WO2024045003A1 - 一种微胶囊壳材及微胶囊制备方法 - Google Patents

一种微胶囊壳材及微胶囊制备方法 Download PDF

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Publication number
WO2024045003A1
WO2024045003A1 PCT/CN2022/116047 CN2022116047W WO2024045003A1 WO 2024045003 A1 WO2024045003 A1 WO 2024045003A1 CN 2022116047 W CN2022116047 W CN 2022116047W WO 2024045003 A1 WO2024045003 A1 WO 2024045003A1
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microcapsule shell
shell material
emulsifier
material according
microcapsule
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PCT/CN2022/116047
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English (en)
French (fr)
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袁彦洁
李芸娇
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重庆小丸生物科技股份有限公司
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Publication of WO2024045003A1 publication Critical patent/WO2024045003A1/zh

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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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/342—Alcohols having more than seven atoms in an unbroken chain
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • 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
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • 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
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/925—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of animal origin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin

Definitions

  • the invention belongs to the technical field of daily chemical products, and specifically relates to a microcapsule wall material and a method for preparing microcapsules by using the wall material through a melting, dispersion and condensation method.
  • Microcapsule refers to a micro container or wrapper with a polymer or inorganic wall.
  • Microencapsulation is a technology that encapsulates solid, liquid or gaseous active substances with materials.
  • the use of microcapsule technology can mask the bad taste and odor of the wrapped substances, control the release rate and mode of active substances, improve the matching between active substances and the environment, reduce incompatibility, and isolate oxygen, water and other factors that have an impact on the stability of active substances. wait.
  • Microcapsule technology has been used in many industrial fields for many years and uses many methods, such as disk coating process, spray drying, spray freezing, fluidized bed, orifice method, interfacial polymerization, in-situ polymerization, etc.
  • melt-dispersion condensation method uses waxy substances and polymer solutions that have a lower softening point and are meltable as microcapsule shell materials. When this kind of material is heated, it will soften and become liquid, and the wrapped core material will be dispersed into it to form a uniform dispersion; when the system cools, a solid shell will be formed around the core material.
  • the melting, dispersion and condensation method utilizes the unique properties of hot melt materials when heated and condensed to achieve microencapsulation. It can be condensed into microencapsulated materials in either a liquid medium or a gaseous medium. When using the melting and dispersion method to make microcapsules, it has the advantages of no solvent, effective light protection, fast and efficient wrapping speed, and has high practical value.
  • Microcapsules are prepared by the melting, dispersion and condensation method.
  • the packaging materials used are usually inert substances that are non-solvent, have high thermal stability and have low reactivity.
  • Solid oils, waxes, fatty acids, fatty alcohols, and solid surfactants are all very commonly used ingredients in cosmetics, and they are also good hot-melt shell materials that can be used in the melting, dispersion, and condensation method.
  • ordinary hot-melt materials whether they are greases, waxes, fatty acids, or fatty alcohols, all have a melting point selection problem.
  • the melting point of hot-melt materials in daily chemicals must be lower than the temperature of 35°C on the skin surface to be easier to spread and spread.
  • Hot-melt materials with melting points lower than 50°C are unstable and can easily melt and become liquid in high temperatures in the summer. The microcapsules are destroyed. Hot-melt materials with a melting point higher than 50°C usually cannot soften on the skin. They are too hard when applied and cannot be spread by pressure and body surface temperature, thus unable to release active substances.
  • polyethylene glycol with a degree of polymerization above 4000 there are also some hot melt raw materials with melting points higher than 50°C, such as polyethylene glycol with a degree of polymerization above 4000.
  • polyethylene glycol 4000-6000 is easily soluble in water. As a wrapping material, it will dissolve in water, causing the microcapsules to disintegrate, and most cosmetics contain water.
  • polyethylene glycol with a degree of polymerization higher than 6000 is not easily soluble in water, it is too hard to be applied to the skin, making it difficult to release active substances.
  • polyethylene glycol also has skin safety issues, and European regulations have restricted the use of polyethylene glycol.
  • liquid polyethylene glycols such as PEG-4 and PEG-100 are easily absorbed by the skin and have been proven to lower blood pressure.
  • by-product pollutants in PEG production include the carcinogen 1,4-dioxane, polycyclic aromatic compounds, heavy metals lead, iron, cobalt, nickel, cadmium, arsenic, etc.
  • the purpose of the present invention is to provide a microcapsule shell material that solves the problem that the melting point, water solubility and hardness of ordinary microcapsule shell materials in the prior art cannot meet the requirements of the melting, dispersion and condensation method for preparing microcapsules at the same time. question.
  • the present invention also provides a method for preparing microcapsules using the microcapsule shell material.
  • the present invention adopts the following technical solutions:
  • a kind of microcapsule shell material the melting point of the shell material is higher than 50°C, and it is solid at temperatures in different climates. It can absorb water, swell and become soft, but does not dissolve or disintegrate in water; under the action of pressure, it can be easily spread to release the wrapped material.
  • the wrapped core material can be a solid or liquid material.
  • the core components of the microcapsule shell material include, in terms of weight percentage: 0-50% of higher fatty alcohol or polyethylene glycol, 10-60% of grease or wax, and 0-20% of oil thickener. %, the balance is emulsifier.
  • the shell material also contains 0-50% fat-soluble pigments or inorganic lakes in terms of weight percentage.
  • the pigment lake refers to synthetic or natural organic pigments or organic lakes; the pigment lake refers to inorganic lakes.
  • the emulsifier is a nonionic emulsifier, an anionic emulsifier, a cationic emulsifier or a zwitterionic emulsifier; preferably a nonionic emulsifier.
  • the grease or wax is any one of vegetable oil esters and vegetable waxes, animal fats and oils, synthetic greases and synthetic waxes, silicone oils and silicone waxes.
  • the higher fatty alcohol refers to a higher carbon alcohol with a melting point greater than 30 degrees; usually a higher carbon alcohol with a carbon number greater than 14 is used.
  • polyethylene glycol ⁇ PEG ⁇ refers to a solid polyethylene glycol with a molecular weight greater than 1000 and a freezing point higher than 25°C.
  • oil thickener refers to a polymer material thickener or solid powder thickener dissolved in oil.
  • the emulsifier is preferably a solid emulsifier with a melting point higher than 30° C., and the HLB value of the emulsifier is between 3-13.
  • nonionic emulsifiers include: alcohol nonionic emulsifiers, polyoxyethylene nonionic emulsifiers, nitrogen-containing nonionic emulsifiers, block polyether type and sterol derived nonionic emulsifiers.
  • alcohol nonionic emulsifiers include: glycol esters, glyceryl esters, polyglycerol fatty acid esters, neopentyl polyol lipids, sugar esters, sorbitol esters, alkyl glycosides One or more types of nonionic emulsifiers.
  • the ethylene glycol ester is a non-ionic emulsifier generated by the reaction of ethylene glycol and fatty acid.
  • the glycerol fatty acid ester is a non-ionic emulsifier generated by the reaction of glycerol and fatty acids, which is glycerol monoester, diester or triester.
  • the polyglycerol fatty acid ester emulsifier is a polyhydroxyester nonionic surfactant formed from polyglycerol and fatty acids.
  • the neopentyl polyol lipid nonionic emulsifier is pentaerythritol fatty acid ester.
  • the sugar ester emulsifier refers to a non-ionic emulsifier obtained by esterifying glucose with multiple hydroxyl groups, sucrose and fatty acids such as lauric acid, stearic acid, oleic acid, palmitic acid, etc.; sugar esters can be divided into different types due to different degrees of esterification. For monoester, diester and triester.
  • the sorbitol esters are partial fatty acid esters (Tweens) of polyoxyethylene sorbitan and fatty acid esters (Span) of polyoxyethylene sorbitan.
  • the alkyl glycosides refer to alkyl glycosides synthesized from glucose and fatty alcohol.
  • the polyoxyethylene nonionic emulsifier includes: one or more of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol polyoxyethylene ether, and polyoxyethylene fatty acid ammonium.
  • the fatty alcohol polyoxyethylene ether is an ether non-ionic emulsifier obtained by adding polyethylene glycol (PEG) and fatty alcohol through ethylene oxide.
  • PEG polyethylene glycol
  • RO(CH2CH2O)nH is the most commonly developed and common emulsifier. emulsifier.
  • the fatty acid polyoxyethylene ester is produced by the addition reaction of fatty acid and ethylene oxide, and its general formula is RCOO(CH2CH2O)nH.
  • the invention also provides a method for preparing microcapsules, using the above-mentioned microcapsule shell material components, and the preparation steps include:
  • step 2) Cool and shape the melted and dispersed liquid obtained in step 2) in the air to obtain microcapsules of the required size, specification and shape.
  • the cooling method is to inject the melted and dispersed liquid into a mold or spread it on a flat surface for cooling to obtain a mold-shaped or sheet-shaped wrapper.
  • the cooling method is to drop or spray the melted and dispersed liquid into cold air, and obtain spherical wrapped microspheres of different specifications through air cooling at a certain distance.
  • the core material is a water-soluble active substance, a fat-soluble active substance or an insoluble substance.
  • the water-soluble active substance is one or more of vitamins B1, B3, B5, B12, vitamin C and its derivatives, ethyl ascorbic acid, tea polyphenols, peptides, amino acids, and plant extracts.
  • the fat-soluble active substances are vitamin E, vitamin E acetate, vitamin A, vitamin A palmitate, vitamin C palmitate, Q10, carotene, astaxanthin, lutein, ceramide, and phytosphingosine One or more alcohols.
  • the fat-soluble active substance is essential oil or essence extracted from plants.
  • the insoluble substances refer to active substances that are not soluble in water or oil, including minerals, probiotics, plant and animal raw powders and/or proteins, etc.
  • the invention also provides another method for preparing microcapsules, using the microcapsule shell component, and the preparation includes the following steps:
  • the core material is crystal or solid particles.
  • the present invention has the following beneficial effects:
  • the melting point of the shell material of the present invention is above 50°C, and it can maintain a stable solid state at any seasonal temperature. At the same time, it can become soft in daily chemicals containing water and oil, and cannot be completely dissolved in water or oil. Under the pressure of fingers, It can be easily spread on the skin and release the wrapped core material; it solves the problem that the melting point, water solubility and hardness of the existing microcapsule shell materials cannot meet the requirements of the melting, dispersion and condensation method of microcapsules in daily chemicals. technical issues.
  • the microcapsule shell material of the present invention is composed of emulsifiers, fatty alcohols, greases or waxes, etc., and uses raw materials approved for the safety of cosmetics, food, and drugs.
  • the raw materials are non-toxic and environmentally friendly, and will not harm human health and the environment. pollute.
  • It is a series of hot-melt raw materials that can be used to make microcapsules by the melting, dispersion and condensation method. They remain solid at room temperature without any sign of melting or softening. In water, they can absorb water and oil, expand and become soft, but do not dissolve or disintegrate in water and oil. Under the action of pressure, the wrapped material can be easily spread and released.
  • the wrapped core material can be a solid or liquid material.
  • the microcapsule preparation method of the present invention adopts the melting, dispersion and condensation method. When using this method to prepare microcapsules, it has the advantages of no solvent, effective light protection, fast and efficient wrapping speed, and has high practical value.
  • microcapsule shell material of the present invention is melted at high temperature, does not contain water, many emulsifiers themselves have antibacterial effects, and are stored in a solid state, so no preservatives are needed.
  • the present invention provides a microcapsule shell material, the melting point of the shell material after mixing is higher than 50°C, and it is solid at temperatures in different climates.
  • its core components include: 0-50% of higher fatty alcohol or polyethylene glycol, 10-60% of grease or wax, 0-20% of oil thickener, and the balance is Emulsifier.
  • the shell material also contains fat-soluble pigments or inorganic lakes.
  • the emulsifier is a nonionic emulsifier.
  • the emulsifier can be an anionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, a nonionic emulsifier or a mixture of emulsifiers.
  • non-ionic emulsifiers refer to ions that do not ionize in any form in aqueous solution and are not dissociated in aqueous solution.
  • the hydrophilic group is mainly composed of a certain number of oxygen-containing groups (generally ether groups or hydroxyl groups). , a surfactant that achieves dissolution by forming hydrogen bonds with water.
  • Nonionic emulsifiers have high stability and are not easily affected by strong electrolytes, inorganic salts, acids and bases; they have good compatibility with other surfactants. It has the advantage of good solubility in both water and organic solvents. Taking into account the incompatibility with various systems, for example, anionic emulsifiers cannot be used in cationic conditioner systems because electropolymerization will cause flocculation and precipitation, etc. Non-ionic emulsifiers are usually preferred, so that the emulsifier has Wider applicability.
  • Nonionic surfactant is an amphiphilic structural compound that does not dissociate into an ionic state in water. Its hydrophilic group is mainly composed of polyethylene glycol group, that is, polyoxyethylene group, and the other is a structure based on polyols (such as glycerol, pentaerythritol, sucrose, glucose, sorbitol, etc.). In addition, there are structures based on monoethanolamine and diethanolamine.
  • the nonionic emulsifiers include: alcohol nonionic emulsifiers, polyoxyethylene nonionic emulsifiers, nitrogen-containing nonionic emulsifiers, block polyether type and sterol derived nonionic emulsifiers.
  • alcohol nonionic emulsifiers are esters generated by the esterification reaction of polyols containing multiple hydroxyl groups and fatty acids; in addition, they also include amino alcohols with NH 2 or NH groups and amino alcohols with -CHO A nonionic emulsifier prepared by reacting sugar-based sugars with fatty acids or esters.
  • the alcohol nonionic emulsifiers include: glycol esters, glyceride nonionic emulsifiers, polyglycerol fatty acid esters nonionic emulsifiers, and neopentyl polyol lipid nonionic emulsifiers. , one or more of sugar ester nonionic emulsifiers, sorbitol esters, and alkyl glycoside nonionic emulsifiers.
  • the glycerolipid non-ionic emulsifier is one or more of monoester, diester or triester; the monoester includes monoglycerol fatty acid lipids; the monoglyceryl fatty acid lipids are monoglycerol fatty acid lipids. Ester ester, monoglyceryl palmitate, monoglyceryl laurate, monoglyceryl monoisostearate or monoglyceryl distearate.
  • polyglycerol fatty acid esters are produced by reacting fatty acids and their derivatives with polyglycerol.
  • the chemical structure and physical and chemical properties of polyglycerol fatty acid esters are related to the degree of polymerization of polyglycerol, the type of fatty acids and the degree of esterification.
  • polyglycerol fatty acid esters The degree of polymerization of glycerol is generally 2 to 10; the carbon chain length of fatty acids is generally 6 to 18, and the carbon chain can be saturated or unsaturated, or linear or branched; in addition, the degree of esterification of the hydroxyl group It can be monoester, diester, polyester, etc., so that a series of polyglycerol fatty acid ester emulsifiers with diverse structures and different properties can be obtained.
  • the polyglycerol fatty acid ester nonionic emulsifier is polyglycerol ricinoleate, tripolyglyceryl distearate, tripolyglycerol diisostearate, polyglycerol 10 palmitate, and polyglycerol 10 meat.
  • the neopentyl polyol lipid nonionic emulsifier is pentaerythritol fatty acid ester.
  • Pentaerythritol fatty acid ester is a good cream excipient. When combined with monoglyceride, it can significantly improve the consistency and stability of the product, and it is easy to emulsify without affecting the viscosity, foam and stability of the product. Creams containing pentaerythritol distearate are lightweight, easily absorbed and spreadable, leaving skin smooth and soft.
  • the sugar ester nonionic emulsifier is sucrose stearate.
  • Glucose, sucrose, etc. all have multiple external hydroxyl groups and can be esterified with lauric acid, palmitic acid, stearic acid, oleic acid, etc. to obtain sugar esters. Since sugars have more hydroxyl groups, they can be esterified into water-soluble products. Most sugar esters are tasteless, odorless, completely biodegradable, non-toxic and non-irritating to the human body.
  • the polyethylene glycol nonionic emulsifier is the product of the addition reaction between ethylene oxide and compounds containing active hydrogen, and belongs to the ethers; including higher alcohol ethylene oxide adducts, alkylphenol epoxy Ethane adduct, fatty acid ethylene oxide adduct, higher fatty acid amide ethylene oxide adduct. There are many varieties and large output, and it is a major category among non-ions.
  • Polyethylene glycol nonionic emulsifiers can be divided into long-chain fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, and polyoxyethylene based on the type of hydrophobic groups.
  • Vinyl alkyl amides and polyethers etc.
  • the higher fatty alcohols refer to aliphatic alcohols containing more than twelve carbon atoms and a chain of 12 to 22 carbon atoms. They are waxy solid saturated monohydric alcohols, also known as higher alkanols. Higher alkanols are stable in nature, not easily oxidized, stable under light, resistant to acids and alkalis, do not absorb moisture, and have good biodegradability and biological activity; they are often white waxy solids at room temperature.
  • This high-carbon fatty alcohol has amphiphilic characteristics, that is, it has hydrophobic groups such as hydrocarbon chains and hydrophilic groups such as hydroxyl groups in the molecule.
  • the fat-soluble pigments or inorganic lakes are organically synthesized pigments or lakes such as red 30, blue 1, yellow 5, yellow 6, green 6, etc., and natural pigments are carotene, lutein, chlorophyll, astaxanthin, tomato Red pigment, lithospermum oil, turmeric, gardenia yellow, etc.
  • the inorganic lake is one or more of ultramarine blue, chrome green, manganese violet, titanium dioxide, mica, carbon black or iron oxide.
  • the emulsifier is solid and has a melting point higher than 40°C.
  • the HLB value of the emulsifier is between 3-13.
  • the oil or wax is hydrogenated vegetable oil, one or more of candelilla wax, rice bran wax, palm wax, ozokerite, microcrystalline wax, myristyl myristate, lanolin or beeswax. These waxes or greases are usually solid or semi-solid at room temperature, with a melting point higher than 35 degrees. Greases and waxes can be of natural origin or synthetic.
  • the oil thickener is a high molecular polymer soluble in oil or a solid powder oil phase thickener insoluble in oil. Thickeners are used to prevent the precipitation of low melting point oil. Polymer materials that dissolve in oil and increase oil viscosity include palmitate dextrin, castor oil IPDI copolymer, dibutyl ethylhexanoyl glutamine, dibutyl lauroyl glutamine, and hydrogenated styrene/butadiene. One or more types of copolymers and silicone elastomers.
  • the oil-insoluble solid powder oil phase thickener is one or more of silica, hectorite, montmorillonite, bentonite, zeolite, clay, and plant cellulose.
  • the shell material of the present invention can encapsulate fat-soluble active substances vitamin E, vitamin E acetate, vitamin A, vitamin A palmitate, vitamin C palmitate, Q10, carotene, astaxanthin, lutein, ceramide, Phytosphingosine, salicylic acid, etc.
  • the shell material of the present invention can encapsulate one or more of the water-soluble active substances vitamins B1, B3, B5, B12, vitamin C and its derivatives, ethyl ascorbic acid, tea polyphenols, peptides, amino acids, and plant extracts.
  • the shell material of the present invention can wrap active ingredients such as proteins, enzymes, probiotics, minerals, and plant or animal tissue insoluble in water or oil.
  • the microcapsule shell material of the present invention has a melting point higher than 50°C and is solid at temperatures in different climates.
  • Embodiment 1-18 in Table 1, each component is calculated by weight percentage.
  • the melting point of this composite shell material is higher than 50°C, and it can remain solid at room temperature in different climates without any signs of melting, softening, or liquid oil. In water and oil, it can absorb water and oil, expand and become soft, but does not dissolve or disintegrate. in water and oil. Under the action of pressure, the wrapped material can be easily spread and released.
  • the wrapped core material can be a solid or liquid material. It solves the problem that the microcapsules prepared by the existing technology using a single molten shell material cannot simultaneously meet the special technical requirements of daily chemicals such as melting point, hardness, high temperature stability, release, and skin feel.
  • the raw materials used in the present invention are hot-melt raw materials, and microcapsules can be made by the melting, dispersion and condensation method. When using this method to make microcapsules, water and any organic solvents are not used, low energy consumption is environmentally friendly, and the wrapping speed is fast. At the same time, the capsule shell can effectively protect from light. Avoid oxygen and have high practical value.
  • Preparation steps include:
  • step 2) Add vitamin A, vitamin E and astaxanthin to the mixture obtained in step 1) and mix evenly;
  • step 3 Drop the melted and dispersed mixture obtained in step 2) into a cooling tower with an inlet air temperature of 10°C and a height of 6 meters through a 0.5 mm orifice;
  • the operator can collect orange wax spherical microcapsules with a diameter of 0.2-0.8 mm at the bottom of the cooling tower.
  • the microcapsules absorb water, oil and swell in water, gel or cream at 25°C, and the diameter increases by 1- 2x and softened, can be spread easily with fingers.
  • a molten composition with a melting point higher than 50 degrees, about 55-65 degrees Celsius is obtained as a capsule shell.
  • the HLB value is in
  • Vitamin A is a coenzyme that regulates glycoprotein synthesis. It stabilizes the cell membrane of epithelial cells and maintains the integrity and function of epithelial cells. Vitamin A deficiency can cause keratinization of dry cells in epithelial tissues. Vitamin E and astaxanthin are both antioxidant and anti-aging active substances. However, these three active substances are unstable and easily oxidized by light and heat. After wrapping, it is more stable to isolate oxygen and air, and is easy to add. The microcapsules in the formula absorb water and swell, making it easy to spread and release the active ingredients.
  • a double-layer color-changing pigment microcapsule A double-layer color-changing pigment microcapsule
  • Element percentage Components monoglyceride 10% Glyceride emulsifier Polyglycerol 10 Palmitate 20% Polyglyceryl ester emulsifier 1618 Alcohol 25% Higher fatty alcohol Myristyl myristyl alcohol 5% Synthetic grease rice bran wax 5% natural wax iron oxide brown 30% inorganic lake Vitamin C Palmitate 5% fat soluble actives total 100%
  • Element percentage Components monoglyceride 10% Glyceride emulsifier Polyglycerol 10 Palmitate 20% Polyglyceryl ester emulsifier 1618 Alcohol 25% Higher fatty alcohol Myristyl myristyl alcohol 5% Synthetic grease rice bran wax 5% natural wax Titanium dioxide 30% inorganic lake Vitamin C Palmitate 5% fat soluble actives total 100%
  • a preparation method of color-changing pigment microcapsules including:
  • step 4 Put the brown microcapsule core obtained in step 3 as a seed core into the tangentially sprayed fluidized bed, and spray and cool the titanium dioxide melted and dispersed liquid in Table 4 in step 2 onto the rotating flowing brown microcapsule core.
  • a white shell wraps the brown core.
  • the spray weight of the white layer is 3 times the weight of the brown core.
  • white direct 0.8-1.2 mm microcapsules are obtained.
  • the fused microcapsules have a double-layer structure, with a brown inner core and a white outer layer.
  • the toner content is as high as 30%. It swells in the gel and cream and becomes white particles. But when applied with pressure, the inner brown layer and outer white layer mix to become skin color. Has a very good concealer effect. It also contains the active whitening ingredient Vitamin C Palmitate.
  • the capsule has physical concealer and whitening effects.
  • the melting point of the mixture is between 55-65 degrees and the HLB value is between 6-9.
  • Preparation methods include:
  • step 3 Rapidly drip the melted and dispersed liquid obtained in step 2) into the heart-shaped mold. After rapid cooling and molding, the required wax block microcapsules with a diameter of approximately 3 mm and a thickness of 0.5 mm are obtained.
  • the melting point of this formula is higher than 55 degrees, and the HLB value is between 4-9.
  • keratin plays a role in scalp care.
  • Ginger essential oil and Shouwu extract have the effect of promoting hair growth.
  • the tablet-shaped capsule can be used in hair conditioner and baking ointment, and has both beautiful appearance and practical effect.
  • the formula raw materials are from natural sources, and the production process is water-free, solvent-free, and preservative-free, which is in line with the new trend of green chemistry in the daily chemical industry.
  • a method for preparing microcapsules including the following steps:
  • step 2) Cool and shape the melted and dispersed liquid obtained in step 2) in the air to obtain microcapsules of the required size, specification and shape.
  • the cooling method is to inject the melted and dispersed liquid into a mold or cool it on a plane to obtain a mold-shaped or sheet-shaped wrapper.
  • the cooling method is to drop or spray the melted and dispersed liquid into cold air, and obtain spherical wrapped microspheres of different specifications through a certain distance.
  • the core material is a water-soluble active substance or a fat-soluble active substance.
  • the water-soluble active substance is one or more of vitamins B1, B3, B5, B12, tea polyphenols, plant extracts or plant powders.
  • the fat-soluble active substance is one or more of vitamin E, vitamin A, Q10, carotene, astaxanthin, lutein, ceramide or phytosphingosine.
  • the present invention also provides another application method of microcapsule shell material.
  • the preparation steps include:
  • the core material is crystal or solid particles.
  • the melting point of the shell material of the microcapsules prepared by the method of the present invention is higher than 50°C, and remains solid at room temperature without signs of melting, softening, or liquid oil; in water, it can absorb water, swell, and become soft, and does not dissolve or disintegrate in water. in water. Under the action of pressure, the wrapped substance can be easily spread and released.
  • the wrapped core material can be a solid or liquid substance, which solves the problems of melting point, hardness, high temperature stability, release of common microcapsule shell materials in the existing technology. The conditions cannot simultaneously meet the technical problems of preparing microcapsules using the melting, dispersion and condensation method for use in daily chemicals.

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Abstract

公开了一种微胶囊壳材及微胶囊制备方法。所述微胶囊壳材按重量百分含量计，包括以下组分：高级脂肪醇或聚乙二醇为0-50％，油脂或蜡为10-60％，油增稠剂为0-20％，余量为乳化剂。微胶囊壳材熔点高于50℃，其在不同气候的温度下是固态；其没有融化变软析出液体油等迹象；在水中又可以吸水膨胀而变软，但是不溶解或崩解在水中。在压力的作用下，可以轻易的涂抹开释放被包裹的物质，被包裹的芯材可以是固体或者液体物质。解决了现有技术使用单一的熔融壳材制备的微胶囊，不能同时满足日化品对熔点、硬度、高温稳定性、释放、肤感等特殊的技术要求。

Description

一种微胶囊壳材及微胶囊制备方法 技术领域
本发明属于日化用品技术领域，具体涉及一种微胶囊璧材及运用该璧材通过熔化分散冷凝法制备微胶囊的方法。
背景技术
在化妆品领域，有很多对皮肤有功效的活性物在水、空气、紫外线等环境中不能稳定存在，而化妆品中的很多成分例如水、油脂、表面活性剂、酸碱调节剂、螯合剂等也很容易与活性物发生配伍反应而使活性物失去活性，不能产生对应的效果。因此，如何将这些有功效的活性物包裹起来，提高其在储存期间的稳定性，又能在使用的时候使其在皮肤上快速释放就变得非常必要。
微胶囊(microcapsule)是指一种具有聚合物或无机物壁的微型容器或包裹物。微胶囊技术(Microencapsulation)是将固态、液态或气态的活性物用材料包裹起来的技术。运用微胶囊技术可以掩盖被包裹物质的不良味道、气味，控制活性物质的释放速度和方式，提高活性物质与环境的匹配度减少配伍禁忌，隔绝氧气、水等对活性物稳定性有影响的因素等。微胶囊技术在许多工业领域已应用多年且方法很多，例如盘涂工艺、喷雾干燥、喷雾冻结、流化床、锐孔法、界面聚合、原位聚合等等。
其中一种微胶囊技术是熔化分散冷凝法。该方法利用蜡状的物质和聚合物溶液等具有较低软化点且可熔融的材料作为微胶囊壳材。当这类物质受热时，会软化并变成液态，将被包裹的芯材分散其中形成均匀的分散液；当体系冷却的时候，在芯材的周围就形成了固态的壳。熔化分散冷凝法就是利用热融材料在受热时和冷凝时的独特性质来实现微囊化的，其既可以在液态介质中冷凝微胶囊化，也可以在气态介质中冷凝微胶囊化。在使用熔化分散法制作微胶囊的时候具有不使用溶剂，有效避光、包裹速度快高效的优点，具有很高的实用价值。
熔化分散冷凝法制备微胶囊，所用包裹材料通常采用非溶剂性、高热稳定性、低反应活性的惰性物质。在化妆品中固态油脂、蜡、脂肪酸、脂肪醇、固态表面活性剂都是非常常用的成分，也是很好的熔化分散冷凝法可以使用的热熔性壳原料。但是普通的热熔材料无论是油脂，蜡、脂肪酸、脂肪醇都有一个熔点选择的问题。通常在日化品中热融物的熔点要低于皮肤表面35℃的温度才能比较容易延展涂抹开，但是熔点低于50℃热熔材料不稳定，在夏天高温时候很容易熔化变成液态导致微胶囊被破坏。而熔点高于50℃的热熔材料通常又不能软化在皮肤上，涂抹时太硬、不能通过压力和体表温度涂抹开，从而无法释 放活性物。
虽然也有一些熔点高于50℃的热熔原料，例如聚合度在4000以上的聚乙二醇。但是聚乙二醇4000—6000易溶于水，作为包裹材料在水中会溶解，导致微胶囊崩解，而绝大多数化妆品含有水。而聚合度高于6000的聚乙二醇，虽然在水中不容易溶解，但是硬度又太大，不能在皮肤上涂抹，存在活性物难以释放的问题。而且聚乙二醇还存在皮肤安全性问题，欧洲法规已经对聚乙二醇有很多限用。此外，PEG-4、PEG-100等液态聚乙二醇很容易被皮肤吸收，已经被证实会降低血压，成分不容易被分解、容易累积在肝脏中，且数字愈小，代表化学成分愈容易被皮肤吸收，危害也越大。另外PEG生产中的副产物污染物包括致癌物1,4-二氧六环(1,4-dioxane)、多环芳香族化合物，重金属铅、铁、钴、镍、镉、砷等。
发明内容
针对现有技术存在的上述不足，本发明的目的在于提供一种微胶囊壳材，解决现有技术普通微胶囊壳材其熔点、水溶性以及硬度不能同时满足熔化分散冷凝法制备微胶囊的技术问题。
进一步，本发明还提供运用所述微胶囊壳材制备微胶囊的方法。
为了解决上述技术问题，本发明采用如下技术方案：
一种微胶囊壳材，所述壳材的熔点高于50℃，其在不同气候的温度下是固态。在水中可以吸水膨胀而变软，但是不溶解或崩解在水中；在压力的作用下，可以轻易的涂抹开释放被包裹的物质，被包裹的芯材可以是固体或者液体物质。
进一步，微胶囊壳材按重量百分含量计，其核心组分包括：高级脂肪醇或聚乙二醇为0-50％，油脂或蜡为10-60％，油增稠剂为0-20％，余量为乳化剂。
进一步，按重量百分含量计，所述壳材还包含0-50％脂溶性色素或者无机色淀。其中，所述色素色淀指合成或天然的有机色素或有机色淀；所述色淀是指无机色淀。
进一步，所述乳化剂为非离子型乳化剂、阴离子乳化剂、阳离子乳化剂或两性离子乳化剂；优选非离子型乳化剂。
进一步，所述油脂或蜡是植物油酯和植物蜡、动物油脂、合成油脂和合成蜡、硅油和硅蜡中的任一种。
进一步，所述高级脂肪醇是指熔点大于30度的高碳醇；通常使用碳数大于14的高碳醇。
进一步，所述聚乙二醇{PEG}是指分子量大于1000的凝固点高于25℃的固态聚乙 二醇。
进一步，所述油增稠剂是指溶解于油的高分子材料增稠剂或固体粉末类增稠剂。
进一步，所述乳化剂优选固态且熔点高于30℃的乳化剂，所述乳化剂的HLB值在3-13之间。
进一步，所述非离子型乳化剂包括：醇类非离子型乳化剂、聚氧乙烯型非离子型乳化剂、含氮非离子乳化剂、嵌段聚醚型以及甾醇衍生的非离子乳化剂。
进一步，所述醇类非离子型乳化剂包括：乙二醇酯类、甘油酯类、聚甘油脂肪酸酯、新戊基型多元醇脂类、糖酯类、山梨醇酯类、烷基糖苷型非离子型乳化剂中的一种或多种。
其中，所述乙二醇酯类是乙二醇和脂肪酸反应生成的非离子型乳化剂。所述甘油脂肪酸酯是甘油和脂肪酸反应生成的非离子型乳化剂为甘油单酯、双酯或三酯。所述聚甘油脂肪酸酯类乳化剂是由聚甘油与脂肪酸形成的多羟基酯类非离子型表面活性剂。所述新戊基型多元醇脂类非离子型乳化剂为季戊四醇脂酸酯。所述糖酯类乳化剂指由具有多个羟基葡萄糖、蔗糖与脂肪酸如月桂酸、硬脂酸、油酸、棕榈酸等酯化得到非离子乳化剂；糖酯由于酯化度不同，可分为单酯、双酯和三酯。所述山梨醇酯类为聚氧乙烯去水山梨醇的部分脂肪酸酯(吐温)类，以及失水山梨醇脂肪酸酯(司盘)类乳化剂。所述烷基糖苷类是指用葡萄糖和脂肪醇合成的烷基糖苷。所述聚氧乙烯型非离子型乳化剂包括：脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯脂、烷基苯酚聚氧乙烯醚、聚氧乙烯脂肪酸铵的一种或多种。所述脂肪醇聚氧乙烯醚是聚乙二醇(PEG)与脂肪醇通过环氧乙烷加成而得的醚类非离子型乳化剂，化学通式RO(CH2CH2O)nH是开发最多最常见的乳化剂。
进一步，所述脂肪酸聚氧乙烯脂是脂肪酸与环氧乙烷的加成反应生成，其通式为RCOO(CH2CH2O)nH。
本发明还提供一种微胶囊的制备方法，采用上述的微胶囊壳材组份，其制备步骤包括：
1)将微胶囊壳材加热至熔化，充分搅拌均匀；
2)将芯材加入到微胶囊壳材中搅拌均匀；
3)将步骤2)所得熔化分散的液体在空气中冷却成型，得到所需要大小、规格、形状的微胶囊。
其中，所述冷却方法为将熔化分散后的液体注入模具内、或者铺在平面上冷却，得到模具形状或片状的包裹物。
进一步，所述冷却方法为将熔化分散的液体滴入或者喷入冷空气中，通过一定距离的落差的空气冷却得到不同规格球状的包裹微球
其中，所述芯材为水溶性活性物、脂溶性活性物或不溶性物质。
所述水溶性的活性物为维生素B1、B3、B5、B12、维生素C及其衍生物、乙基抗坏血酸、茶多酚、肽、氨基酸、植物提取物中的一种或多种。
所述脂溶性的活性物为维生素E、维生素E醋酸酯、维生素A、维生素A棕榈酸脂、维生素C棕榈酸酯、Q10、胡萝卜素、虾青素、叶黄素、神经酰胺、植物鞘氨醇中的一种或多种。
所述脂溶性的活性物为植物提取精油或香精。
所述不溶性物质是指在水和油中都不溶解的的活性物包括矿物质、益生菌、植物动物原粉和/或蛋白质等。
本发明还提供另一种微胶囊的制备方法，采用所述的微胶囊壳材组份，其制备包括如下步骤：
1)将微胶囊壳材加热至熔化，充分搅拌均匀；
2)将熔化的壳材溶液盘涂到被包裹的芯材上，冷却后制得微胶囊。
其中，所述芯材为晶体或固体颗粒。
相比现有技术，本发明具有如下有益效果：
1、本发明壳材熔点在50℃以上，能够在任何季节气温保持稳定的固态，同时在含水和油的日化品中能够变软，且不能完全溶解于水或油，在手指的压力下又能够轻松的在皮肤上涂展，释放被包裹的芯材；解决了现有技术普通微胶囊壳材其熔点、水溶性以及硬度不能同时满足熔化分散冷凝法制备的微胶囊在日化品中的技术问题。
2、本发明微胶囊壳材是由乳化剂、脂肪醇、油脂或蜡等组成，使用的是化妆品、食品、药品安全认可的原材料，原料无毒环保，不会危害人的身体健康和造成环境污染。是一系列热熔原料，可用熔化分散冷凝法制作微胶囊，在室温保持固态没有融化变软等迹象；在水中又可以吸水吸油膨胀而变软，又不溶解或崩解在水和油中。在压力的作用下，可以轻易的涂散并释放被包裹的物质，被包裹的芯材可以是固体或者液体物质。
3、本发明微胶囊制备方法采用的是熔化分散冷凝法，使用该方法制作微胶囊的时候具有不使用溶剂，有效避光、包裹速度快高效的优点，具有很高的实用价值。
4、本发明的微胶囊壳材通过高温熔化、不含水、很多乳化剂本身就有抗菌的效果、并且固态保存，所以不需要防腐剂。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案，下面结合具体实施例对本发明 作进一步的说明，但本发明的实施方式不仅限于此。
本发明提供一种微胶囊壳材，所述壳材混合后的熔点高于50℃，其在不同气候的温度下是固态。其按重量百分含量计，其核心组分包括：高级脂肪醇或聚乙二醇为0-50％，油脂或蜡为10-60％，油增稠剂为0-20％，余量为乳化剂。
另外，所述壳材还含有脂溶性色素或者无机色淀。
其中，所述乳化剂为非离子型乳化剂。事实上，乳化剂可以是阴离子乳化剂、阳离子乳化剂、两性乳化剂、非离子型乳化剂或多种乳化剂的混合物。其中，非离子型乳化剂是指在水溶液中不电离出任何形式的离子，在水溶液中不是解离状态，亲水基主要由具有一定数量的含氧基团(一般为醚基或羟基)构成，靠与水形成氢键实现溶解的表面活性剂。非离子型乳化剂具有稳定性高，不易受强电解质、无机盐、酸碱影响；与其他表面活性剂相容性好；。在水和有机溶剂中皆有较好溶解性的优点。考虑到和各种体系的配伍禁忌，例如阴离子乳化剂不能使用在阳离子的护发素体系里面会发生电聚合反应产生絮凝沉淀等问题，通常优先选用非离子型乳化剂，这样可以让乳化剂具有更广泛的适用性。
非离子表面活性剂是一种在水中不离解成离子状态的两亲结构化合物。其亲水基主要是由聚乙二醇基即聚氧乙烯基构成，另外就是以多元醇(如甘油、季戊四醇、蔗糖、葡萄糖、山梨醇等)为基础的结构。此外还有以单乙醇胺、二乙醇胺为基础的结构。
所述非离子型乳化剂包括：醇类非离子型乳化剂、聚氧乙烯型非离子型乳化剂、含氮非离子乳化剂、嵌段聚醚型以及甾醇衍生的非离子乳化剂。
其中，醇类非离子型乳化剂是由含多个羟基的多元醇与脂肪酸进行酯化反应而生成的酯类；此外，还包括由带有NH 2或NH基的氨基醇以及带有-CHO基的糖类与脂肪酸或酯进行反应制得的非离子型乳化剂。
所述醇类非离子型乳化剂包括：乙二醇酯类、甘油酯类非离子型乳化剂、聚甘油脂肪酸酯类非离子型乳化剂、新戊基型多元醇脂类非离子型乳化剂、糖酯类非离子型乳化剂、山梨醇酯类、烷基糖苷型非离子型乳化剂中的一种或多种。
其中，所述甘油脂非离子型乳化剂为单酯、双酯或三酯中的一种或多种；所述单酯包括单甘油脂肪酸脂类；所述单甘油脂肪酸脂类为单甘油硬酯酸脂，单甘油棕榈酸酯，单甘油月桂酸脂、单异硬脂酸甘油酯或单甘油二硬脂酸酯。
其中，聚甘油脂肪酸酯类是由脂肪酸及其衍生物与聚甘油反应制得，聚甘油脂肪酸酯的化学结构和理化性质与聚甘油的聚合度、脂肪酸种类及酯化度有关，其中：聚甘油的聚合度一般为2～10；脂肪酸的碳链长度一般为6～18，而且碳链可以是饱和或者不饱和的， 也可以是直链或者带支链的；另外，羟基的酯化度可为单酯、双酯以及多酯等，从而可以得到一系列结构多样、性质各异的聚甘油脂肪酸酯类乳化剂。
所述聚甘油脂肪酸酯类非离子型乳化剂为聚甘油蓖麻醇酯、三聚甘油二硬酯酸脂、三聚甘油二异硬酯酸脂、聚甘油10棕榈酸脂、聚甘油10肉豆蔻酸酯、聚甘油-6聚蓖麻醇酸酯、聚甘油-2二聚羟基硬脂酸酯中的一种或多种。
其中，所述新戊基型多元醇脂类非离子型乳化剂为季戊四醇脂酸酯。季戊四醇脂酸酯是良好的膏霜赋型剂，与单甘脂复配可显著提高产品的稠度和稳定性，且容易乳化，不影产品的粘度，泡沫和稳定性。含有季戊四醇双硬脂酸酯的膏霜质感轻盈，易吸收，易铺展，令肌肤光滑和柔软。
所述糖酯类非离子型乳化剂为蔗糖硬脂酸酯。葡萄糖、蔗糖等均具有多外羟基,可与月桂酸、棕榈酸、硬脂酸、油酸等酯化而得到糖酯。由于糖类具有较多的羟基,因此,可以酯化成水溶性产品。糖酯大都无味、无臭、可完全生物降解完全,对人体无毒、无刺激性。
所述聚乙二醇型非离子型乳化剂为环氧乙烷与含有活泼氢的化合物进行加成反应的产物，属于醚类；包括高级醇环氧乙烷加成物，烷基酚环氧乙烷加成物，脂肪酸环氧乙烷加成物，高级脂肪酰胺环氧乙烷加成物。品种多、产量大，是非离子中的大类。聚乙二醇型非离子型乳化剂根据疏水基的种类可分为长链脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯、聚氧乙烯烷基胺、聚氧乙烯烷基酰胺和聚醚类等。例如：peg-20甲基葡糖倍半硬脂酸酯、peg-20硬脂酸酯、peg-100硬酯酸酯、鲸蜡硬脂醇聚醚6、鲸蜡硬脂醇聚醚25，硬脂醇聚醚-2、硬脂醇聚醚-21或鲸蜡硬脂基葡糖苷中的一种或多种。。
所述高级脂肪醇是指含有十二个碳原子以上具有12至22碳原子链的脂肪族醇类，是蜡状固体的饱和一元醇，又称为高级烷醇。高级烷醇性质稳定，不易氧化，光照下稳定，耐酸碱，不吸潮，具有良好的生物降解性和生物活性；常温下常以白色蜡状固体。这种高碳脂肪醇原具有两亲的特性，即在分子中有疏水基如碳氢链，又有亲水基如羟基。
所述脂溶性色素或者无机色淀为有机合成的色素或色淀红30、蓝1、黄5、黄6、绿6等、天然色素为胡萝卜素、叶黄素、叶绿素、虾青素、番茄红素、紫草油、姜黄、栀子黄等。无机色淀为群青、铬绿、锰紫、二氧化钛、云母、炭黑或氧化铁中的一种或多种。
所述乳化剂为固态且熔点高于40℃。
所述乳化剂的HLB值在3-13之间。
所述油脂或蜡为氢化植物油，小烛树蜡、米糠蜡、棕榈蜡、地蜡、微晶蜡、肉豆蔻酸肉豆蔻酯、羊毛脂或蜂蜡中的一种或多种。这些蜡或油脂通常在室温成固态或半固态，熔 点高于35度，油脂和蜡可以是天然来源的也可以是合成的。
所述的油增稠剂为溶解于油的高分子聚合物或不溶于油的固体粉末油相增稠剂。增稠剂是为了避免低熔点油的析出。溶解于油中增加油粘度的高分子材料为棕榈酸糊精、蓖麻油IPDI共聚物、二丁基乙基己酰基谷氨酰胺、二丁基月桂酰谷氨酰胺、氢化苯乙烯/丁二烯共聚物、硅弹体中的一种或多种。不溶于油的固体粉末油相增稠剂为二氧化硅、水辉石、蒙脱石、膨润土、沸石、黏土、植物纤维素中的一种或多种。
本发明的壳材可以包裹脂溶性活性物维生素E、维生素E醋酸酯、维生素A、维生素A棕榈酸脂、维生素C棕榈酸酯、Q10、胡萝卜素、虾青素、叶黄素、神经酰胺、植物鞘氨醇、水杨酸等。
本发明的壳材可以包裹水溶性活性物维生素B1、B3、B5、B12、维生素C及其衍生物、乙基抗坏血酸、茶多酚、肽、氨基酸、植物提取物中的一种或多种。
本发明的壳材可以包裹水油都不溶解活性物蛋白质、酶、益生菌、矿物质、植物或动物组织的原粉等。
一、本发明微胶囊壳材，熔点高于50℃，其在不同气候的温度下是固态状。
实施例1－18，表1中，各成份按重量百分含量计
表1微胶囊壳材的组成
Figure PCTCN2022116047-appb-000001
Figure PCTCN2022116047-appb-000002
该组合壳材熔点高于50℃，能在不同气候下的室温保持固态，没有融化变软析出液体油等迹象；在水中和油中又可以吸水吸油膨胀而变软，但是不溶解或崩解在水和油中。在压力的作用下，可以轻易的涂抹开释放被包裹的物质，被包裹的芯材可以是固体或者液体物质。解决了现有技术使用单一的熔融壳材制备的微胶囊，不能同时满足日化品对熔点、 硬度、高温稳定性、释放、肤感等特殊的技术要求。本发明所用原料为热熔原料，可用熔化分散冷凝法制作微胶囊，使用该方法制作微胶囊的时候具有不使用水和任何有机溶剂，低能耗环保、包裹速度快同时，囊壳能够有效避光避氧，具有很高的实用价值。
二、微胶囊壳材的应用
实施例19
表1、一种橙色微胶囊
成分 百分比 组分种类
鲸蜡硬脂醇和鲸蜡硬脂基葡糖苷 55％ 糖苷类乳化剂
PEG100硬脂酸酯 30％ 脂肪醇聚氧乙烯醚乳化剂
峰蜡 10％ 蜡
维生素A 2.5％ 脂溶性活性物
维生素E 2％ 脂溶性活性物
虾青素 0.5％ 脂溶性活性物天然颜料
合计 100％  
制备步骤包括：
1)将鲸蜡硬脂醇和鲸蜡硬脂基葡糖苷、PEG100硬脂酸酯单甘酯、在水浴中加热到70℃完全熔化，混合均匀；
2)向步骤1)所得混合物中加入维生素A、维生素E和虾青素并混合均匀；
3)将步骤2)所得熔化分散后的混合物用0.5毫米的锐孔滴入到进风温度为10℃，高度为6米的冷却塔中；
4)在冷却塔底部收集微胶囊。
通过上述步骤完成本实施例，操作者能够在冷却塔底部收集到直径为0.2-0.8毫米的橙色蜡球状微胶囊，该微胶囊在25℃水、啫喱或膏霜中吸水吸油膨胀直径增加1-2倍并软化，可以用手指轻易的涂开。
从上面的组合得到一个熔点高于50度，大约在55-65℃度的熔融组合物作为囊壳的。HLB值在
维生素A是调节糖蛋白合成的一种辅酶，对上皮细胞的细胞膜起稳定作用，维持上皮细胞的形态完整和功能健全维生素A缺乏会造成上皮组织干燥细胞角化。维生素E和虾青素都是抗氧化物抗衰老的活性物。但是这三个活性物都不稳定见光和热容易氧化。包裹 后隔绝氧和空气更加稳定，易于添加、在配方中微胶囊吸水溶胀易于涂抹开释放活性成分
实施例20
一种双层变色色素微胶囊
表3(内层色素芯的配方)
成分 百分比 组分
单甘酯 10％ 甘油酯类乳化剂
聚甘油10棕榈酸脂 20％ 聚甘油酯类乳化剂
1618醇 25％ 高级脂肪醇
肉豆蔻醇肉豆蔻酯 5％ 合成油脂
米糠蜡 5％ 天然蜡
氧化铁棕 30％ 无机色淀
维生素C棕榈酸酯 5％ 脂溶性活性物
合计 100％  
表4(外层色素壳配方)
成分 百分比 组分
单甘酯 10％ 甘油酯类乳化剂
聚甘油10棕榈酸脂 20％ 聚甘油酯类乳化剂
1618醇 25％ 高级脂肪醇
肉豆蔻醇肉豆蔻酯 5％ 合成油脂
米糠蜡 5％ 天然蜡
钛白粉 30％ 无机色淀
维生素C棕榈酸酯 5％ 脂溶性活性物
合计 100％  
一种变色色素微胶囊的制备方法，包括：
1)将单甘酯、聚甘油10棕榈酸脂、1618醇按表3和表4的比例加热至熔化，充分搅拌均匀；
2)分别将氧化铁色淀和钛白粉色淀微胶囊壳材中搅拌均匀；
3)将步骤2的表3氧化铁棕熔化分散液体喷雾到冷却空气中冷却空气中得到直径0.4-0.6毫米的球型微胶囊芯；
4)将步骤3得到的棕色微胶囊芯作为种芯投入到切向喷雾的流化床中，将步骤2的表4钛白粉熔化分散液体喷雾冷却到旋转流动的棕色微胶囊芯上。在棕色芯上包裹上了一层白色的壳。白色层的喷涂重量是棕色芯重量的3倍。最终得到白色直接0.8-1.2毫米的微胶囊。
该融熔微胶囊具有双层的结构、内芯是棕色外层是白色。色粉含量高达30％。在着哩和霜乳中膨胀，是白色的颗粒。但是在压力涂抹的时候，内层棕色和外层白色混合变成肤色。有很好的遮瑕效果。同时包裹的美白活性成分维生素C棕榈酸酯。该胶囊有物理遮瑕和美白的作用。混合物的熔点在55-65度，HLB值在6-9之间。
实施例21
表5、一种心型胶囊
成分 百分比 组分种类
聚甘油10棕榈酸脂 15％ 聚甘油类乳化剂
聚甘油-6聚蓖麻醇酸酯 20％ 聚甘油类乳化剂
22醇 10％ 高级脂肪醇
1618醇 10％ 高级脂肪醇
氢化荷荷巴油 40％ 油脂
水解角蛋白 2％ 水溶性活性物
首乌提取物 2％ 植物提取活性物
生姜精油 0.5％ 功能性芳香精油
山苍子精油 0.5％ 功能性芳香精油
番茄红素 适量 天然色素
合计 100％  
制备方法包括：
1)将微胶囊壳材聚甘油10棕榈酸脂、聚甘油-6聚蓖麻醇酸酯、22醇和1618醇、氢化荷荷巴油加热至熔化，充分搅拌均匀；
2)将芯材水解角蛋白粉、首乌提取物、生姜精油、山苍子精油、番茄红素加入到微胶囊壳材中搅拌均匀；
3)将步骤2)所得熔化分散的液体快速滴注到心型模具中。快速冷却成型，得到所需要直径大约3毫米厚度0.5毫米蜡块状微胶囊。
该配方熔点高于55度，HLB值在4-9之间。其中角蛋白护理头皮的作用。生姜精油 和首乌提取物有乌发生发的功效。该片状胶囊可以用于护发素、焗油膏中，既有漂亮的外观又有实际的功效。利用氢化荷荷巴油替代硅油的的调理顺滑功能。配方原料来源天然、生产过程无水、无溶剂、无防腐剂，符合日化产业绿色化学的新趋势。
三、微胶囊壳材的应用方法
1、一种微胶囊的制备方法，包括以下步骤：
1)将微胶囊壳材加热至熔化，充分搅拌均匀；
2)将芯材加入到微胶囊壳材中搅拌均匀；
3)将步骤2)所得熔化分散的液体在空气中冷却成型，得到所需要大小、规格、形状的微胶囊。
其中，所述冷却方法为将熔化分散后的液体注入模具内或在平面上冷却，得到模具形状或片状的包裹物。
所述冷却方法为将熔化分散的液体滴入或者喷入冷空气中，通过一定距离的落差得到不同规格球状的包裹微球。
所述芯材为水溶性活性物或脂溶性活性物。
所述水溶性的活性物为维生素B1、B3、B5、B12、茶多酚、植物提取物或植物粉末中的一种或多种。
所述脂溶性的活性物为维生素E、维生素A、Q10、胡萝卜素、虾青素、叶黄素、神经酰胺或植物鞘氨醇中的一种或多种。
2、本发明还提供另外一种微胶囊壳材的应用方法，制备步骤包括：
1)将微胶囊壳材加热至熔化，充分搅拌均匀；
2)将熔化的壳材溶液盘涂到被包裹的芯材上，冷却后制得微胶囊。
其中，所述芯材为晶体或固体颗粒。
采用本发明方法制备的微胶囊，其壳材熔点高于50℃，在室温保持固态没有融化变软析出液体油等迹象；在水中中又可以吸水膨胀而变软，又不溶解或崩解在水中。在压力的作用下，可以轻易的涂散并释放被包裹的物质，被包裹的芯材可以是固体或者液体物质，解决了现有技术普通微胶囊壳材其熔点、硬度、高温稳定性、释放条件不能同时满足熔化分散冷凝法制备微胶囊在日化品中使用的的技术问题。
最后需要说明的是，以上实施例仅用以说明本发明的技术方案而非限制技术方案，本领域的普通技术人员应当理解，那些对本发明的技术方案进行修改或者等同替换，而不脱离本技术方案的宗旨和范围，均应涵盖在本发明的权利要求范围当中。

Claims (33)

  1. 一种微胶囊壳材，其特征在于，所述壳材的熔点高于50℃，其在不同气候的温度下是固态；在水中可以吸水膨胀而变软，但不溶解或崩解在水中；在压力的作用下，可以轻易的涂抹开释放被包裹的物质，被包裹的芯材是固体或者液体物质。
  2. 根据权利要求1所述的微胶囊壳材，其特征在于，按重量百分含量计，其核心组分包括：高级脂肪醇或聚乙二醇为0-50％，油脂或蜡为10-60％，油增稠剂为0-20％，脂溶性色素或者无机色淀0-50％，余量为乳化剂。
  3. 根据权利要求2所述的微胶囊壳材，其特征在于，所述乳化剂为非离子型乳化剂、阴离子乳化剂、阳离子乳化剂或两性离子乳化剂；优选非离子型乳化剂。
  4. 根据权利要求2所述的微胶囊壳材，其特征在于，所述油脂或蜡是植物油酯和植物蜡、动物油脂、合成油脂和合成蜡、硅油和硅蜡。
  5. 根据权利要求2所述的微胶囊壳材，其特征在于，所述高级脂肪醇是指熔点大于30度的高碳醇；通常使用碳数大于14的高碳醇。
  6. 根据权利要求2所述的微胶囊壳材，其特征在于，所述聚乙二醇{PEG}是指分子量大于1000的凝固点高于25℃的固态聚乙二醇。
  7. 根据权利要求2所述的微胶囊壳材，其特征在于，所述油增稠剂是指溶解于油的高分子材料增稠剂或固体粉末类增稠剂。
  8. 根据权利要求2所述的微胶囊壳材中包裹的色素色淀，其特征在于，所述色素色淀指合成或天然的有机色素或有机色淀。
  9. 根据权利要求2所述的微胶囊壳材中的色素色淀，其特征在于，所述色淀是指无机色淀。
  10. 根据权利要求3所述的微胶囊壳材，其特征在于，所述乳化剂优选固态且熔点高于30℃的乳化剂。
  11. 根据权利要求3所述的微胶囊壳材，其特征在于，所述乳化剂的HLB值在3-13之间。
  12. 根据权利要求3所述的微胶囊壳材，其特征在于，所述非离子型乳化剂包括：醇类非离子型乳化剂、聚氧乙烯型非离子型乳化剂、含氮非离子乳化剂、嵌段聚醚型以及甾醇衍生的非离子乳化剂。
  13. 根据权利要求12所述的微胶囊壳材，其特征在于，所述醇类非离子型乳化剂包括：乙二醇酯类、甘油酯类、聚甘油脂肪酸酯、新戊基型多元醇脂类、糖酯类、山梨醇酯类、烷基糖苷型非离子型乳化剂中的一种或多种。
  14. 根据权利要求13所述的微胶囊壳材，其特征在于，所述乙二醇酯类是乙二醇和脂肪酸反应生成的非离子型乳化剂。
  15. 根据权利要求13所述的微胶囊壳材，其特征在于，所述甘油脂肪酸酯是甘油和脂肪酸反应生成的非离子型乳化剂为甘油单酯、双酯或三酯。
  16. 根据权利要求13所述的微胶囊壳材，其特征在于，所述聚甘油脂肪酸酯类乳化剂是由聚甘油与脂肪酸形成的多羟基酯类非离子型表面活性剂。
  17. 根据权利要求13所述的微胶囊壳材，其特征在于，所述新戊基型多元醇脂类非离子型乳化剂为季戊四醇脂酸酯。
  18. 根据权利要求13所述的微胶囊壳材，其特征在于，所述糖酯类乳化剂指由具有多个羟基葡萄糖、蔗糖与脂肪酸如月桂酸、硬脂酸、油酸、棕榈酸等酯化得到非离子乳化剂；糖酯由于酯化度不同，可分为单酯、双酯和三酯。
  19. 根据权利要求13所述的微胶囊壳材，其特征在于，所述山梨醇酯类为聚氧乙烯去水山梨醇的部分脂肪酸酯(吐温)类，以及失水山梨醇脂肪酸酯(司盘)类乳化剂。
  20. 根据权利要求13所述的微胶囊壳材，其特征在于，所述烷基糖苷类是指用葡萄糖和脂肪醇合成的烷基糖苷。
  21. 根据权利要求13所述的微胶囊壳材，其特征在于，所述聚氧乙烯型非离子型乳化剂包括：脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯脂、烷基苯酚聚氧乙烯醚、聚氧乙烯脂肪酸铵的一种或多种。
  22. 根据权利要求21所述的微胶囊壳材，其特征在于，所述脂肪醇聚氧乙烯醚是聚乙二醇(PEG)与脂肪醇通过环氧乙烷加成而得的醚类非离子型乳化剂，化学通式RO(CH2CH2O)nH。
  23. 根据权利要求21所述的微胶囊壳材，其特征在于，所述脂肪酸聚氧乙烯脂是脂肪酸与环氧乙烷的加成反应生成，其通式为RCOO(CH2CH2O)nH。
  24. 一种微胶囊的制备方法，其特征在于，采用权利要求2-23所述的微胶囊壳材组份，其制备步骤包括：
    1)将微胶囊壳材加热至熔化，充分搅拌均匀；
    2)将芯材加入到微胶囊壳材中搅拌均匀；所述芯材固体或者液体物质。
    3)将步骤2)所得熔化分散的液体在空气中冷却成型，得到所需要大小、规格、形状的微胶囊。
  25. 根据权利要求24所述的微胶囊的制备方法，其特征在于，所述冷却方法为将熔 化分散后的液体注入模具内、或者铺在平面上冷却，得到模具形状或片状的包裹物。
  26. 根据权利要求24所述的微胶囊的制备方法，其特征在于，所述冷却方法为将熔化分散的液体滴入或者喷入冷空气中，通过一定距离的落差的空气冷却得到不同规格球状的包裹微球。
  27. 根据权利要求24所述微胶囊的制备方法，其特征在于，所述芯材为水溶性活性物、脂溶性活性物或不溶性物质。
  28. 根据权利要求27所述的微胶囊的制备方法，其特征在于，所述水溶性的活性物为维生素B1、B3、B5、B12、维生素C及其衍生物、乙基抗坏血酸、茶多酚、肽、氨基酸、植物提取物中的一种或多种。
  29. 根据权利要求27所述的微胶囊的制备方法，其特征在于，所述脂溶性的活性物为维生素E、维生素E醋酸酯、维生素A、维生素A棕榈酸脂、维生素C棕榈酸酯、Q10、胡萝卜素、虾青素、叶黄素、神经酰胺、植物鞘氨醇中的一种或多种。
  30. 根据权利要求27所述的微胶囊的制备方法，其特征在于，所述脂溶性的活性物为植物提取精油或香精。
  31. 根据权利要求27所述的微胶囊的制备方法，其特征在于，所述不溶性物质是指在水和油中都不溶解的的活性物包括矿物质、益生菌、植物动物原粉、蛋白质等。
  32. 一种微胶囊的制备方法，其特征在于，采用权利要求2-24任一所述的微胶囊壳材组份，其制备包括如下步骤：
    1)将微胶囊壳材加热至熔化，充分搅拌均匀；
    2)将熔化的壳材溶液盘涂到被包裹的芯材上，冷却后制得微胶囊。
  33. 根据权利要求32所述微胶囊的制备方法，其特征在于，所述芯材为晶体或固体颗粒。
PCT/CN2022/116047 2022-08-29 2022-08-31 一种微胶囊壳材及微胶囊制备方法 WO2024045003A1 (zh)

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