerating agent in the nano-sulfur-containing composition is from 1 to 10: 0.5 to 20. In some embodiments, the mass ratio of the nanosulfur to the anti-agglomerating agent in the nano-sulfur-containing composition is from 1 to 10:0.5 to 10. In some embodiments, the mass ratio of the nanosulfur to the anti-agglomerating agent in the nano-sulfur-containing composition is from 1 to 10:0.5 to 5. According to a specific aspect of the present invention, the mass ratio of the nanosulfur to the anti-agglomerating agent in the nano-sulfur-containing composition may be from 1 to 5: 0.5 to 5.
  • the nano-sulfur has a particle diameter of 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 5 nm to 3000 nm, further preferably 10 nm to 2000 nm, and still more preferably 20 nm to 500 nm.
  • the nanosulfur may have a particle size of 20 to 400 nm, 20 to 300 nm, 20 to 200 nm, or 20 to 150 nm.
  • the nanosulfur may have a particle size of from 30 to 100 nm.
  • the nanosulfur may have a particle size of 30 to 90 nm.
  • the nanosulfur may have a particle size of 40 to 100 nm.
  • the size of the nanoparticles can be controlled and adjusted.
  • the anti-agglomerating agent component and its amount can be adjusted to adjust the size of the nanoparticles.
  • the average particle size change of the nano-sulfur is generally less than 30%, preferably less than 20%, more preferably less than 10%.
  • the nano-sulphur-containing composition further comprises a solvent, and the nano-sulfur and anti-agglomerating agent are dispersed in the solvent.
  • the solvent is a combination of one or more selected from the group consisting of water, ethanol, glycerol, and polyethylene glycol. According to a particular aspect of the invention, the solvent is water.
  • the nano-sulphur-containing composition is in a liquid state.
  • the nano-sulfur-containing composition has a mass content of the nano-sulfur of 0.01% to 10%. In some embodiments of the present invention, the nano-sulfur composition may have a mass content of the nano-sulfur of 0.01% to 7%. In some embodiments of the present invention, the nano-sulfur composition may have a mass content of the nano-sulfur of 0.1% to 7%.
  • the anti-agglomerating agent has a mass content of from 0.01 to 25%. In certain embodiments of the invention, the anti-agglomerating agent may have a mass content of from 0.5 to 25%. In certain embodiments of the invention, the anti-agglomerating agent may have a mass content of from 0.5 to 15%. In certain embodiments of the invention, the anti-agglomerating agent may have a mass content of from 0.5 to 5%.
  • the nanosulfur-containing composition consists essentially of the nanosulfur, anti-agglomerating agent.
  • the nano-sulfur-containing composition is mainly composed of nano-sulfur, an anti-agglomerating agent, and a solvent, wherein the solvent is not particularly limited, but is preferably those commonly used in the art, especially water, an alcohol solvent. Wait.
  • the specific solvent may be, for example, a combination of one or more of water, ethanol, propylene glycol, glycerin, polyethylene glycol, and the like.
  • the nanosulfur-containing composition is prepared by the following method (a) or (b) or (c):
  • a nano-sulfur-containing composition is prepared by a microemulsion method using a thiosulfate or a polysulfide and an acid as a reaction raw material.
  • the nano-sulfur-containing composition prepared by the method (b) or (c), wherein the nano-sulfur particle size is used Smaller, more uniform, more stable, and the effect is significantly better.
  • the thiosulfate salt may be a combination of one or more selected from the group consisting of sodium thiosulfate, ammonium thiosulfate, and potassium thiosulfate.
  • Sx a polysulfide
  • x 2, 3, 4, 5, 6, ..., 9.
  • the polysulfide is acidified, hydrogen sulfide and sulfur are released: Sx+2H ⁇ H 2 S+(x-1)S.
  • the polysulfide may be a combination of one or more selected from the group consisting of sodium polysulfide, potassium polysulfide, and ammonium polysulfide.
  • the acid may be selected from any inorganic acid, organic acid or a combination of the two, wherein the organic acid includes, but is not limited to, citric acid, tartaric acid, salicylic acid, benzoic acid, carboxylic acid, lactic acid, etc.
  • the inorganic acids include, but are not limited to, hydrochloric acid, sulfuric acid, boric acid, nitric acid, and the like.
  • the acid may be a combination of one or more selected from the group consisting of hydrochloric acid, benzoic acid, acetic acid, citric acid, tartaric acid, boric acid, salicylic acid, lactic acid, sulfuric acid, and nitric acid. .
  • a preparation method of a nano-sulfur-containing composition as described above comprising: making thiosulfate or more The sulfide-containing acid is reacted with an acid in the presence of an anti-agglomerating agent to obtain a nano-sulfur-containing composition.
  • the thiosulfate salt is a combination of one or more selected from the group consisting of sodium thiosulfate, ammonium thiosulfate, and potassium thiosulfate.
  • the polysulfide is selected from the group consisting of sodium polysulfide, potassium polysulfide, ammonium polysulfide.
  • the acid is a combination of one or more selected from the group consisting of hydrochloric acid, benzoic acid, acetic acid, citric acid, tartaric acid, boric acid, salicylic acid, lactic acid, sulfuric acid, nitric acid.
  • yet another technical solution adopted by the present invention is as follows: The use of the nano-sulfur-containing composition as described above for the preparation of a sulfur-containing product.
  • the sulfur-containing product is a skin care product for human or animal skin, a drug for treating skin diseases, a drug for treating tumors, a drug for treating hair diseases, a pesticide, a preservative for vegetables, fruits and plants, and the like.
  • animal food additive paint anti-mold additive, fabric anti-mold agent or fabric acaricide.
  • the sulfur-containing product is a skin care product for human or animal skin, a drug for treating skin diseases, a drug for treating tumors, a drug for treating hair diseases, a pesticide, a preservative for vegetables, fruits and plants, and the like.
  • animal food additive paint anti-mold additive, fabric anti-mold agent or fabric acaricide.
  • the nano-sulfur-containing composition improved according to the present invention can maintain the nano-sulfur in a nano-dispersed state for a long period of time, thereby effectively improving the activity and efficacy of sulfur, and helping to reduce the amount of sulfur, particularly suitable.
  • a care product or a drug for the surface of a human or animal skin in addition to being suitable for adding a drug for treating a tumor, a drug for treating a hair disease, a preservative for a pesticide, a vegetable and a fruit plant, an animal food additive, a coating anti-mold additive, A fabric antifungal or (fabric) acaricide.
  • a care product prepared in accordance with the teachings of the present invention is effective to prevent, ameliorate, alleviate or eliminate fungal skin infections.
  • the toiletries are a cream, a cream, a shower gel, a shampoo, a lotion, a body lotion, a facial cleanser, a hand lotion, a toilet water, a soap, a cleansing foam, a mask, Shampoo, cream, anti-cracking oil, serum, whitening cream, sunscreen lotion, freckle cream, hand cream, moisturizing balance, moisturizer, toner, firming lotion or astringent water.
  • the nano-sulfur-containing composition may be added in a small amount in the toiletries, usually in an amount of about 0.005 to 0.25% of the content of the nano-sulfur. Add to.
  • the pharmaceutical composition prepared according to the inventive concept is effective for treating skin fungal infections and treating various skin diseases such as skin dermatitis, dermatitis, pityriasis, eczema and the like.
  • the nano-sulfur containing composition is added in an effective amount.
  • the nano-sulfur-containing composition may be added to the pharmaceutical composition in an amount less than the amount of nano-sulfur added to the prior art, usually in the form of nano-sulfur
  • the amount of the pharmaceutical composition is added in an amount of about 0.01% to 0.5%.
  • the pharmaceutical composition further comprises a synergist.
  • the synergist may, for example, be a combination of one or more selected from the group consisting of alum, zinc oxide or borax.
  • the synergist may have a mass content of from 1 to 5%.
  • the pharmaceutical composition may further comprise a humectant.
  • the humectant may be, for example, a combination of one or more selected from the group consisting of polyhydric alcohols, hyaluronic acid, ceramides, collagen, urea, chitin derivatives, aloe vera or seaweed extracts.
  • the humectant may be present in the pharmaceutical composition in an amount of from 2 to 10% by mass.
  • the pharmaceutical composition may be in the form of an ointment, a gel, a cream or a liquid.
  • the pharmaceutical composition may further comprise an active substance other than the nano-sulfur composition that can treat a skin condition.
  • nano-sulfur-containing composition of the present invention since the added amount of nano-sulfur is a small amount, only a few thousandths of the sulfur content in the whole product can be obtained, thereby weakening or even avoiding the drying and peeling of the skin.
  • the prepared nano-sulfur-containing composition may be directly added to other substrates, and although it contains a small amount of a sodium salt, a potassium salt or an ammonium salt, etc., it is not actually removed, such as sodium chloride. Very small amount of use is harmless, and as sodium acetate, it also has antiseptic effect, so the prepared nano-sulfur-containing composition can be directly applied to the product without additional operations to remove other substances. The effect of additional factors on the maintenance of the nanostate of nanosulphur is reduced or even avoided.
  • the present invention has the following advantages compared with the prior art:
  • the invention overcomes the defects of the nano-sulfur easy agglomeration in the preparation or use of the traditional nano-sulfur, realizes that the nano-sulfur can maintain the nano-state for a long time, and the inventors have prepared the nano-sulfur-containing composition for a long time after standing (currently more than In the half year period, the nano-sulfur was still maintained in the nano-state and uniformly dispersed in the dispersion medium, which basically eliminated the occurrence of agglomeration.
  • the nano-sulphur-containing composition of the present invention can be added to any product requiring sulfur, and a better effect can be obtained with a lower added amount.
  • the sulfur-containing product of the invention wherein the nano-sulfur maintains a very good dispersibility and a small particle size, the sulfur activity can be more fully exerted, and the application effect is remarkably superior. At the same time, since the activity of sulfur can be more fully exerted, the amount of sulfur can be greatly reduced, thereby reducing or avoiding the negative problems caused by the large amount of sulfur. Furthermore, the sulfur-containing products of the present invention are relatively low in cost. Therefore, the sulfur-containing product of the present invention is extremely easy to promote.
  • Example 1 is a photograph of a nano-sulfur containing composition prepared in Example 1 of the present invention after standing for half a year;
  • the nano-sulfur still maintains the initial state and is still uniformly dispersed in the dispersion medium.
  • the conventional preparation method of the sulfur-containing product is to first obtain a high-purity solid sulfur powder, and then disperse the sulfur powder into other components of the sulfur-containing product, and mix to obtain a sulfur-containing product.
  • the sulfur-containing product obtained by the conventional method has a small particle size of the raw material sulfur powder used and various auxiliary dispersing means, and sulfur is liable to agglomerate and affect the use effect.
  • the inventors have discovered through accidental discovery that an additive (or an anti-agglomeration agent) which can prevent or delay the agglomeration thereof is added before the formation of nano-sulfur and the nano-sulfur formed is retained after the formation of the nano-sulfur. It is not easy to agglomerate. Further, when the composition of the nano-sulfur and the auxiliary agent thus obtained is used for preparing a sulfur-containing product, the nano-sulfur continues to maintain a very good dispersing property and a small particle diameter, and thus the sulfur-containing activity of the prepared sulfur-containing product Can be more fully played, the application effect is significantly better. Further, since the activity of sulfur can be more fully exerted, the amount of sulfur can be greatly reduced, thereby reducing or avoiding the negative problems caused by the large amount of sulfur.
  • the invention proposes to overcome the traditional prejudice that the high-purity sulfur powder is prepared first (it is generally believed that there may be a small amount of impurities in the raw material, but the by-products are not tolerated, otherwise the quality is not good, for example, in many literatures on nano-sulfur Emphasis is placed on purity).
  • the nano-sulfur-containing composition of some embodiments of the present invention contains an auxiliary agent (anti-agglomerating agent) and residual thiosulfate, polysulfide and acid, etc. It is harmless, but it is beneficial in most cases.
  • auxiliary agent anti-agglomerating agent
  • Sodium Chloride (Salt) A by-product of the production of sulfur by the reaction of sodium thiosulfate with hydrochloric acid, which is beneficial in skin care products such as shampoos and soaps, and is also beneficial in animal feed.
  • Sodium lactate The by-product of the reaction of sodium thiosulfate with lactic acid to produce sulfur, which can be used as a humectant, is beneficial in skin and hair care products and medicines. Sulfur causes dry skin and even causes peeling and has undesirable side effects. Sodium lactate has a moisturizing effect, which solves the problem of dry skin. To make nano-sulfur drugs and skin care products, it is necessary to add moisturizers, and even moisturizers must be used to eliminate the adverse side effects of nano-sulfur.
  • Ammonium lactate a by-product produced by the reaction of ammonium thiosulfate with lactic acid to produce sulfur, which is widely used in foods, beverages, dairy products, nutrient solutions, medicines, etc., and can also be used as a feed additive.
  • Sodium citrate A by-product produced by the reaction of sodium thiosulfate with citric acid to prepare sulfur, which is often used as a food additive, a preservative, etc., and may also be added to a skin care and toiletries.
  • Ammonium chloride A by-product produced by the reaction of ammonium thiosulfate with hydrochloric acid to produce sulfur, which can be used as a fertilizer. When a nano-sulfur mixture is used as a pesticide, a small amount of ammonium chloride is not only harmless but also can be used as a fertilizer.
  • Sodium tartrate a by-product of the production of sulfur by the reaction of sodium thiosulfate with tartaric acid, which is often used in foods, beverage additives, antioxidants, in the pharmaceutical and food industries.
  • Sodium Benzoate A by-product of the production of sulfur by the reaction of sodium thiosulfate with benzoic acid, which is often used as a bactericide, preservative, antimicrobial agent, etc., and can be used in skin care and toiletries.
  • Sodium borate a by-product produced by the reaction of sodium thiosulfate with boric acid to prepare sulfur, which can be used for disinfection and antisepsis of skin mucosa, athlete's foot, fungal vaginitis, cervical erosion, hemorrhoids, hemorrhoids, external ear canal eczema, herpes virus skin It can be used for the treatment of tumors and as a feed additive.
  • Boron-containing trace element fertilizers in agriculture have fertilizer effects on many crops, which can improve crop quality and increase yield.
  • Sodium acetate a by-product of sodium thiosulfate and acetic acid, which can be used as a buffering agent, a flavoring agent, a flavoring agent and a pH adjusting agent, and has certain antifungal and antifungal effects, and can be used for skin care products. in.
  • a suitable anti-agglomerating agent and a thiosulfate or polysulfide and an acid for preparation can be selected, and at the same time, a beneficial additive can be obtained at the same time, which is a two-fold effect. More significant is the elimination of complex, costly purification processes. Greatly reduce the cost of nano-sulfur production.
  • the anti-agglomerating agent of the present invention may be any substance which can prevent or delay the agglomeration of nano-sulfur, and may be any anti-agglomerating substance or a combination of a plurality of anti-agglomerating substances, and is not particularly limited.
  • the types of substances that can prevent or delay nano-sulfur agglomeration are very broad, including but not limited to various thickeners, suspending agents, dispersing agents, emulsions, coupling agents, antistatic agents, surfactants, and sols. , gel, etc. These specific anti-agglomerating agents all have anti-agglomeration effects, but only the difference in the degree of effect.
  • the thickener of the present invention is not particularly limited and may be selected from any one or a combination of a natural thickener and a chemically synthesized thickener.
  • Natural thickeners include, but are not limited to, various starches (wheat flour, rice flour, potato flour, pueraria powder, etc.), dextrin, gelatin, gum arabic, carrageenan, pectin, agar, alginic acid thickener, tamarind Gum, chitin, geranium gum, linseed gum, tianjing gum, guar gum, locust bean gum, xanthan gum.
  • Chemically synthesized thickeners include, but are not limited to, sodium carboxymethyl starch, hydroxypropyl starch ether, sodium starch phosphate, acetyl disodium phosphate, phosphorylated distarch phosphate, hydroxypropyl distarch phosphate, and the like.
  • Suspening agents are additives that increase the viscosity of the dispersion medium to reduce the sedimentation rate of the particles or increase the hydrophilicity of the particles.
  • the suspending agent of the present invention may be of various suspending agents, and is not particularly limited. For example, it may be a low molecular suspending agent such as glycerin, syrup, etc., and glycerin is often added to the external suspension; Polymer suspending agent.
  • Polymer suspending agents include:
  • Natural polymer suspending agent mainly gum trees, such as gum arabic, western gum, gum and so on. Acacia and tragacanth can be used in powders or pastes. There are also plant polysaccharides such as sodium alginate, agar, starch slurry and the like.
  • suspending agents celluloses such as methylcellulose, sodium carboxymethylcellulose, hydroxypropylcellulose. Others such as carbopol, povidone, dextran and the like. Most of these suspending agents are stable in nature and are less affected by pH, but care should be taken that certain suspending agents can be compatible with drugs or other additives.
  • Silicone bentonite It is a natural hydrous aluminum silicate, which is a grayish yellow or milky white very fine powder with a diameter of 1 to 150 ⁇ m. It is insoluble in water or acid, but swells in water and increases in volume by about 10 times to form a high viscosity. Thixotropy and pseudoplastic gels have greater swellability, higher viscosity and better suspending effect at pH >7.
  • Thixotropic rubber The thixotropy of the thixotropic gel, that is, the property of the gel and the sol to change at a constant temperature. When standing, a gel is formed to prevent the particles from settling, and when it is shaken, it becomes a sol to facilitate pouring.
  • the use of thixotropic suspending agents facilitates the stability of the suspension.
  • Aluminum monostearate is dissolved in vegetable oil to form a typical thixotropic gel.
  • Some aqueous solutions of polymer compounds with plastic flow and pseudoplastic flow are often thixotropic and can be used selectively.
  • suspending agents are specifically employed, for example, as colloidal silica, carboxymethylcellulose (CMC), sodium alginate, sodium carboxymethylcellulose (CMC-Na), and the like.
  • Dispersants are agents that promote the uniform dispersion of material particles in a medium to form a stable suspension. Dispersants are generally classified into two types: inorganic dispersants and organic dispersants. Common inorganic dispersants are silicates (such as water glass) and alkali metal phosphates (such as sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, etc.). Organic dispersants include triethylhexylphosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyethylene glycol esters, and the like.
  • inorganic dispersants are silicates (such as water glass) and alkali metal phosphates (such as sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, etc.).
  • Organic dispersants include triethylhexylphosphoric acid, sodium lauryl sulfate
  • the oil, surfactant, water (aqueous electrolyte solution) or co-surfactant is uniformly mixed, and then a co-surfactant or water (aqueous electrolyte solution) is added to the system to form a microemulsion within a certain ratio.
  • surfactants are: double-chain ionic surfactants, such as sodium dioctyl sulfosuccinate (AOT); anionic surfactants such as sodium dodecyl sulfonate (SDS), dodecyl benzene Sodium sulfonate (DBS); cationic surfactants such as cetyltrimethylammonium bromide (CTAB); nonionic surfactants such as Triton X series (polyoxyethylene ethers).
  • AOT sodium dioctyl sulfosuccinate
  • anionic surfactants such as sodium dodecyl sulfonate (SDS), dodecyl benzene Sodium sulfonate (DBS)
  • cationic surfactants such as cetyltrimethylammonium bromide (CTAB)
  • CTAB cetyltrimethylammonium bromide
  • nonionic surfactants such as Triton X series (polyoxyethylene ether
  • the colloid includes various sols, gels, and the like, and specifically, for example, a colloidal gel, a starch colloid, a protein colloid, a soybean milk, or the like.
  • Various colloidal substances facilitate the dispersion of nano-sulfur and prevent the aggregation of nano-sulfur.
  • anti-agglomerating agents such as coupling agents, antistatic agents, surfactants, emulsions and the like can exert an anti-agglomeration effect by improving the surface characteristics of the particles or the interaction between the particles.
  • the type of the surfactant is not limited, and may be a combination of one or more of a double-chain ionic surfactant, an anionic surfactant, a cationic surfactant, and a nonionic surfactant, wherein the double-stranded ion
  • the surfactant may be, for example, sodium dioctyl sulfonate sulfonate
  • the anionic surfactant may be, for example, sodium dodecyl sulfate or sodium dodecylbenzene sulfonate
  • the cationic surfactant may be, for example, hexadecane.
  • the trimethylammonium bromide, nonionic surfactant may be, for example, a polyoxyethylene ether surfactant.
  • the emulsion is, for example, Tween 60 and Span 20.
  • the anti-agglomerating agent is a food additive or a pharmaceutically acceptable adjuvant.
  • the particle size of the nano-sulfur composition was tested by GBT 19627-2005 particle size analysis photon correlation spectroscopy and GB/T 29022-2012 particle size analysis dynamic light scattering method (DLS).
  • the test temperature was room temperature 25 °C.
  • nano-sulfur composition for preparing antifungal drugs or toiletries
  • the nano-sulfur-containing composition of the invention can make the nano-sulfur maintain the nano-state for a long period of time without agglomeration, avoid agglomeration into a large particle state, and is difficult to be absorbed by the skin, thereby exhibiting antifungal effect and treating skin diseases, and at the same time, It can be used as an active ingredient in a toiletries and a pharmaceutical composition, and the toiletries and the pharmaceutical composition are not limited to the nano-sulfur-containing composition of the present invention as an active ingredient, and other ingredients may be used. It is suitable for the needs of the consumer; and the toiletries and the pharmaceutical composition can be selected according to the actual situation, such as a paste, a liquid, and the like.
  • the invention is applied to an antifungal medicine or a toiletries, and solves the problem that the nano sulfur in the traditional nano sulfur-containing product is not a true nano state (the large particle sulfur is hard to be absorbed by the skin and plays a bactericidal effect), on the one hand
  • the use of nano-sulfur is easily absorbed by the skin, which can greatly reduce the amount of sulfur used, reduce or even eliminate the side effects of dry skin caused by traditional sulfur-containing products, and, on the other hand, greatly reduce the amount of sulfur used.
  • There is almost no smell of sulfur, its appearance and aroma (additional addition) is no different from ordinary skin care products.
  • the use of the nanosulphur-containing product of the present invention does not contain hormones (the addition of hormones to traditional antifungal drugs)
  • the purpose is anti-allergic, anti-inflammatory, anti-itching, etc., and the use of hormones has obvious side effects, long-term use will cause disorder of its physiological functions), can replace traditional anti-fungal external medicine, to treat various dermatitis, stubborn ⁇ , eczema, etc.
  • the toiletries according to the present invention especially refer to toiletries for use on the skin surface of humans or animals.
  • the toiletries are a cream, a cream, a shower gel, a shampoo, a lotion, a body lotion, a facial cleanser, a hand lotion, a toilet water, a soap, a cleansing foam, a mask, Shampoo, cream, anti-cracking oil, serum, whitening cream, sunscreen lotion, freckle cream, hand cream, moisturizing balance, moisturizer, toner, firming lotion or astringent water.
  • a cream, a cream, a shower gel a shampoo, a lotion, a body lotion, a facial cleanser, a hand lotion, a toilet water, a soap, a cleansing foam, a mask, Shampoo, cream, anti-cracking oil, serum, whitening cream, sunscreen lotion, freckle cream, hand cream, moisturizing balance, moisturizer, toner, firming lotion or astringent water.
  • the nano-sulfur-containing composition may be added in a small amount in the toiletries, usually in an amount of about 0.005 to 0.25% of the content of the nano-sulfur. Add to.
  • the nanosulfur-containing composition is added in an effective amount.
  • the nano-sulfur-containing composition may be added in the antifungal topical drug in a smaller amount than the prior art nano-sulfur, usually in nanometers.
  • the sulfur is added in an amount of about 0.01% to 0.5% by weight of the antifungal external preparation.
  • the antifungal topical drug further comprises a synergist.
  • the synergist may, for example, be a combination of one or more selected from the group consisting of alum, zinc oxide or borax.
  • the synergist may have a mass content of 1 to 5%.
  • the antifungal topical drug may further comprise a humectant.
  • the humectant may be, for example, a combination of one or more selected from the group consisting of polyhydric alcohols, hyaluronic acid, ceramides, collagen, urea, chitin derivatives, aloe vera or seaweed extracts.
  • the humectant may have a mass content of 2 to 10%.
  • the antifungal topical drug is in the form of an ointment, a gel, a cream or a liquid.
  • the antifungal topical drug may further comprise an active substance other than the nano-sulfur composition which can treat a skin disease.
  • nano-sulfur-containing composition of the present invention since the added amount of nano-sulfur is a small amount, only a few thousandths of the sulfur content in the whole product can be obtained, thereby weakening or even avoiding the drying and peeling of the skin.
  • the prepared nano-sulfur-containing composition may be directly added to other substrates, and although it contains a small amount of a sodium salt, a potassium salt or an ammonium salt, etc., it is not actually removed, such as sodium chloride. Very small amount of use is harmless, and as sodium acetate, it also has antiseptic effect, so the prepared nano-sulfur-containing composition can be directly applied to the product without additional operations to remove other substances. The effect of additional factors on the maintenance of the nanostate of nanosulphur is reduced or even avoided.
  • the sulfur-containing product comprises (iii) thiosulfate ion or sulfur ion and/or (in addition to (i) elemental sulfur, (ii) anti-agglomerating agent.
  • Iv) Acid ion In the absence of evidence to the contrary, a sulfur-containing product having both (i), (ii), (iii) or a sulfur-containing product having both (i), (ii), (iv) or both Sulfur-containing products of the substances shown in (i), (ii), (iii), (iv) shall be considered to fall within the scope of protection of this patent.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate pentahydrate, hydroxypropyl starch ether, hydrochloric acid and water.
  • the preparation method is as follows:
  • the content of nano-sulfur in the obtained nano-sulfur-containing composition is about 3.06%.
  • the nano-sulfur-containing composition prepared in this embodiment contains sodium chloride as a by-product, and sodium chloride is used in skin care products such as shampoo. It is beneficial in soaps and is also beneficial in animal feeds, so there is no need to remove them as directed by conventional biases, while measuring the average particle size of sulfur therein to be about 132 nanometers. After the preparation was completed at room temperature for 6 months, the photograph taken is shown in Fig. 1.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, guar gum, acetic acid, and water.
  • the preparation method is as follows:
  • the content of nano-sulfur in the obtained nano-sulfur-containing composition is about 2.17%.
  • the nano-sulfur-containing composition prepared in this embodiment further contains sodium acetate as a by-product, and sodium acetate can be used as a buffering agent, a flavoring agent and a flavoring agent.
  • pH adjuster has certain anti-mold and anti-fungal effects, can be used in skin care products, so it is not necessary to remove it as directed by conventional bias, and the average particle size of sulfur is determined to be about 173 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, phosphorylated distarch phosphate, acetic acid and water.
  • the preparation method is as follows:
  • the content of nano-sulfur in the obtained nano-sulfur-containing composition is about 5.9%.
  • the nano-sulfur-containing composition prepared in this embodiment further contains sodium acetate as a by-product, and sodium acetate can be used as a buffering agent, a flavoring agent and a flavoring agent.
  • pH adjuster has certain anti-mold and anti-fungal effects, can be used in skin care products, so it is not necessary to remove it as directed by conventional bias.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, xanthan gum, acetic acid and water.
  • the preparation method is as follows:
  • the nano-sulfur-containing composition prepared in this embodiment further contains sodium acetate as a by-product, and sodium acetate can be used as a buffering agent, a flavoring agent and a flavoring agent.
  • pH adjuster has certain anti-mold and anti-fungal effects, can be used in skin care products, so it is not necessary to remove it as directed by conventional bias, and the average particle size of sulfur is determined to be about 285 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, carboxymethylcellulose, hydrochloric acid, benzoic acid, and water.
  • the preparation method is as follows:
  • the content of nano-sulfur in the obtained nano-sulfur-containing composition is about 1.75%.
  • the nano-sulfur-containing composition prepared in this embodiment contains sodium chloride and sodium benzoate as by-products, and sodium chloride is used in skin care products, for example. It is beneficial in shampoos and soaps. It is also beneficial in animal feed. Sodium benzoate is often used as a fungicide, preservative, antimicrobial agent, etc. It can also be used in skin care products, so there is no need for traditional prejudice. The two were removed as directed, and the average particle size of sulfur therein was measured to be about 46 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, hydroxyethyl cellulose, acetic acid, and water.
  • the preparation method is as follows:
  • the content of nano-sulfur in the obtained nano-sulfur-containing composition is about 2.22%, and the nano-sulfur-containing composition prepared in this embodiment further contains sodium acetate as a by-product, and sodium acetate can be used as a buffering agent, a flavoring agent and a flavoring agent.
  • pH adjuster has certain anti-mold and anti-fungal effects, can be used in skin care products, so it is not necessary to remove it as directed by conventional bias, and the average particle size of sulfur is determined to be about 43 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, polyethylene glycol, citric acid, and water.
  • the preparation method is as follows:
  • the nano-sulfur-containing composition prepared in this embodiment also contains sodium citrate as a by-product, and sodium citrate is often used as a food additive and a preservative. It can also be added to skin care toiletries, so it is not necessary to remove it as directed by conventional biases, and the average particle size of sulfur therein is measured to be about 180 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, povidone, tartaric acid and water.
  • the preparation method is as follows:
  • the mass content of the nano-sulfur in the obtained nano-sulfur-containing composition is about 1.81%, and the nano-sulfur-containing composition prepared in the embodiment contains the by-product sodium tartrate, which is often used for foods, beverage additives, antioxidants, and drugs. There are also applications in the food industry, so there is no need to remove them as directed by conventional biases, and the average particle size of sulfur therein is about 132 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, sodium alginate, benzoic acid and water.
  • the preparation method is as follows:
  • the nano-sulfur-containing composition prepared in this embodiment contains sodium benzoate as a by-product, and the substance is often used as a bactericide, a preservative, an antimicrobial agent, etc. It can be used in skin care toiletries, so it is not necessary to remove it as directed by conventional bias, and the average particle size of sulfur therein is measured to be about 30 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, starch, boric acid, and water.
  • the preparation method is as follows:
  • Nano-sulfur composition The content of nano-sulfur in the obtained nano-sulfur-containing composition is about 2.06%.
  • the nano-sulfur-containing composition prepared in this embodiment contains sodium borate as a by-product, and the substance can be used for disinfection and antisepsis of skin mucous membrane, ankle, and fungal vagina. Inflammation, cervical erosion, hemorrhoids, hemorrhoids, external ear canal eczema, herpes viral skin disease, can be used for the treatment of tumors, but also as a feed additive. Agricultural boron-containing micronutrient fertilizers are effective for many crops, improve crop quality and increase yield, so there is no need to remove them as directed by conventional biases, and the average particle size of sulfur is about 310 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, colloidal silica, salicylic acid, and water.
  • the preparation method is as follows:
  • the nano-sulfur content in the obtained nano-sulfur-containing composition is about 1.07%, and the nano-sulfur-containing composition prepared in the embodiment contains sodium salicylate as a by-product, and the substance can be used in foods, medicines, and preservatives. Therefore, it is not necessary to remove it as directed by conventional bias, and the average particle diameter of sulfur therein is measured to be about 40 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, gum arabic, lactic acid and water.
  • the preparation method is as follows:
  • the nano-sulfur-containing composition prepared in this embodiment contains sodium lactate as a by-product, and the substance can be used as a moisturizing agent in skin and hair care products and medicines. It is beneficial; sulfur makes the skin dry, even leading to peeling, has adverse side effects, and sodium lactate has a moisturizing effect, which solves the problem of dry skin.
  • a moisturizer To make nano-sulfur drugs and skin care products, it is necessary to add a moisturizer, and even a moisturizer must be used to eliminate the adverse side effects of nano-sulfur, so it is not necessary to remove it as directed by conventional bias, and the average particle size of sulfur is measured. It is 58 nanometers.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include ammonium thiosulfate, pectin, lactic acid and water.
  • the preparation method is as follows:
  • the nano-sulfur content in the obtained nano-sulfur-containing composition is about 1.58%, and the nano-sulfur-containing composition prepared in the embodiment contains ammonium lactate as a by-product, and the material is widely used in foods, beverages, dairy products, nutrient liquids, and medicines. Etc., it can also be used as a feed additive, so it is not necessary to remove it as directed by conventional bias, and the average particle size of sulfur therein is measured to be about 71 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, glycol alginate, acetic acid, and water.
  • the preparation method is as follows:
  • the content of nano-sulfur in the obtained nano-sulfur-containing composition is about 1.21%, and the nano-sulfur-containing composition prepared in this embodiment further contains sodium acetate as a by-product, and sodium acetate can be used as a buffering agent, a flavoring agent, and a flavoring agent.
  • pH adjuster has certain anti-mold and anti-fungal effects, can be used in skin care products, so it is not necessary to remove it as directed by conventional bias, and the average particle size of sulfur is determined to be about 42 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, lignin, benzoic acid and water.
  • the preparation method is as follows:
  • the nano-sulfur-containing composition prepared in this embodiment contains sodium benzoate as a by-product, and the substance is often used as a bactericide, a preservative, an antimicrobial agent, etc. It can be used in skin care toiletries, so it is not necessary to remove it as directed by conventional bias, and the average particle size of sulfur therein is about 230 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium polysulfide (Na 2 S 2 ), sodium carboxymethyl starch, lactic acid, and water.
  • the preparation method is as follows:
  • the nano-sulfur-containing composition prepared in this embodiment contains sodium lactate as a by-product, which can be used as a moisturizing agent, and is beneficial in skin and hair care products and medicines; sulfur causes dry skin, even causes peeling, and has undesirable side effects.
  • sodium lactate has a moisturizing effect, which solves the problem of dry skin.
  • the production of nano-sulfur drugs and skin care products requires the addition of humectants and even the use of humectants to eliminate the undesirable side effects of nano-sulphur, so there is no need to remove them as directed by traditional biases.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include potassium polysulfide (K 2 S 2 ), guar gum, acetic acid, benzoic acid, and water.
  • K 2 S 2 potassium polysulfide
  • guar gum guar gum
  • acetic acid benzoic acid
  • water water
  • the mass content of nano-sulfur in the obtained nano-sulfur-containing composition is about 2.79%.
  • the nano-sulfur-containing composition prepared in this embodiment contains potassium lactate as a by-product, and the substance can be used as an edible preservative; the anti-microbial agent is mainly used in foods such as margarine, diluted margarine, wine, etc., so there is no need for traditional prejudice It is to be removed as directed.
  • This embodiment provides a nano-sulfur-containing composition whose raw materials include ammonium polysulfide ((NH 4 ) 2 S 2 ), agar, lactic acid, and water.
  • the preparation method is as follows:
  • the content of nano-sulfur in the obtained nano-sulfur-containing composition is about 1.60%, and the nano-sulfur-containing composition prepared in the embodiment contains ammonium lactate as a by-product, and the material is widely used in foods, beverages, dairy products, nutrient liquids, medicines. Etc., it can also be used as a feed additive, so it is not necessary to remove it as directed by conventional bias, and the average particle size of sulfur therein is measured to be about 84 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include potassium thiosulfate, hydroxypropylcellulose, hydrochloric acid and water.
  • the preparation method is as follows:
  • the nano-sulfur-containing composition prepared in this embodiment contains potassium chloride as a by-product, and the material is a kind of potassium fertilizer in agriculture, and the fertilizer effect is fast.
  • Direct application to farmland can increase the moisture in the lower layer of the soil and have the effect of resisting drought. It can directly cooperate with nano-sulfur to play a better role, so it is not necessary to remove it as directed by traditional bias.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, Span 20, citric acid, and water.
  • the preparation method is as follows:
  • the composition is in a microemulsion state.
  • the content of nano-sulfur in the obtained nano-sulfur-containing composition is about 2.07%.
  • the nano-sulfur-containing composition prepared in this embodiment also contains sodium citrate as a by-product, and sodium citrate is often used as a food additive and a preservative. It can also be added to skin care toiletries, so it is not necessary to remove it as directed by conventional biases, and the average particle size of sulfur therein is about 310 nm.
  • This embodiment provides a nano-sulfur-containing composition, the raw materials of which include sodium thiosulfate, Tween 60, acetic acid, and water.
  • the preparation method is as follows:
  • nano-sulfur-containing composition prepared in this embodiment further contains sodium acetate as a by-product, and sodium acetate can be used as a buffering agent, a flavoring agent and a flavoring agent.
  • pH adjuster has certain anti-mold and anti-fungal effects, can be used in skin care products, so it is not necessary to remove it as directed by conventional bias.
  • This example provides a pharmaceutical composition for the treatment of acne, head lice, acne, seborrheic dermatitis, rosacea, pityriasis and chronic eczema, as shown in Table 1 below.
  • the preparation method of the pharmaceutical composition comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 2; and step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and The remaining raw materials are mixed and prepared.
  • This example provides a pharmaceutical composition for the treatment of acne, head lice, acne, seborrheic dermatitis, rosacea, pityriasis and chronic eczema, as shown in Table 2 below.
  • the preparation method of the pharmaceutical composition comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 10; step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and in Table 2 The remaining raw materials are mixed and prepared.
  • This embodiment provides a vanishing cream in a toiletries, and the specific formulation is shown in Table 3 below.
  • the preparation method of the cream comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 6; and step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and the remaining materials in Table 3. Mixed, that is, made.
  • This embodiment provides a cold cream (skin cream) in a toiletries, and the specific formulation is shown in Table 4 below.
  • the preparation method of the cold cream comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 12; and step (2): then preparing the nano-sulfur-containing composition prepared in the step (1)
  • the remaining materials in Table 4 were mixed and prepared.
  • This embodiment provides a moisturizer in a toiletries, and the specific formulation is shown in Table 5 below.
  • the preparation method of the moisturizer comprises the following steps: Step (1): preparing a nano-sulfur-containing composition according to Example 7; Step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and Table 5 The remaining raw materials are mixed and prepared.
  • This embodiment provides a moisturizing lotion in a toiletries, and the specific formulation is shown in Table 6 below.
  • the preparation method of the emollient emulsion comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 15; step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and The remaining raw materials are mixed and prepared.
  • This embodiment provides a skin care gel/massage gel/cleansing gel/anti-acne gel in a toiletries, and the specific formulation is shown in Table 7 below.
  • the preparation method of the skin care gel/massage gel/cleansing gel/anti-acne gel comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 12; step (2): then step (1) The prepared nano-sulfur-containing composition was mixed with the remaining raw materials in Table 7, and was prepared.
  • This embodiment provides a cleaning cream, and the specific formulation is shown in Table 8 below.
  • the preparation method of the cleaning cream comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 1; step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) with the rest in Table 8. The raw materials are mixed and prepared.
  • This embodiment provides a facial cleanser, and the specific formulation is shown in Table 9 below.
  • the preparation method of the facial cleanser comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 5; and step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) with the rest in Table 9.
  • the raw materials are mixed and prepared.
  • This embodiment provides a soap-based facial cleanser, and the specific formulation is shown in Table 10 below.
  • the preparation method of the soap-based facial cleanser comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 11; step (2): then preparing the nano-sulfur-containing composition prepared by the step (1) The remaining materials in 10 are mixed and prepared.
  • This embodiment provides a surfactant type cleanser, and the specific formulation is shown in Table 11 below.
  • the preparation method of the surfactant type cleansing milk comprises the following steps: Step (1): preparing a nano-sulfur-containing composition according to Example 14; Step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) The remaining materials in 11 are mixed and prepared.
  • This embodiment provides a noodle cream/grinding cream, and the specific formulation is shown in Table 12 below.
  • the method for preparing the noodle cream/ground cream comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 9; step (2): then combining the nano-sulfur-containing compound prepared in step (1) The mixture was prepared by mixing with the remaining materials in Table 12.
  • This embodiment provides a peeling mask, and the specific formulation is shown in Table 13 below.
  • the preparation method of the peeling mask comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 11; step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and remaining in Table 13 The raw materials are mixed and prepared.
  • This embodiment provides a molding mask liquid (including for oily skin or moisturizing), and the specific formulation is shown in Table 14 below.
  • the preparation method of the molding mask liquid comprises: step (1): preparing a nano-sulfur-containing composition according to the embodiment 12; and step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and the table 14 The remaining raw materials are mixed and prepared.
  • This embodiment provides a bath liquid, and the specific formulation is shown in Table 15 below.
  • the preparation method of the bath comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 1; step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and remaining in Table 15
  • the raw materials are mixed and prepared.
  • This embodiment provides a shampoo in a shampoo, and the specific formulation is shown in Table 16 below.
  • the preparation method of the shampoo comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 9; step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and the remaining materials in the table 16 Mixed, that is, made.
  • This embodiment provides a shampoo in a shampoo, and the specific formulation is shown in Table 17 below.
  • the preparation method of the shampoo comprises: Step (1): preparing a nano-sulfur-containing composition according to Example 6; Step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and Table 17 The remaining raw materials are mixed and prepared.
  • This embodiment provides a hair cream in a hair care product, and the specific formulation is shown in Table 18 below.
  • the preparation method of the hair cream comprises: step (1): preparing a nano-sulfur-containing composition according to embodiment 12; and step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and remaining in Table 18 The raw materials are mixed and prepared.
  • This embodiment provides a hair conditioner in a hair care product, and the specific formulation is shown in Table 19 below.
  • the preparation method of the conditioner includes: Step (1): preparing a nano-sulfur-containing composition according to Example 14; Step (2): then preparing the nano-sulfur-containing composition prepared in the step (1) and Table 19 The remaining raw materials are mixed and prepared.
  • This embodiment provides a soap, which can be added to a certain proportion of the nano-sulfur composition prepared in the first embodiment of the present invention.
  • this example provides a soap of the following formula
  • the nano-sulfur composition prepared in Example 1 is 3%
  • the fragrance is 1%
  • the antioxidant BHT 0.08%
  • the EDTA is 0.1%
  • the pigment small or no
  • a fat stearic acid
  • titanium dioxide about 0.04% or not
  • water about 13%
  • the rest is a soap base.
  • the above-mentioned formula materials are all dissolved by heating and stirring, and then cooled and molded.
  • the present embodiment provides a pesticide, and the nano-sulfur-containing composition prepared in Example 19 of the present invention can be added on the basis of common pesticides, and can be used for treating powdery mildew of crops and the like. It is also possible to add a synergist, other excipients, etc. to the liquid nano-sulfur composition of the present invention, and at the same time, the prepared pesticide can be appropriately diluted according to the specific conditions, and then the crop can be sprayed.
  • the present embodiment provides a feed, which can directly add the nano-sulfur-containing composition prepared in Example 13 of the present invention to an ordinary feed, thereby improving the disease resistance of the animal and the like.
  • the present embodiment provides a vegetable and fruit preservative preservative, and the nano-sulfur-containing composition prepared according to the embodiment 9 of the present invention can be directly used as a preservative for vegetables and fruits. Specifically, it is diluted as needed and used directly for preservation of vegetables and fruits.
  • Examples 22-44 merely exemplarily provide some sulfur-containing products made using the nano-sulfur-containing composition prepared by the inventive concept, wherein only a nano-sulfur-containing composition is exemplarily specified and provided In each formulation, but each formulation is not limited to each of the nano-sulfur-containing compositions used in the above components, and the sulfur-containing products are merely exemplarily listed as common or commonly used general-purpose products, it being understood that the nano-containing using the inventive concept Sulfur-containing products made from sulfur compositions are all within the scope of the present invention.
  • the above examples only exemplarily provide some sulfur-containing products prepared by using the nano-sulfur-containing composition prepared by the inventive concept and a preparation method thereof, and the invention emphasizes that the nano-sulfur-containing composition of the invention is added to various kinds.
  • the nano-sulfur-containing composition of the present invention is added to the formulation or the new formulation of the existing products, and then the mixture is uniformly stirred, and at the same time, it is prepared first.
  • the nano-sulfur-containing composition of the present invention is also prepared according to the formula, and various basic care products or pharmaceutical compositions are not specifically required, and there is no difference between the two steps.
  • the inventors of the present invention were diagnosed with seborrheic dermatitis because of multiple redness, peeling, and pain in the facial skin. After applying the ointment prescribed by the doctor, the dermatitis will be good for a few days, but if you do not use the ointment, it will recur after about one or two weeks. For many years, it has been the case, and many times you see a doctor, it has not been cured.
  • the doctors prescribed ointments, all of which are hormone-containing ointments.
  • the inventors were concerned about the side effects of hormones. After the inventors searched the data themselves, they found that sulfur cream can treat seborrheic dermatitis, so they bought sulfur ointment or cream, but used After that, it was found that these sulfur creams and the like have no effect.
  • the reason for the inefficiency is that the particle size of sulfur is too large to be absorbed by the skin to take advantage of its antifungal property, even if it has about 5% in the existing ointment, it is effective. Micro, it also makes the ointment have a strong pungent odor, which does not meet the actual needs.
  • the inventors used their homemade nano-sulfur cream, the sulfur content can be only a few thousandths, but it is very useful, and the inventors have used it for more than a year, and there are no side effects such as dry skin peeling.
  • the inventors have used their homemade nano-sulfur shampoo (obtained from the nano-sulfur-containing composition of the present invention to the existing shampoo), which is excellent in effect, has been used for more than a year, and has not found any adverse side effects, and Basic control of the massive production of dandruff.

Abstract

一种含纳米硫组合物及其应用，所述含纳米硫组合物含有纳米硫，还含有用以阻止或延缓所述纳米硫团聚的抗团聚剂。该含纳米硫组合物可广泛用于制备用于人或动物皮肤表面的洗护用品、治疗皮肤病的药物组合物、农药、蔬菜水果植物等保鲜剂、动物食料添加剂、涂料防霉添加剂、织物防霉剂或（织物）杀螨虫剂。该含纳米硫组合物制备简单，实现了纳米硫能够长时间维持纳米状态，削弱甚至消除了纳米硫团聚现象的发生，同时将其应用于各种产品中，可添加极少量就能实现抗真菌等目的。

Description

一种含纳米硫组合物及其应用 技术领域
本发明涉及一种含纳米硫组合物及其应用。
背景技术
硫是一种非常活泼的非金属元素，其用途很广泛，可用于制造硫酸、农药、化学纤维、橡胶、染料、造纸、医药、炸药、火柴等。硫在我们的日常生活中扮演着重要的角色，例如用来消毒的硫酸、用来治疗皮肤病的硫磺软膏等等。自然界中的硫也和我们的健康有着密切的关系，如硫磺温泉被称为“皮肤之汤”，有软化皮肤角质层的作用，并有止痒、解毒、排毒的效能，泡硫磺温泉对关节炎、皮肤炎、神经痛的改善特别有用，主要是因为其中的硫磺有消毒、杀菌之功效；向人体补充含多硫化物丰富的食物，如大蒜、洋葱、韭菜、高丽菜、绿花椰菜等特别有益健康，主要是因为其中的一些含硫化合物在起作用。
虽然硫用途广泛，但其具体应用受到较大限制。例如市售的硫制剂例如硫磺软膏或称硫磺乳膏，虽在其使用说明中指明了可以治疗很多的皮肤病，但在实际的临床应用中，效果并不好，几乎被市场淘汰，究其原因主要有以下几点：1)因为硫磺不溶于水，膏中硫磺的颗粒较大(通常为几十微米)，难以被皮肤吸收，抑菌活性低、生物利用率低，医疗效果不好；2)硫磺软膏或乳膏，使用硫磺量较多，有刺激性，很多患者使用后会过敏，还会引起脱皮，皮肤干燥的现象，长时间应用还可能会导致出现皮炎；3)硫磺使用比例较大，一般为5％左右，有的达到10％，有很浓的硫磺臭味。
针对市售硫制剂制备时所用的原料均是微米级颗粒，有人提出采用纳米硫来代替微米硫制备含硫制剂。例如CN105708770A公开了一种祛痘柔肤水，由载体和功效成分两部分混合组成，按重量百分比计，包括：载体：丙二醇3-15％，1,3丁二醇6-10％，山梨醇5-8％，去离子水64.9-85.2％；功效成分：纳米硫0.5-1.3％；其他功效成分0.3-0.8％。然而，该专利对于纳米硫的描述仅限于纳米硫的粒径为50nm以及其可通过利用纳米技术加工单质硫得到(见说明书[0006]和[0031]段)，即该专利并未具体描述如何获得粒径为50nm左右的纳米硫粉体以及纳米硫粉体的表征数据。而根据已有的文献记载(例如CN1453205A和CN104944381)，纳米硫粉体的制备工艺通常都非常复杂，导致高昂的成本；此外，虽然作为原料的纳米硫粉体的粒径较小，但是一旦加入到整个祛痘柔肤水体系或其他应用体系中后，纳米硫粉体会发生明显的团聚，形成较大粒径的硫颗粒，从而难以有效地作用在皮肤表面或毛孔中的细菌/病菌上，同样地，也难以对其它附带病菌或者细菌的基体进行有效地杀菌。
纵观现有技术的含硫产品，均是首先获得高纯度的、固态的硫粉，然后将硫粉分散到含硫产品的其他组分中，混合得到含硫产品。这种方法得到的含硫产品，硫容易团聚，活性较低，效果较差，应用受限。
发明内容
本发明的目的之一是提供一种含纳米硫组合物，其可以代替现有的纳米硫或微米硫应用于各种含硫产品中，使硫活性成分的作用得到更充分的发挥。
本发明的目的之二是提供一种含纳米硫组合物的制备方法，该方法工艺简便，且获得的组合物中纳米硫可以长时间保持较小的粒径。
本发明的目的之三是提供一种含硫产品，其中硫活性成分的作用可以得到更充分的发挥，具有更好的应用效果。
为实现上述目的或解决上述问题，本发明采取的一种技术方案如下：本发明提供了一种含纳米硫组合物，其包含纳米硫以及用以阻止或延缓所述纳米硫团聚的抗团聚剂。
根据本发明的一些具体方面，所述抗团聚剂为选自增稠剂、助悬剂、分散剂、乳化液、粘合剂、反絮凝剂、偶联剂、防静电剂、表面活性剂、胶体中的一种或多种的组合。
根据本发明的更进一步方面，所述增稠剂为选自天然增稠剂和化学合成增稠剂中的任一种或多种的组合，其中，天然增稠剂包括淀粉、糊精、阿拉伯胶、卡拉胶、果胶、琼胶、海藻酸及其盐或衍生物、罗望子胶、甲壳素、黄蜀葵胶、亚麻籽胶、田菁胶、瓜尔胶、槐豆胶、黄原胶；所述化学合成增 稠剂包括羧甲基淀粉钠、羟丙基淀粉醚、淀粉磷酸酯钠、乙酰基二淀粉磷酸脂、磷酸化二淀粉磷酸酯、羟丙基二淀粉磷酸酯。
根据本发明的更进一步方面，所述助悬剂为选自甘油、糖浆剂、胶树类助悬剂、植物多糖类助悬剂、纤维素类助悬剂、卡波普、聚维酮、葡聚糖、硅皂土、触变胶中的一种或多种的组合。
根据本发明的更进一步方面，所述的分散剂为选自水玻璃、三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、瓜尔胶、聚乙二醇、脂肪酸聚乙二醇酯中的一种或多种的组合。
根据本发明的更进一步方面，所述表面活性剂为选自双链离子型表面活性剂、阴离子表面活性剂、阳离子表面活性剂和非离子表面活性剂中的一种或多种的组合。具体地，包括但不限于如下一些具体方面，双链离子型表面活性剂，如琥珀酸二辛酯磺酸钠(AOT)；阴离子表面活性剂，如十二烷基磺酸钠(SDS)、十二烷基苯磺酸钠(DBS)；阳离子表面活性剂，如十六烷基三甲基溴化铵(CTAB)；非离子表面活性剂，如TritonX系列(聚氧乙烯醚类)等。
根据本发明的更进一步方面，所述胶体为选自硅酸胶体、淀粉胶体、蛋白质胶体、豆浆、胶体二氧化硅中的一种或多种的组合。
根据本发明的一些具体方面，所述的抗团聚剂为食品添加剂和/或药用辅料。
在本发明的一些实施方式中，所述抗团聚剂为选自淀粉、糊精、阿拉伯胶、卡拉胶、果胶、琼胶、海藻酸、海藻酸钠、海藻酸二醇酯、罗望子胶、甲壳素、黄蜀葵胶、亚麻籽胶、田菁胶、瓜尔胶、槐豆胶、黄原胶、羧甲基淀粉钠、羟丙基淀粉醚、淀粉磷酸酯钠、乙酰基二淀粉磷酸脂、磷酸化二淀粉磷酸酯、羟丙基二淀粉磷酸酯、甘油、糖浆剂、卡波普、聚维酮、葡聚糖、硅皂土、触变胶、水玻璃、三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、木质素、羧甲基纤维素、羟乙基纤维素、羟丙基纤维素、聚丙烯酰胺、聚乙二醇、脂肪酸聚乙二醇酯、琥珀酸二辛酯磺酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、烷基酚聚氧乙烯醚、硅酸胶体、蛋白质胶体、豆浆、胶体二氧化硅、司盘20、司盘60、司盘80、吐温20、吐温60和吐温80中的一种或多种的组合。
根据本发明，虽然上述列举了一些常用或常见的抗团聚剂，但本发明所述的抗团聚剂可以为任何可以阻止或延缓纳米硫团聚的物质，可以是任一抗团聚物质或多种抗团聚物质的组合，没有特别限制。
根据本发明的一些优选方面，所述的含纳米硫组合物中所述纳米硫与所述抗团聚剂的质量比为1～10：0.5～20。在某些实施方式中，所述的含纳米硫组合物中所述纳米硫与所述抗团聚剂的质量比为1～10：0.5～10。在某些实施方式中，所述的含纳米硫组合物中所述纳米硫与所述抗团聚剂的质量比为1～10：0.5～5。根据本发明的一个具体方面，所述的含纳米硫组合物中纳米硫与抗团聚剂的质量比可以为1～5：0.5～5。
在本发明的一些实施方式中，所述纳米硫的粒径小于等于10微米，优选小于等于5微米，更优选为5nm～3000nm，进一步优选为10nm～2000nm，更进一步优选为20nm～500nm。某些实施例中，纳米硫的粒径可以为20～400nm、20～300nm、20～200nm或20～150nm。在某些实施例中，纳米硫的粒径可以为30～100nm。另一些实施例中，纳米硫的粒径可以为30～90nm。还一些实施例中，纳米硫的粒径可以为40～100nm。
根据本发明，纳米颗粒的大小是可以控制和调整的。具体可以调整抗团聚剂组分以及其用量来调整纳米颗粒的大小。
在本发明中，所述的含纳米硫组合物在室温放置6个月后，其中纳米硫的平均粒径变化一般低于30％，优选低于20％，更优选低于10％。
根据本发明的一些具体且优选的方面，所述的含纳米硫组合物还含有溶剂，所述纳米硫和抗团聚剂分散在所述溶剂中。
根据本发明的一些优选方面，所述溶剂为选自水、乙醇、丙三醇、聚乙二醇中的一种或多种的组合。根据本发明的一个具体方面，所述溶剂为水。
根据本发明的一个具体且优选的方面，所述含纳米硫组合物为液态。
根据本发明的一些优选方面，所述的含纳米硫组合物中，所述纳米硫的质量含量为0.01％～10％。在本发明的某些实施方式中，所述的含纳米硫组合物中，所述纳米硫的质量含量可以为0.01％～7％。在本发明的某些实施方式中，所述的含纳米硫组合物中，所述纳米硫的质量含量可以为0.1％～7％。
根据本发明，抗团聚剂用量越多，防团聚效果越好，但若太多，则溶解不了，或太浓稠，成为果冻状。根据本发明的一些优选方面，所述抗团聚剂的质量含量为0.01～25％。在本发明的某些实施方式中，所述抗团聚剂的质量含量可以为0.5～25％。在本发明的某些实施方式中，所述抗团聚剂的质量含量可以为0.5～15％。在本发明的某些实施方式中，所述抗团聚剂的质量含量可以为0.5～5％。
根据本发明的一些方面，所述的含纳米硫组合物主要由所述的纳米硫、抗团聚剂组成。
根据本发明的另一些方面，所述的含纳米硫组合物主要由纳米硫、抗团聚剂、溶剂组成，其中溶剂没有特别限制，但优选是本领域常用的那些，尤其是水、醇类溶剂等。具体的溶剂可以是例如水、乙醇、丙二醇、丙三醇、聚乙二醇等中的一种或多种的组合。
根据本发明的一些具体且优选的方面，所述的含纳米硫组合物通过如下方法(a)或(b)或(c)制备：
(a)将粉末状纳米级硫与溶剂、抗团聚剂混合，分散均匀得到含纳米硫组合物；
(b)使硫代硫酸盐或多硫化物与酸在抗团聚剂存在下，在溶剂中反应得到含纳米硫组合物；
(c)以硫代硫酸盐或多硫化物、酸为反应原料，通过微乳法制备得到含纳米硫组合物。
上述方法(a)、(b)和(c)中，以方法(b)和(c)为更优选方案，采取方法(b)或(c)制备的含纳米硫组合物，其中纳米硫粒度更小，更均匀，更稳定，使用效果明显更好。
根据本发明的一些具体且优选的方面，所述硫代硫酸盐可以为选自硫代硫酸钠、硫代硫酸铵、硫代硫酸钾中的一种或多种的组合。
根据本发明，所述多硫化物是含有多硫离子Sx的化合物，x＝2,3,4,5,6,...,9。多硫化物酸化时即放出硫化氢和硫：Sx+2H→H 2S+(x-1)S。根据本发明的一些具体且优选的方面，所述的多硫化物可以为选自多硫化钠、多硫化钾、多硫化铵中的一种或多种的组合。
根据本发明，所述酸可以选用任意的无机酸、有机酸或者两者的组合，其中所述有机酸包括但不限于柠檬酸、酒石酸、水杨酸、苯甲酸、羧酸、乳酸等，所述无机酸包括但不限于盐酸、硫酸、硼酸、硝酸等。根据本发明的一些具体且优选的方面，所述酸可以为选自盐酸、苯甲酸、乙酸、柠檬酸、酒石酸、硼酸、水杨酸、乳酸、硫酸和硝酸中的一种或多种的组合。
为实现上述目的或解决上述问题，本发明采取的又一种技术方案如下：一种如上述所述的的含纳米硫组合物的制备方法，所述制备方法包括：使硫代硫酸盐或多硫化物与酸在抗团聚剂存在下，在溶剂中反应得到含纳米硫组合物。
根据本发明的一些具体且优选的方面，所述硫代硫酸盐为选自硫代硫酸钠、硫代硫酸铵、硫代硫酸钾中的一种或多种的组合。
根据本发明的一些具体且优选的方面，所述的多硫化物为选自多硫化钠、多硫化钾、多硫化铵中的一种或多种的组合。
根据本发明的一些具体且优选的方面，所述酸为选自盐酸、苯甲酸、乙酸、柠檬酸、酒石酸、硼酸、水杨酸、乳酸、硫酸、硝酸中的一种或多种的组合。
为实现上述目的或解决上述问题，本发明采取的又一种技术方案如下：如上述所述的含纳米硫组合物用于制备含硫产品的用途。
在本发明的一些具体实施方式中，所述含硫产品为人或动物皮肤表面的洗护用品、治疗皮肤病的药物、治疗肿瘤的药物、治疗毛发疾病的药物、农药、蔬菜水果植物等保鲜剂、动物食料添加剂、涂料防霉添加剂、织物防霉剂或织物杀螨虫剂。
为实现上述目的或解决上述问题，本发明采取的又一种技术方案如下：一种含硫产品，所述含硫产品通过以下步骤制备得到：
(1)提供如上述所述的含纳米硫组合物；
(2)将如上述所述的含纳米硫组合物与含硫产品的其他组分混合。
在本发明的一些具体实施方式中，所述含硫产品为人或动物皮肤表面的洗护用品、治疗皮肤病的药物、治疗肿瘤的药物、治疗毛发疾病的药物、农药、蔬菜水果植物等保鲜剂、动物食料添加剂、涂料防霉添加剂、织物防霉剂或织物杀螨虫剂。
具体地，根据本发明改进的含纳米硫组合物，其能使纳米硫较长时间内均保持为纳米分散状态，进而能够有效提高硫的活性作用和功效，有助于降低硫用量，特别适于制备针对人或动物皮肤表面的洗护用品或者药物，此外还适于添加到治疗肿瘤的药物、治疗毛发疾病的药物、农药、蔬菜水果植物等保鲜剂、动物食料添加剂、涂料防霉添加剂、织物防霉剂或(织物)杀螨虫剂中。
例如根据本发明构思制备的洗护用品，其能够有效防止、改善、缓解或消除皮肤真菌感染。在本发明的一些具体实施方式中，所述洗护用品为面霜、乳膏、沐浴露、洗发水、润肤乳、润肤露、洗面奶、洗手液、花露水、香皂、洁面泡沫、面膜、香波、雪花膏、防裂油、精华素、美白霜、防晒水、雀斑霜、护手霜、保湿平衡液、保湿霜、柔肤水、紧肤水或收敛水。虽然公开了上述一些洗护用品的具体名目，但本发明并不仅限于这些具体的洗护用品，也可以为其他类似的日常使用产品。(洗护用品中，添加含纳米硫组合物后，用于全身任何皮肤表面，都有抗真菌作用，治疗、减轻、和预防癣、皮炎、糠疹、湿疹等多种皮肤病。用于洗发、护发，治疗真菌性头皮屑。用于足部则治疗和预防脚气等真菌性皮肤病。
在本发明的一些具体实施方式中，所述的含纳米硫组合物在所述洗护用品中的添加量可以非常少，通常以纳米硫占洗护用品的含量为约0.005～0.25％的量添加。
又如根据本发明构思制备的药物组合物，其能够有效治疗皮肤真菌感染，治疗各种皮癣、皮炎、糠疹、湿疹等皮肤疾病。药物组合物中，含纳米硫组合物以有效量添加。一般来说，在本发明的一些具体实施方式中，所述的含纳米硫组合物在所述药物组合物中的添加量可以比添加现有技术的纳米硫的量更少，通常以纳米硫占药物组合物的含量为约0.01％～0.5％的量添加。
在本发明的一些具体实施方式中，所述药物组合物还包含增效剂。增效剂例如可以为选自明矾、氧化锌或硼砂中的一种或多种的组合。一般地，在所述药物组合物中，所述增效剂的质量含量可以为1～5％。
在本发明的一些具体实施方式中，所述药物组合物还可以包含保湿剂。所述保湿剂可以为例如选自多元醇、透明质酸、神经酰胺、胶原蛋白、尿素、甲壳素衍生物、芦荟或海藻提取物中的一种或多种的组合。一般地，在药物组合物中，保湿剂的质量含量可以为2～10％。
在本发明的一些具体实施方式中，所述药物组合物的形式可以为软膏形式、凝胶形式、乳膏形式或液体形式。
在本发明的一些具体实施方式中，所述药物组合物中还可以包括除纳米硫组合物以外的其他可以治疗皮肤病的活性物质。
在本发明的含纳米硫组合物的实际应用中，由于加入的纳米硫为少量的，在整个产品中可以只有千分之几的硫含量，从而减弱甚至避免了皮肤的干燥、脱皮现象。
同时在本发明中，可以将制备的所述含纳米硫组合物直接加入其它基体中，虽然其中含有少量的钠盐、钾盐或铵盐等，但实际上不用脱除，例如氯化钠，极少量的使用是无害的，又如乙酸钠，其本身还具有防腐作用，所以制备的含纳米硫组合物是可以直接应用于产品中的，无需进行额外的操作以脱除其它物质，也减少甚至避免了额外因素对纳米硫维持纳米状态的影响。
由于以上技术方案的采用，本发明与现有技术相比具有如下优点：
本发明克服了传统的纳米硫制备或者使用过程中纳米硫易团聚的缺陷，实现了纳米硫能够长时间保持纳米状态，且本发明人将制备的含纳米硫组合物长期静置后(目前超过半年时间)，经检测其中的纳米硫仍然维持着纳米状态并均匀分散在分散介质中，基本消除了其团聚现象的发生。本发明的含纳米硫组合物可添加于任何需要硫的产品中，且能以较低的添加量获得更好的效果。
本发明的含硫产品，其中纳米硫保持了非常好的分散性和较小的粒径，硫的活性可以得到更充分的发挥，应用效果显著更优。同时，由于硫的活性可以得到更充分的发挥，硫的用量可以大幅减少，由此可以减少或避免硫用量多所带来的负面问题。此外，本发明的含硫产品成本较低。因此，本发明 的含硫产品极容易推广。
说明书附图
图1为本发明实施例1制备的含纳米硫组合物在静置半年后的照片；
其中，纳米硫仍然维持着初始的状态，依然均匀的分散在分散介质中。
具体实施方式
含硫产品的传统制备方法是首先获得高纯固态的硫粉，然后将硫粉分散到含硫产品的其他组分中，混合得到含硫产品。采用该传统方法得到的含硫产品，即便其使用的原料硫粉的粒径很小和采用各种辅助分散手段，其中硫仍然容易发生团聚，而影响使用效果。
本发明人通过研究意外发现，在纳米硫形成前加入可以阻止或延缓其团聚的助剂(或称抗团聚剂)并且在纳米硫形成后还继续保留该助剂时，所形成的纳米硫就不易发生团聚。进一步地将由此得到的纳米硫与助剂的组合物用于制备含硫产品时，纳米硫继续保持了非常好的分散性能和较小的粒径，因而所制备的含硫产品其中硫的活性可以得到更充分的发挥，应用效果显著更优。进一步地，由于硫的活性可以得到更充分的发挥，硫的用量可以大幅减少，由此可以减少或避免硫用量多所带来的负面问题。
本发明提出克服了要先制备高纯硫粉再使用的传统偏见(一般认为原料中可以有少量杂质，但不能容忍副产品混杂其中，否则就是品质不好，例如在关于纳米硫的很多文献中均强调了纯度)，本发明一些实施例的含纳米硫组合物中除了纳米硫外，还含有助剂(抗团聚剂)和残留的硫代硫酸盐、多硫化物和酸等，这些组分不仅无害，反而在多数情况下都是有利的。以下举例说明：
A.氯化钠(食盐)：硫代硫酸钠与盐酸反应制备硫所产生的副产物，其在肤发洗护品例如洗发水、香皂中是有益的，在动物饲料中也是有益的。
B.乳酸钠：硫代硫酸钠与乳酸反应制备硫所产生的副产物，可以作为保湿剂，在皮肤和头发洗护品以及药物中是有益的。硫使皮肤干燥，甚至导致脱皮，有不良副作用。而乳酸钠有保湿作用，正好解决了皮肤干燥的问题。制作纳米硫药物和护肤品，正好需要添加保湿剂，甚至必须使用保湿剂以消除纳米硫的不良副作用。
C.乳酸铵：硫代硫酸铵与乳酸反应制备硫所产生的副产物，广泛应用于食品、饮料、乳制品、营养液、药品等，也可用作饲料添加剂。
D.柠檬酸钠：硫代硫酸钠与柠檬酸反应制备硫所产生的副产物，常被用作食品添加剂和防腐剂等，还可以添加在肤发洗护用品中。
E.氯化铵：硫代硫酸铵与盐酸反应制备硫所产生的副产物，可作为化肥。纳米硫混合物用作农药时，其中少量的氯化铵，不仅无害，还可以作为肥料。
F.酒石酸钠：硫代硫酸钠与酒石酸反应制备硫所产生的副产物，该物质常被用于食物、饮料添加剂、抗氧化剂，在药物、食品工业中应用。
G.苯甲酸钠：硫代硫酸钠与苯甲酸反应制备硫所产生的副产物，该物质常被用作杀菌剂、防腐剂、抗微生物剂等，可用于肤发洗护用品之中。
H.硼酸钠：硫代硫酸钠与硼酸反应制备硫所产生的副产物，可用于皮肤黏膜的消毒防腐、足癣、霉菌性阴道炎、宫颈糜烂、褥疮、痤疮、外耳道湿疹、疱疹病毒性皮肤病，可用于肿瘤的治疗，还可作为饲料添加剂。农业上含硼微量元素肥料，对许多作物有肥效，能增进作物品质和提高产量。
I.乙酸钠：硫代硫酸钠与乙酸的副产品，可用作缓冲剂、调味剂、增香剂及pH值调节剂，具有一定的防霉作用、抗真菌作用，可用于肤发洗护品中。
其他没有举例说明的各种副产物等虽然没有一一列举，但他们都是有利的，至少是无害的。
具体地，根据不同应用的含硫产品，可选择适当的抗团聚剂和制备用的硫代硫酸盐或多硫化物和酸，得到纳米硫的同时，还同时得到有益的添加剂，可谓是一举两得。更有意义是，免去了复杂的、高代价的提纯工艺。极大地降低了纳米硫制作成本。
抗团聚剂
本发明所述的抗团聚剂可以为任何可以阻止或延缓纳米硫团聚的物质，可以是任一抗团聚物质或 多种抗团聚物质的组合，没有特别限制。
具体地，可以阻止或延缓纳米硫团聚的物质的种类非常广泛，包括但不限于各种增稠剂、助悬剂、分散剂、乳化液、偶联剂、防静电剂、表面活性剂、溶胶、凝胶等。这些具体抗团聚剂均具有抗团聚效果，只是效果程度的差别。
(1)增稠剂
本发明所述的增稠剂没有特别限制，可以选自天然增稠剂和化学合成增稠剂中的任一种或多种的组合。天然增稠剂包括但不限于各种淀粉(麦粉、米粉、薯粉、葛根粉等)、糊精、明胶、阿拉伯胶、卡拉胶、果胶、琼胶、海藻酸类增稠剂、罗望子胶、甲壳素、黄蜀葵胶、亚麻籽胶、田菁胶、瓜尔胶、槐豆胶、黄原胶。化学合成增稠剂包括但不限于羧甲基淀粉钠、羟丙基淀粉醚、淀粉磷酸酯钠、乙酰基二淀粉磷酸脂、磷酸化二淀粉磷酸酯、羟丙基二淀粉磷酸酯等。
(2)助悬剂
助悬剂(suspending agents)指能增加分散介质的黏度以降低微粒的沉降速度或增加微粒亲水性的附加剂。本发明所述的助悬剂可以是各种助悬剂类型，没有特别限制，例如：可以是低分子助悬剂如甘油、糖浆剂等，在外用混悬剂中常加入甘油；可以是各类高分子助悬剂。高分子助悬剂包括：
A.天然的高分子助悬剂：主要是胶树类，如阿拉伯胶、西黄蓍胶、桃胶等。阿拉伯胶和西黄蓍胶可用其粉末或胶浆。还有植物多糖类，如海藻酸钠、琼脂、淀粉浆等。
B.合成或半合成高分子助悬剂：纤维素类，如甲基纤维素、羧甲基纤维素钠、羟丙基纤维素。其他如卡波普、聚维酮、葡聚糖等。此类助悬剂大多数性质稳定，受pH值影响小，但应注意某些助悬剂能与药物或其他附加剂有配伍变化。
C.硅皂土：是天然的含水硅酸铝，为灰黄或乳白色极细粉末，直径为1～150μm，不溶于水或酸，但在水中膨胀，体积增加约10倍，形成高粘度并具触变性和假塑性的凝胶，在pH值>7时，膨胀性更大，粘度更高，助悬效果更好。
D.触变胶：利用触变胶的触变性，即凝胶与溶胶恒温转变的性质，静置时形成凝胶防止微粒沉降，振摇时变为溶胶有利于倒出。使用触变性助悬剂有利于混悬剂的稳定。单硬脂酸铝溶解于植物油中可形成典型的触变胶，一些具有塑性流动和假塑性流动的高分子化合物水溶液常具有触变性，可选择使用。
根据本发明的一些实施方式，助悬剂具体采用的是例如胶体二氧化硅、羧甲基纤维素(CMC)、海藻酸钠、羧甲基纤维素钠(CMC-Na)等。
(3)分散剂
分散剂是促使物料颗粒均匀分散于介质中形成稳定悬浮体的药剂。分散剂一般分为无机分散剂和有机分散剂两大类。常用的无机分散剂有硅酸盐类(例如水玻璃)和碱金属磷酸盐类(例如三聚磷酸钠、六偏磷酸钠和焦磷酸钠等)。有机分散剂包括三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、瓜尔胶、脂肪酸聚乙二醇酯等。
(4)乳化液
将油、表面活性剂、水(电解质水溶液)或助表面活性剂混合均匀，然后向体系中加入助表面活性剂或水(电解质水溶液)，在一定配比范围内可形成微乳液。
常用的表面活性剂有：双链离子型表面活性剂，如琥珀酸二辛酯磺酸钠(AOT)；阴离子表面活性剂，如十二烷基磺酸钠(SDS)、十二烷基苯磺酸钠(DBS)；阳离子表面活性剂，如十六烷基三甲基溴化铵(CTAB)；非离子表面活性剂，如TritonX系列(聚氧乙烯醚类)等。利用微乳液的分散作用，可将纳米硫颗粒分散，并阻止纳米硫团聚。
(5)胶体
胶体包括各种溶胶、凝胶等，具体例如硅酸胶体、淀粉胶体、蛋白质胶体、豆浆等。各种胶状物质都有利于纳米硫的分散并阻止纳米硫团聚。
(6)其他抗团聚剂
其他抗团聚剂如偶联剂、防静电剂、表面活性剂、乳化液等可通过改善颗粒表面特性或颗粒之间 的相互作用来起到抗团聚效果。
所述表面活性剂的类型不限，可以是双链离子型表面活性剂、阴离子表面活性剂、阳离子表面活性剂和非离子表面活性剂中的一种或多种的组合，其中，双链离子型表面活性剂例如可以是琥珀酸二辛酯磺酸钠，阴离子表面活性剂例如可以是十二烷基磺酸钠、十二烷基苯磺酸钠，阳离子表面活性剂例如可以是十六烷基三甲基溴化铵，非离子表面活性剂例如可以是聚氧乙烯醚类表面活性剂。
乳化液例如为吐温60、司盘20。
根据本发明的一些优选方面，所述的抗团聚剂是食品添加剂或药用辅料。
纳米硫粒径的测试方法
采用GBT 19627-2005粒度分析光子相关光谱法和GB/T 29022-2012粒度分析动态光散射法(DLS)对纳米硫组合物中的粒径进行测试，测试温度为室温25℃。
纳米硫组合物用于制备抗真菌药物或洗护用品的应用
本发明的含纳米硫组合物，其能够使得纳米硫长期维持纳米状态而不发生团聚，避免团聚成大颗粒状态而难以被皮肤吸收进而表现为抗真菌、治疗皮肤病效果不好，同时其还可作为有效成分用于洗护用品以及药物组合物中，在所述洗护用品和药物组合物中，并不仅限于本发明的含纳米硫组合物作为有效成分，也可还有其它的成分，以消费者需求为宜；且所述洗护用品和药物组合物均可根据实际情况选择合适的形式，例如膏状、液体状等。
本发明用于抗真菌药物或洗护用品，解决了传统的含纳米硫产品中的纳米硫并不是真正的纳米状态的问题(大颗粒硫很难被皮肤吸收而起到杀菌作用)，一方面，利用纳米硫容易被皮肤吸收的特性，可极大的减少硫的使用量，减少甚至消除了传统含硫产品造成的皮肤干燥的副作用，又一方面，因极大减少了硫的使用量，几乎没有硫的臭味道，其外观和香味(可额外添加)与普通的护肤品无异，再一方面，使用本发明的含纳米硫的产品中不含激素(传统抗真菌药物中加入激素的目的是抗过敏、抗炎、止痒等作用，而激素的使用具有明显的副作用，长期使用会造成自身生理功能的紊乱)，可替代传统的抗真菌外用药，以治疗各种皮炎、顽癣、湿疹等。
本发明所述的洗护用品尤其指用于人或动物皮肤表面的洗护用品。
在本发明的一些具体实施方式中，所述洗护用品为面霜、乳膏、沐浴露、洗发水、润肤乳、润肤露、洗面奶、洗手液、花露水、香皂、洁面泡沫、面膜、香波、雪花膏、防裂油、精华素、美白霜、防晒水、雀斑霜、护手霜、保湿平衡液、保湿霜、柔肤水、紧肤水或收敛水。虽然公开了上述一些洗护用品的具体名目，但本发明并不仅限于这些具体的洗护用品，也可以为其他类似的日常使用产品。(洗护用品中，添加纳米硫后，用于全身任何皮肤表面，都有抗真菌作用，治疗、减轻、和预防癣、皮炎、糠疹、湿疹等多种皮肤病。用于洗发、护发，治疗真菌性头皮屑。用于足部则治疗和预防脚气等真菌性皮肤病)。
在本发明的一些具体实施方式中，所述的含纳米硫组合物在所述洗护用品中的添加量可以非常少，通常以纳米硫占洗护用品的含量为约0.005～0.25％的量添加。
本发明所述的抗真菌外用药物中，含纳米硫组合物以有效量添加。一般来说，在本发明的一些具体实施方式中，所述的含纳米硫组合物在所述抗真菌外用药物中的添加量可以比添加现有技术的纳米硫的量更少，通常以纳米硫占抗真菌外用药物的含量为约0.01％～0.5％的量添加。
在本发明的一些具体实施方式中，所述抗真菌外用药物还包含增效剂。增效剂例如可以为选自明矾、氧化锌或硼砂中的一种或多种的组合。一般地，在所述抗真菌外用药物中，所述增效剂的质量含量可以为1～5％。
在本发明的一些具体实施方式中，所述抗真菌外用药物还可以包含保湿剂。所述保湿剂可以为例如选自多元醇、透明质酸、神经酰胺、胶原蛋白、尿素、甲壳素衍生物、芦荟或海藻提取物中的一种或多种的组合。一般地，在抗真菌外用药物中，保湿剂的质量含量可以为2～10％。
在本发明的一些具体实施方式中，所述抗真菌外用药物的形式为软膏形式、凝胶形式、乳膏形式或液体形式。
在本发明的一些具体实施方式中，所述抗真菌外用药物中还可以包括除纳米硫组合物以外的其他 可以治疗皮肤病的活性物质。
在本发明的含纳米硫组合物的实际应用中，由于加入的纳米硫为少量的，在整个产品中可以只有千分之几的硫含量，从而减弱甚至避免了皮肤的干燥、脱皮现象。
同时在本发明中，可以将制备的所述含纳米硫组合物直接加入其它基体中，虽然其中含有少量的钠盐、钾盐或铵盐等，但实际上不用脱除，例如氯化钠，极少量的使用是无害的，又如醋酸钠，其本身还具有防腐作用，所以制备的含纳米硫组合物是可以直接应用于产品中的，无需进行额外的操作以脱除其它物质，也减少甚至避免了额外因素对纳米硫维持纳米状态的影响。
根据本发明的一些实施方式中，所述的含硫产品除了包含有(i)单质硫、(ii)抗团聚剂外，还包含有(iii)硫代硫酸根离子或硫离子和/或(iv)酸根离子。在没有相反证据时，同时具有(i)、(ii)、(iii)所示物质的含硫产品或同时具有(i)、(ii)、(iv)所示物质的含硫产品或同时具有(i)、(ii)、(iii)、(iv)所示物质的含硫产品应认为落入本专利的保护范围中。
以下结合具体实施例对上述方案做进一步说明；应理解，这些实施例是用于说明本发明的基本原理、主要特征和优点，而本发明不受以下实施例的范围限制；实施例中采用的实施条件可以根据具体要求做进一步调整，未注明的实施条件通常为常规实验中的条件。下述中，所有原料均来自于商购或者通过本领域的常规方法制备而得下述中，硫粒子的粒径通过GB/T 29022-2012/粒度分析/动态光散射法(DLS)测得。
实施例1
本实施例提供一种含纳米硫组合物，其原料包括五水硫代硫酸钠、羟丙基淀粉醚、盐酸和水。其制备方法如下：
称取50g的五水硫代硫酸钠和1g羟丙基淀粉醚，将五水硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为50％的硫代硫酸钠水溶液，再向硫代硫酸钠水溶液中加入羟丙基淀粉醚，最后将质量分数为10％的盐酸溶液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为3.06％，本实施例中制成的含纳米硫组合物中含有副产品氯化钠，然氯化钠在肤发洗护品例如洗发水、香皂中是有益的，在动物饲料中也是有益的，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为132纳米。制备完成常温放置6个月后，拍摄的照片如图1所示。
实施例2
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、瓜尔胶、乙酸和水。其制备方法如下：
称取50g的硫代硫酸钠和1.5g瓜尔胶，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为60％的硫代硫酸钠水溶液，再向硫代硫酸钠水溶液中加入瓜尔胶，最后将质量分数为10％的乙酸溶液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1.05∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为2.17％，本实施例制成的含纳米硫组合物中还含有副产品乙酸钠，然乙酸钠可用作缓冲剂、调味剂、增香剂及pH值调节剂，具有一定的防霉作用、抗真菌作用，可用于肤发洗护品中，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为173纳米。
实施例3
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、磷酸化二淀粉磷酸酯、乙酸和水。其制备方法如下：
称取50g的硫代硫酸钠和2g磷酸化二淀粉磷酸酯，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为65％的硫代硫酸钠水溶液；将磷酸化二淀粉磷酸酯加入质量分数为40％的乙酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔浓度比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为5.9％，本实施例制成的含纳米硫组合物中还含有副产品乙酸钠，然乙酸钠可用作缓冲剂、调味剂、增香剂及pH值调节剂，具有一定的防霉作用、抗真菌作用，可用于肤发洗护品中，因此无 需如传统偏见所指导地要将其除去。
实施例4
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、黄原胶、乙酸和水。其制备方法如下：
称取50g的硫代硫酸钠和2g黄原胶，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为60％的硫代硫酸钠水溶液；将黄原胶加入质量分数为10％的乙酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为2.19％，本实施例制成的含纳米硫组合物中还含有副产品乙酸钠，然乙酸钠可用作缓冲剂、调味剂、增香剂及pH值调节剂，具有一定的防霉作用、抗真菌作用，可用于肤发洗护品中，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为285纳米。
实施例5
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、羧甲基纤维素、盐酸、苯甲酸和水。其制备方法如下：
称取50g的硫代硫酸钠和2g羧甲基纤维素，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为65％的硫代硫酸钠水溶液；将羧甲基纤维素加入质量分数为10％的盐酸和苯甲酸的复合酸溶液(氯化氢与苯甲酸投料摩尔比为1∶1)中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为1.75％，本实施例中制成的含纳米硫组合物中含有副产品氯化钠、苯甲酸钠，然氯化钠在肤发洗护品例如洗发水、香皂中是有益的，在动物饲料中也是有益的，苯甲酸钠常被用作杀菌剂、防腐剂、抗微生物剂等，也可用于肤发洗护用品之中，因此无需如传统偏见所指导地要将两者除去，同时测得其中硫的平均粒径约为46纳米。
实施例6
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、羟乙基纤维素、乙酸和水。其制备方法如下：
称取50g的硫代硫酸钠和2g羟乙基纤维素，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为65％的硫代硫酸钠水溶液；将羟乙基纤维素加入质量分数为10％的乙酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为2.22％，本实施例制成的含纳米硫组合物中还含有副产品乙酸钠，然乙酸钠可用作缓冲剂、调味剂、增香剂及pH值调节剂，具有一定的防霉作用、抗真菌作用，可用于肤发洗护品中，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为43纳米。
实施例7
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、聚乙二醇、柠檬酸和水。其制备方法如下：
称取50g的硫代硫酸钠和20g聚乙二醇，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为60％的硫代硫酸钠水溶液；将聚乙二醇加入质量分数为10％的柠檬酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为2.07％，本实施例制成的含纳米硫组合物中还含有副产品柠檬酸钠，然柠檬酸钠常被用作食品添加剂和防腐剂等，还可以添加在肤发洗护用品中，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为180纳米。
实施例8
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、聚维酮、酒石酸和水。其制备方法如下：
称取50g的硫代硫酸钠和2g聚维酮，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为60％的硫代硫酸钠水溶液；将聚维酮加入质量分数为10％的酒石酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为1.81％，本实施例制备的含纳米硫组合物中含有副产品酒石酸钠，然该物质常被用于食物、饮料添加剂、抗氧化剂，在药物、食品工业中也存在应用，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为132纳米。
实施例9
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、海藻酸钠、苯甲酸和水。其制备方法如下：
称取50g的硫代硫酸钠和2g海藻酸钠，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为50％的硫代硫酸钠水溶液；将海藻酸钠加入质量分数为10％的苯甲酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为1.16％，本实施例制备的含纳米硫组合物中含有副产品苯甲酸钠，然该物质常被用作杀菌剂、防腐剂、抗微生物剂等，可用于肤发洗护用品之中，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为30纳米。
实施例10
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、淀粉、硼酸和水。其制备方法如下：
称取50g的硫代硫酸钠和8g淀粉，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为50％的硫代硫酸钠水溶液；将淀粉加入质量分数为10％的硼酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为2.06％，本实施例制备的含纳米硫组合物中含有副产品硼酸钠，然该物质可用于皮肤黏膜的消毒防腐、足癣、霉菌性阴道炎、宫颈糜烂、褥疮、痤疮、外耳道湿疹、疱疹病毒性皮肤病，可用于肿瘤的治疗，还可作为饲料添加剂。农业上含硼微量元素肥料，对许多作物有肥效，能增进作物品质和提高产量，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为310纳米。
实施例11
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、胶体二氧化硅、水杨酸和水。其制备方法如下：
称取50g的硫代硫酸钠和10g胶体二氧化硅，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为65％的硫代硫酸钠水溶液；将胶体二氧化硅加入质量分数为10％的水杨酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为1.07％，本实施例制备的含纳米硫组合物中含有副产品水杨酸钠，然该物质可用于食品、药物中，也可作为防腐剂，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为40纳米。
实施例12
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、阿拉伯胶、乳酸和水。其制备方法如下：
称取50g的硫代硫酸钠和2g阿拉伯胶，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为65％的硫代硫酸钠水溶液；将阿拉伯胶加入质量分数为10％的乳酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为1.57％，本实施例制备的含纳米硫组合物中含有副产品乳酸钠，然该物质可以作为保湿剂，在皮肤和头发洗护品以及药物中是有益的；硫使皮肤干燥，甚至导致脱皮，有不良副作用，而乳酸钠有保湿作用，正好解决了 皮肤干燥的问题。制作纳米硫药物和护肤品，正好需要添加保湿剂，甚至必须使用保湿剂以消除纳米硫的不良副作用，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为58纳米。
实施例13
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸铵、果胶、乳酸和水。其制备方法如下：
称取50g的硫代硫酸铵和2g果胶，将硫代硫酸铵溶于水，制成含硫代硫酸铵的质量分数为65％的硫代硫酸铵水溶液；将果胶加入质量分数为10％的乳酸溶液中形成混合液，再将混合液加入硫代硫酸铵水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为1.58％，本实施例制备的含纳米硫组合物中含有副产品乳酸铵，然该物质广泛应用于食品、饮料、乳制品、营养液、药品等，也可用作饲料添加剂，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为71纳米。
实施例14
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、海藻酸二醇酯、乙酸和水。其制备方法如下：
称取50g的硫代硫酸钠和2g海藻酸二醇酯，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为65％的硫代硫酸钠水溶液；将海藻酸二醇酯加入质量分数为10％的乙酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为1.21％，本实施例制成的含纳米硫组合物中还含有副产品乙酸钠，然乙酸钠可用作缓冲剂、调味剂、增香剂及pH值调节剂，具有一定的防霉作用、抗真菌作用，可用于肤发洗护品中，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为42纳米。
实施例15
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、木质素、苯甲酸和水。其制备方法如下：
称取50g的硫代硫酸钠和5g木质素，将硫代硫酸钠溶于水，制成含硫代硫酸钠的质量分数为65％的硫代硫酸钠水溶液；将木质素加入质量分数为10％的苯甲酸溶液中形成混合液，再将混合液加入硫代硫酸钠水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为1.19％，本实施例制备的含纳米硫组合物中含有副产品苯甲酸钠，然该物质常被用作杀菌剂、防腐剂、抗微生物剂等，可用于肤发洗护用品之中，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为230纳米。
实施例16
本实施例提供一种含纳米硫组合物，其原料包括多硫化钠(Na 2S 2)、羧甲基淀粉钠、乳酸和水。其制备方法如下：
称取50g的多硫化钠和2g羧甲基淀粉钠，将多硫化钠溶于水，制成含多硫化钠的质量分数为65％的多硫化钠水溶液；将羧甲基淀粉钠加入质量分数为40％的乳酸溶液中形成混合液，再将混合液加入多硫化钠水溶液中(其中，加入的多硫离子与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为5.17％。本实施例制备的含纳米硫组合物中含有副产品乳酸钠，然该物质可以作为保湿剂，在皮肤和头发洗护品以及药物中是有益的；硫使皮肤干燥，甚至导致脱皮，有不良副作用，而乳酸钠有保湿作用，正好解决了皮肤干燥的问题。制作纳米硫药物和护肤品，正好需要添加保湿剂，甚至必须使用保湿剂以消除纳米硫的不良副作用，因此无需如传统偏见所指导地要将其除去。
实施例17
本实施例提供一种含纳米硫组合物，其原料包括多硫化钾(K 2S 2)、瓜尔胶、乙酸、苯甲酸和水。 其制备方法如下：
称取50g的多硫化钾和2g瓜尔胶，将多硫化钾溶于水，制成含多硫化钾的质量分数为60％的多硫化钾水溶液；将瓜尔胶加入质量分数为20％的乙酸和苯甲酸的复合酸溶液((其中乙酸和苯甲酸的投料摩尔比为1∶1))中形成混合液，再将混合液加入多硫化钾水溶液中(其中，加入的多硫离子与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为2.79％。本实施例制备的含纳米硫组合物中含有副产品乳酸钾，然该物质可用作食用防腐剂；抗微生物剂，主要用于人造奶油、稀人造奶油、葡萄酒等食品中，因此无需如传统偏见所指导地要将其除去。
实施例18
本实施例提供一种含纳米硫组合物，其原料包括多硫化铵((NH 4) 2S 2)、琼胶、乳酸和水。其制备方法如下：
称取50g的多硫化铵和3g琼胶，将多硫化铵溶于水，制成含多硫化铵的质量分数为50％的多硫化铵水溶液；将琼胶加入质量分数为10％的乳酸溶液中形成混合液，再将混合液加入多硫化铵水溶液中(其中，加入的多硫离子与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为1.60％，本实施例制备的含纳米硫组合物中含有副产品乳酸铵，然该物质广泛应用于食品、饮料、乳制品、营养液、药品等，也可用作饲料添加剂，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为84纳米。
实施例19
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钾、羟丙基纤维素、盐酸和水。其制备方法如下：
称取50g的硫代硫酸钾和2g羟丙基纤维素，将硫代硫酸钾溶于水，制成含硫代硫酸钾的质量分数为65％的硫代硫酸钾水溶液；将羟丙基纤维素加入质量分数为40％的盐酸溶液中形成混合液，再将混合液加入硫代硫酸钾水溶液中(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得含纳米硫组合物。所得含纳米硫组合物中纳米硫的质量含量约为6.74％，本实施例制备的含纳米硫组合物中含有副产品氯化钾，然该物质在农业上则是一种钾肥，其肥效快，直接施用于农田，能使土壤下层水分上升，有抗旱的作用.可直接配合纳米硫起到更好的共同作用，因此无需如传统偏见所指导地要将其除去。
实施例20
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、司盘20、柠檬酸和水。其制备方法如下：
(1)称取50g的硫代硫酸钠并加入水中制成含硫代硫酸钠的质量分数为60％的硫代硫酸钠水溶液；
(2)加入20g玉米油，加入5g司盘20，搅拌成油水乳化液；
(3)然后加入质量分数为10％的柠檬酸溶液(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)，采用超声波搅拌，直至反应完全，即得液态的含纳米硫组合物，且呈微乳液状态。所得含纳米硫组合物中纳米硫的质量含量约为2.07％，本实施例制成的含纳米硫组合物中还含有副产品柠檬酸钠，然柠檬酸钠常被用作食品添加剂和防腐剂等，还可以添加在肤发洗护用品中，因此无需如传统偏见所指导地要将其除去，同时测得其中硫的平均粒径约为310纳米。
实施例21
本实施例提供一种含纳米硫组合物，其原料包括硫代硫酸钠、吐温60、乙酸和水。其制备方法如下：
(1)称取50g的硫代硫酸钠并加入水中制成含硫代硫酸钠的质量分数为50％的硫代硫酸钠水溶液；
(2)加入20g蓖麻油，加入5g吐温60，搅拌成油水乳化液；
(3)然后加入质量分数为30％的乙酸溶液(其中，加入的硫代硫酸根与氢离子的摩尔比为1∶2)， 采用超声波搅拌，直至反应完全，即得液态的含纳米硫组合物，且呈微乳液状态。所得含纳米硫组合物中纳米硫的质量含量约为4.47％，本实施例制成的含纳米硫组合物中还含有副产品乙酸钠，然乙酸钠可用作缓冲剂、调味剂、增香剂及pH值调节剂，具有一定的防霉作用、抗真菌作用，可用于肤发洗护品中，因此无需如传统偏见所指导地要将其除去。
实施例22
本例提供一种药物组合物，其可用于治疗疥疮、头癣、痤疮、脂溢性皮炎、酒渣鼻、糠疹和慢性湿疹等，具体配方如下表1所示。
表1
原料 质量分数/％
实施例2制备的含纳米硫组合物 10
氧化锌 2
硬脂酸 14.0
单硬脂酸甘油酯 1.0
十六醇 1.0
白油 2.0
甘油 8.0
KOH(100％) 0.5
香精 适量
去离子水 余量
所述药物组合物的制备方法包括：步骤(1)：按照实施例2制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表1中其余原料相混合，即制成。
实施例23
本例提供一种药物组合物，其可用于治疗疥疮、头癣、痤疮、脂溢性皮炎、酒渣鼻、糠疹和慢性湿疹等，具体配方如下表2所示。
表2
原料 质量分数/％
实施例10制备的含纳米硫组合物 10
明矾 2
尿素 2
白油 5.0
异壬基异壬醇酯 5.0
聚山梨糖油酸酯 1.0
聚山梨酸酯 1.0
聚甲基丙烯酸甲酯 2.0
Sepigel 501((赛比克501) 3.0
香精 适量
去离子水 余量
所述药物组合物的制备方法包括：步骤(1)：按照实施例10制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表2中其余原料相混合，即制成。
实施例24
本实施例提供了一种洗护用品中的雪花膏，具体配方如下表3所示。
表3
原料 质量分数/％
实施例6制备的含纳米硫组合物 3
硬脂酸 14.0
单硬脂酸甘油酯 1.0
十六醇 1.0
白油 2.0
甘油 8.0
KOH(100％) 0.5
香精 适量
去离子水 余量
所述雪花膏的制备方法包括：步骤(1)：按照实施例6制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表3中其余原料相混合，即制成。
实施例25
本实施例提供了一种洗护用品中的冷霜(护肤霜)，具体配方如下表4所示。
表4
冷霜配方 质量分数/％
实施例12制备的含纳米硫组合物 3
蜂蜡 10.0
白凡士林 5.0
白油18# 45.0
水 36.4
硼砂 0.6
香精、抗氧剂 适量
所述冷霜(护肤霜)的制备方法包括：步骤(1)：按照实施例12制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表4中其余原料相混合，即制成。
实施例26
本实施例提供了一种洗护用品中的润肤霜，具体配方如下表5所示。
表5
Figure PCTCN2018099661-appb-000001
Figure PCTCN2018099661-appb-000002
所述润肤霜的制备方法包括：步骤(1)：按照实施例7制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表5中其余原料相混合，即制成。
实施例27
本实施例提供了一种洗护用品中的润肤乳液，具体配方如下表6所示。
表6
原料 质量分数/％
实施例15制备的含纳米硫组合物 3
白油 5.0
异壬基异壬醇酯 5.0
聚山梨糖油酸酯 1.0
聚山梨酸酯 1.0
聚甲基丙烯酸甲酯 2.0
Sepigel 501((赛比克9501) 3.0
香精 适量
去离子水 80.0
所述润肤乳液的制备方法包括：步骤(1)：按照实施例15制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表6中其余原料相混合，即制成。
实施例28
本实施例提供了一种洗护用品中的护肤凝胶/按摩凝胶/洁面凝胶/防粉刺凝胶，具体配方如下表7所示。
表7
Figure PCTCN2018099661-appb-000003
Figure PCTCN2018099661-appb-000004
所述护肤凝胶/按摩凝胶/洁面凝胶/防粉刺凝胶的制备方法分别包括：步骤(1)：按照实施例12制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表7中其余原料相混合，即制成。
实施例29
本实施例提供了一种清洁霜，具体配方如下表8所示。
表8
Figure PCTCN2018099661-appb-000005
所述清洁霜的制备方法包括：步骤(1)：按照实施例1制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表8中其余原料相混合，即制成。
实施例30
本实施例提供了一种洗面奶，具体配方如下表9所示。
表9
原料 质量分数/％
实施例5制备的含纳米硫组合物 5
白油 6.0
肉豆蔻酸肉豆蔻醇酯 2.0
异壬基酸异壬基醇酯 4.0
聚山梨醇油酸酯 2.0
Sepigel 501(赛比克501) 8.0
丙二醇 2.0
香精 适量
去离子水 余量
所述洗面奶的制备方法包括：步骤(1)：按照实施例5制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表9中其余原料相混合，即制成。
实施例31
本实施例提供了一种皂基型洁面乳，具体配方如下表10所示。
表10
原料 质量分数/％
实施例11制备的含纳米硫组合物 5
硬脂酸 10.0
棕榈酸 10.0
羊毛脂 2.0
椰子油 2.0
甘油单硬脂酸酯 2.0
N-酰基-N-甲基牛磺酸钠 2.0
氢氧化钾 4.0
EDTA二钠 0.1
甘油 10.0
香精 0.3
去离子水 余量
所述皂基型洁面乳的制备方法包括：步骤(1)：按照实施例11制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表10中其余原料相混合，即制成。
实施例32
本实施例提供了一种表面活性剂型洁面乳，具体配方如下表11所示。
表11
原料 质量分数/％
实施例14制备的含纳米硫组合物 5
N-酰基-N-甲基牛磺酸钠 5.0
POE-POP嵌段共聚物 5.0
POE(15)油醇醚 21
PEG-10甲基葡萄酸苷 12
霍霍巴油 2.0
羊毛醇 1.0
EDTA二钠 0.1
甘油 8.0
山梨醇 3.0
香精 0.3
去离子水 余量
所述表面活性剂型洁面乳的制备方法包括：步骤(1)：按照实施例14制备含纳米硫组合物；步 骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表11中其余原料相混合，即制成。
实施例33
本实施例提供了一种磨面膏/磨面乳，具体配方如下表12所示。
表12
Figure PCTCN2018099661-appb-000006
所述磨面膏/磨面乳的制备方法分别包括：步骤(1)：按照实施例9制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表12中其余原料相混合，即制成。
实施例34
本实施例提供了一种剥离面膜，具体配方如下表13所示。
表13
Figure PCTCN2018099661-appb-000007
所述剥离面膜的制备方法包括：步骤(1)：按照实施例11制备含纳米硫组合物；步骤(2)： 然后将步骤(1)制备的所述含纳米硫组合物与表13中其余原料相混合，即制成。
实施例35
本实施例提供了一种成型面膜液(包括针对油性皮肤用或者保湿用)，具体配方如下表14所示。
表14
Figure PCTCN2018099661-appb-000008
所述成型面膜液的制备方法包括：步骤(1)：按照实施例12制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表14中其余原料相混合，即制成。
实施例36
本实施例提供了一种浴液，具体配方如下表15所示。
表15
Figure PCTCN2018099661-appb-000009
所述浴液的制备方法包括：步骤(1)：按照实施例1制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表15中其余原料相混合，即制成。
实施例37
本实施例提供了一种洗发品中的香波，具体配方如下表16所示。
表16
原料 质量分数/％
实施例9制备的含纳米硫组合物 5
月桂醇醚硫酸钠(70％) 20.0
月桂酸二乙醇酰胺 4.0
乙二醇单硬脂酸酯 2.0
丙二醇 2.0
羊毛脂 1.5
香精 0.5
去离子水 余量
所述香波的制备方法包括：步骤(1)：按照实施例9制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表16中其余原料相混合，即制成。
实施例38
本实施例提供了一种洗发品中的洗发膏，具体配方如下表17所示。
表17
Figure PCTCN2018099661-appb-000010
所述洗发膏的制备方法包括：步骤(1)：按照实施例6制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表17中其余原料相混合，即制成。
实施例39
本实施例提供了一种护发品中的发乳，具体配方如下表18所示。
表18
Figure PCTCN2018099661-appb-000011
Figure PCTCN2018099661-appb-000012
所述发乳的制备方法包括：步骤(1)：按照实施例12制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表18中其余原料相混合，即制成。
实施例40
本实施例提供了一种护发品中的护发素，具体配方如下表19所示。
表19
Figure PCTCN2018099661-appb-000013
所述护发素的制备方法包括：步骤(1)：按照实施例14制备含纳米硫组合物；步骤(2)：然后将步骤(1)制备的所述含纳米硫组合物与表19中其余原料相混合，即制成。
实施例41
本实施例提供了一种香皂，可在普通香皂制作工艺中，添加一定比例本发明实施例1制备的纳米硫组合物.
具体地，本例提供如下配方的一种香皂，实施例1制备的纳米硫组合物3％，香精1％，抗氧剂(BHT0.08％)，EDTA0.1％，色素(少量或不加)，多脂剂(硬脂酸)1％,钛白粉(约0.04％或不加)，水约13％，其余为香皂皂基。将上述配方原料加热搅拌全部溶解后，冷却成型，即得。
实施例42
本实施例提供了一种农药，可以在普通农药的基础上添加本发明实施例19制备的含纳米硫组合物，可以用于治疗农作物的白粉病等。也可以自行调配，在本发明液态纳米硫组合物的基础上添加增效剂、其它辅料等，同时可根据具体情况将配制出的农药进行适当稀释，然后喷洒农作物。
实施例43
本实施例提供了一种饲料，可以直接在普通饲料中加入本发明实施例13制备的含纳米硫组合物，进而可以提高动物抗病能力等。
实施例44
本实施例提供了一种蔬菜水果保鲜防腐剂，可直接使用按照本发明构思实施例9制备得到的含纳米硫组合物作为蔬菜水果保鲜防腐剂。具体地，根据需要将其稀释并直接用于蔬菜水果保鲜。
上述实施例22-44仅示例性地提供了一些采用本发明构思制备的含纳米硫组合物制成的含硫产品，其中仅示例性地指明并提供了一种含纳米硫组合物并应用于各个配方中，但各配方不仅限于上述组分采用的各含纳米硫组合物，且含硫产品也仅示例性地列举了常见或常用的通用产品，应理解，凡使用本发明构思的含纳米硫组合物制成的含硫产品均应在本发明的保护范围内。
上述实施例仅示例性地提供了一些采用本发明构思制备的含纳米硫组合物制成的含硫产品及其制备方法，本发明强调地是将本发明的含纳米硫组合物添加入各种膏状、液状、霜状等等的含硫产品中，具体为在现有各产品的配方或新配方中加入本发明的含纳米硫组合物，然后搅拌均匀，即可，同时对于是先制备本发明的含纳米硫组合物还是按照配方先制备各种基本的洗护用品或药物组合物等不作具体要求，两个步骤之间并无先后之分。
实施例45
本发明的发明人自身因面部皮肤多次发红、脱皮、疼痛，被诊断患有脂溢性皮炎。涂抹医生开的药膏后，皮炎几天便好，但若不使用药膏，大约一、两周后又复发，多年以来，一直如此，多次多地看医生，都未能治愈。
同时医生所开药膏，全是含有激素的药膏，发明人担心激素的副作用，后经发明人自己查资料，发现硫磺膏可以治疗脂溢性皮炎，于是买回来硫磺软膏或乳膏等，然而使用后，发现这些硫磺膏等并无疗效。经发明人研究发现，产生此种无疗效的原因确为硫磺的粒径过大，难以被皮肤吸收以利用其抗真菌性，即使在现有的药膏中具有约5％的含量，但收效甚微，还使得药膏具有强烈的刺激性气味，不符合现实需求。
后来，发明人利用其自制的纳米硫磺膏，含硫量可以只有千分之几，但非常管用，且发明人使用了一年多，没有出现皮肤干燥脱皮等副作用。
另外，基于同样的原因，发明人头发有大量的头皮屑，普通洗发香波已经无效了，例如含吡啶硫酮锌ZPT、煤焦油等各种洗发香波都无效。发明人同样去求助医生，医生(加拿大)给其推荐的是含酮康唑洗发香波，国内有同类产品“康王”。但在使用酮康唑两三年后，也无效了。后来，又使用含硫化硒的洗发水(以前国内没有，现在也有了)，有一定效果，但硫化硒是剧毒或高毒化学物质，不宜多用。
现在发明人使用的是其自制的纳米硫磺洗发液(由本发明的含纳米硫组合物加入现有洗发液得到)，效果极佳，使用了一年多，也没有发现任何不良副作用，且基本控制了头皮屑的大量产生。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (23)

  1. 一种含纳米硫组合物，其特征在于：包含纳米硫以及用以阻止或延缓所述纳米硫团聚的抗团聚剂。
  2. 根据权利要求1所述的含纳米硫组合物，其特征在于：所述抗团聚剂为选自增稠剂、助悬剂、分散剂、乳化液、粘合剂、反絮凝剂、偶联剂、防静电剂、表面活性剂、胶体中的一种或多种的组合。
  3. 根据权利要求2所述的含纳米硫组合物，其特征在于：所述增稠剂为选自天然增稠剂和化学合成增稠剂中的任一种或多种的组合，其中，天然增稠剂包括淀粉、糊精、阿拉伯胶、卡拉胶、果胶、琼胶、海藻酸及其盐或衍生物、罗望子胶、甲壳素、黄蜀葵胶、亚麻籽胶、田菁胶、瓜尔胶、槐豆胶、黄原胶；所述化学合成增稠剂包括羧甲基淀粉钠、羟丙基淀粉醚、淀粉磷酸酯钠、乙酰基二淀粉磷酸脂、磷酸化二淀粉磷酸酯、羟丙基二淀粉磷酸酯。
  4. 根据权利要求2所述的含纳米硫组合物，其特征在于：所述助悬剂为选自甘油、糖浆剂、胶树类助悬剂、植物多糖类助悬剂、纤维素类助悬剂、卡波普、聚维酮、葡聚糖、硅皂土、触变胶中的一种或多种的组合。
  5. 根据权利要求2所述的含纳米硫组合物，其特征在于：所述的分散剂为选自水玻璃、三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、瓜尔胶、聚乙二醇、脂肪酸聚乙二醇酯中的一种或多种的组合。
  6. 根据权利要求2所述的含纳米硫组合物，其特征在于：所述表面活性剂为选自双链离子型表面活性剂、阴离子表面活性剂、阳离子表面活性剂和非离子表面活性剂中的一种或多种的组合。
  7. 根据权利要求2所述的含纳米硫组合物，其特征在于：所述胶体为选自硅酸胶体、淀粉胶体、蛋白质胶体、豆浆、胶体二氧化硅中的一种或多种的组合。
  8. 根据权利要求1所述的含纳米硫组合物，其特征在于：所述抗团聚剂为选自淀粉、糊精、阿拉伯胶、卡拉胶、果胶、琼胶、海藻酸、海藻酸钠、海藻酸二醇酯、罗望子胶、甲壳素、黄蜀葵胶、亚麻籽胶、田菁胶、瓜尔胶、槐豆胶、黄原胶、羧甲基淀粉钠、羟丙基淀粉醚、淀粉磷酸酯钠、乙酰基二淀粉磷酸脂、磷酸化二淀粉磷酸酯、羟丙基二淀粉磷酸酯、甘油、糖浆剂、卡波普、聚维酮、葡聚糖、硅皂土、触变胶、水玻璃、三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、木质素、羧甲基纤维素、羟乙基纤维素、羟丙基纤维素、聚丙烯酰胺、聚乙二醇、脂肪酸聚乙二醇酯、琥珀酸二辛酯磺酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、烷基酚聚氧乙烯醚、硅酸胶体、蛋白质胶体、豆浆、胶体二氧化硅、司盘20、司盘60、司盘80、吐温20、吐温60和吐温80中的一种或多种的组合。
  9. 根据权利要求1所述的含纳米硫组合物，其特征在于：所述的含纳米硫组合物中所述纳米硫与所述抗团聚剂的质量比为1～10：0.5～20。
  10. 根据权利要求1所述的含纳米硫组合物，其特征在于：所述纳米硫的粒径小于等于10微米，优选小于等于5微米，更优选为5nm～3000nm，进一步优选为10nm～2000nm，更进一步优选为20nm～500nm。
  11. 根据权利要求1所述的含纳米硫组合物，其特征在于：所述的含纳米硫组合物还含有溶剂，所述纳米硫和抗团聚剂分散在所述溶剂中。
  12. 根据权利要求11所述的含纳米硫组合物，其特征在于：所述溶剂为选自水、乙醇、丙二醇、丙三醇、聚乙二醇中的一种或多种的组合。
  13. 根据权利要求11所述的含纳米硫组合物，其特征在于：所述的含纳米硫组合物中，所述纳米硫的质量含量为0.01％～10％，所述抗团聚剂的质量含量为0.01～25％。
  14. 根据权利要求11所述的含纳米硫组合物，其特征在于：所述的含纳米硫组合物通过如下方法(a)或(b)或(c)制备：
    (a)将粉末状纳米级硫与溶剂、抗团聚剂混合，分散均匀得到含纳米硫组合物；
    (b)使硫代硫酸盐或多硫化物与酸在抗团聚剂存在下，在溶剂中反应得到含纳米硫组合物；
    (c)以硫代硫酸盐或多硫化物、酸为反应原料，通过微乳法制备得到含纳米硫组合物。
  15. 根据权利要求14所述的含纳米硫组合物，其特征在于：所述硫代硫酸盐为选自硫代硫酸钠、硫代硫酸铵、硫代硫酸钾中的一种或多种的组合；和/或，所述的多硫化物为选自多硫化钠、多硫化钾、多硫化铵中的一种或多种的组合。
  16. 根据权利要求14所述的含纳米硫组合物，其特征在于：所述酸为有机酸、无机酸或者两者的组合。
  17. 根据权利要求16所述的含纳米硫组合物，其特征在于：所述有机酸包括苯甲酸、乙酸、柠檬酸、酒石酸、水杨酸、乳酸，所述无机酸包括盐酸、硫酸、硝酸、硼酸。
  18. 一种如权利要求1至14中任一项权利要求所述的的含纳米硫组合物的制备方法，其特征在于：所述制备方法包括使硫代硫酸盐或多硫化物与酸在抗团聚剂存在下，在溶剂中反应得到含纳米硫组合物。
  19. 根据权利要求18所述的制备方法，其特征在于：所述硫代硫酸盐为选自硫代硫酸钠、硫代硫酸铵、硫代硫酸钾中的一种或多种的组合；和/或，所述的多硫化物为选自多硫化钠、多硫化钾、多硫化铵中的一种或多种的组合；所述酸为有机酸、无机酸或者两者的组合。
  20. 如权利要求1-17中任一项权利要求所述的含纳米硫组合物用于制备含硫产品的用途。
  21. 根据权利要求20所述的用途，其特征在于：所述含硫产品为人或动物皮肤表面的洗护用品、治疗皮肤病的药物、治疗肿瘤的药物、治疗毛发疾病的药物、农药、蔬菜水果植物保鲜剂、动物食料添加剂、涂料防霉添加剂、织物防霉剂或织物杀螨虫剂。
  22. 一种含硫产品，其特征在于：所述含硫产品通过以下步骤制备得到：
    (1)提供如权利要求1-17中任一项权利要求所述的含纳米硫组合物；
    (2)将如权利要求1-17中任一项权利要求所述的含纳米硫组合物与含硫产品的其他组分混合。
  23. 根据权利要求22所述的含硫产品，其特征在于：所述含硫产品为人或动物皮肤表面的洗护用品、治疗皮肤病的药物、治疗毛发疾病的药物、治疗肿瘤的药物、农药、蔬菜水果植物保鲜剂、动物食料添加剂、涂料防霉添加剂、织物防霉剂或织物杀螨虫剂。
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