WO2023006012A1 - 一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊及其制备与应用 - Google Patents

一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊及其制备与应用 Download PDF

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WO2023006012A1
WO2023006012A1 PCT/CN2022/108472 CN2022108472W WO2023006012A1 WO 2023006012 A1 WO2023006012 A1 WO 2023006012A1 CN 2022108472 W CN2022108472 W CN 2022108472W WO 2023006012 A1 WO2023006012 A1 WO 2023006012A1
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lignosulfonate
catechol
sunscreen
colored
microcapsules
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French (fr)
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钱勇
邱学青
杨东杰
楼宏铭
欧阳新平
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South China University of Technology SCUT
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South China University of Technology SCUT
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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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • 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
    • A61K8/37—Esters of carboxylic acids
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • 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
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • 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
    • A61P17/04—Antipruritics
    • 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
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/592—Mixtures of compounds complementing their respective functions

Definitions

  • the invention belongs to the field of fine chemicals, and in particular relates to a light-colored catechol lignosulfonate sunscreen microcapsule and its preparation and application.
  • ultraviolet radiation the light radiation with a wavelength between 10 and 400 nm is called ultraviolet radiation.
  • ultraviolet radiation can be divided into UVA band (320-400nm), UVB band (290-320nm), UVC band (200-290nm), EUV (10-100 nm). Prolonged exposure to UV radiation can cause sunburn, aging and even skin cancer. EUV and UVC have been absorbed by the ozone layer at high altitudes, while 1% to 10% of UVB and more than 90% of UVA can still pass through the atmosphere and reach the earth's surface. The penetrating performance of ultraviolet rays in the UVB band is weak. When it is irradiated on the human body, most of it is absorbed by the epidermal cells of the human body.
  • UVB band due to the relatively high energy of ultraviolet rays in the UVB band, it will cause photodamage to the skin and make the skin appear red. , The phenomenon of blisters. If exposed for a long time, it will also cause skin inflammation, aging and other adverse reactions, and in severe cases, it will also cause skin cancer.
  • Ultraviolet rays in the UVA band have strong penetrating properties and can reach the deep dermis of the human body, which in turn will lead to the deposition of melanin in the human body. After long-term accumulation, the skin of the human body will be aged and damaged.
  • ROS Reactive oxygen species
  • protective agents can be divided into two categories, namely physical sunscreens and chemical sunscreens.
  • Physical sunscreens are relatively thick, have a poor sense of use, and are prone to photocatalytic reactions. Therefore, more chemical sunscreens are used on the market.
  • the commonly used chemical sunscreen additives on the market include benzophenone-3, xylene, avobenzone, and cinnamate.
  • it will be absorbed by the skin, further penetrate the stratum corneum, or enter the epidermal cells through the follicles, causing allergic reactions and even damaging DNA.
  • lignin ranks second among natural polymers in nature, and is also the highest content of natural polymers containing benzene rings. It protects the inner tissues of plants from damage caused by ultraviolet light. This is because after ultraviolet rays irradiate plants, lignin in plants produces phenylpropane conjugates, which can effectively shield ultraviolet rays. Lignin contains a large number of structures such as phenolic hydroxyl groups, benzene rings, carbonyl groups, and methoxyl groups, which can effectively absorb ultraviolet rays, and can also scavenge free radicals to play an antioxidant role (Industrial crops and products, 2011, 33, 259-276).
  • lignin/sunscreen agent composite nanocapsules were prepared by wrapping avobenzone and cinnamon with lignin, and the ratio of lignin and sunscreen was adjusted to strengthen the synergistic effect of lignin and sunscreen. Adding 10 wt% lignin The SPF value of the sunscreen mixed with the blank hand cream can reach up to 408, and it can show good UV protection performance within 8 hours (ACS Applied Bio Materials, 2018, 1, 1276).
  • Nanoscale lignin capsules provide a new direction for the development of natural high-efficiency sunscreens because of their excellent and long-lasting UV protection properties.
  • the particle size of lignin microcapsules is relatively small and has almost no bioadhesion, so there is still a hidden danger of skin penetration. Therefore, it is necessary to modify lignin to increase the content of phenolic hydroxyl groups in lignin, thereby enhancing the bioadhesion ability of lignin and lignin microcapsules, and improving the safety of sodium lignosulfonate for UV protection. performance and performance.
  • the preparation of existing lignin-based sunscreens mainly uses alkali lignin and enzymatic lignin as raw materials.
  • the color of these two types of lignin is relatively dark. It has a lighter color than enzymatic lignin, but because lignin sulfonate itself is easy to cause demulsification of the cream body, the stability of the prepared sunscreen is worse than that of general lignin sunscreen, thus limiting its use.
  • lignosulfonate itself has a low content of phenolic hydroxyl groups, so its free radical scavenging ability is poor, and its absorption ability in the ultraviolet region is limited.
  • the primary purpose of the present invention is to provide a method for preparing light-colored catechol lignosulfonate sunscreen microcapsules.
  • Lignin molecules contain many methoxy groups, which can be modified by vulcanization method to convert the potential methoxy groups in lignosulfonate into hydroxyl groups through nucleophilic substitution reaction with SO 3 2- .
  • the vulcanization process has been improved, and the reaction conditions are relatively milder, so that the molecular weight will not decrease significantly during the vulcanization process, which proves that the molecular structure of lignosulfonate itself has not suffered obvious damage. destroy.
  • Another object of the present invention is to provide a light-colored catechol lignosulfonate sunscreen microcapsule prepared by the above method.
  • Another object of the present invention is to provide the application of the light-colored catechol lignosulfonate sunscreen microcapsules.
  • a method for preparing light-colored catechol lignosulfonate sunscreen microcapsules comprising the following steps:
  • the weight ratio of lignosulfonate to vulcanizing agent in step (1) is 1-10:0.2-2; more preferably 10:0.7-2; most preferably 8:1-5:1.
  • the vulcanizing agent in step (1) is at least one of sulfite, pyrosulfite, thiosulfate and bisulfite.
  • the lignosulfonate in step (1) is at least one of sodium lignosulfonate, magnesium lignosulfonate and calcium lignosulfonate.
  • the lignin in the lignosulfonate is bamboo pulp lignosulfonate, wheat straw pulp lignosulfonate, reed lignosulfonate, bagasse pulp lignosulfonate, asparagus At least one of pulp lignosulfonate and cotton pulp lignosulfonate.
  • Enzymatic lignin is a type of lignin obtained by depolymerizing and dissolving lignin raw materials by using cellulase and hemicellulose.
  • Alkali lignin mainly comes from alkaline pulping waste liquor such as sulfate method, alkane-alkali method, etc.
  • 3Organic solvent lignin Organic solvent lignin is produced by organic reagents such as methanol, ethanol, acetone, etc.
  • Lignosulfonate Lignosulfonate comes from sulfite pulping waste liquor, which has good water solubility and broad application prospects.
  • the alkaline solution in step (1) is 1-20wt% sodium hydroxide solution, more preferably 1.5-15wt% sodium hydroxide solution, most preferably 5-15wt% sodium hydroxide solution;
  • the weight ratio of lignosulfonate to alkali solution is 1-10:30.
  • the temperature of the reaction in step (1) is 70-140° C., and the time is 1-2.5 hours.
  • the time for the dialysis treatment in step (1) is 2-8 days, more preferably 4-6 days, and the dialysate is water.
  • the pH range of the solution obtained after dissolving the catechol lignosulfonate in the aqueous solution in step (2) should be 6-8.
  • the sunscreen in step (2) is at least one of UVA and UVB sunscreens; more preferably avobenzone, ethylhexyl methoxycinnamate, homosalate and oxybenzone At least one of them; when there are more than one sunscreens, they need to have good mutual solubility.
  • the surfactant in step (2) is at least one of Tween, alkyl polyglycosides and sucrose esters.
  • the power of the ultrasonic cavitation in step (2) is 200-1500 W, and the time is 1-20 min; more preferably, the ultrasonic cavitation is performed at 400-1000 W for 3-10 min.
  • the catechol lignosulfonate/chemical sunscreen agent microcapsule emulsion in step (2) can remove excess catechol lignosulfonate by centrifugal washing to obtain catechol lignosulfonate salt/chemical sunscreen microcapsules.
  • the centrifugation speed is 5000-15000 r/min, and the centrifugation washing time is 20-40 min.
  • the invention provides a light-colored catechol lignosulfonate sunscreen microcapsule prepared by the above method.
  • the light-colored catechol lignosulfonate sunscreen microcapsules of the present invention have an amphiphilic spherical structure, a particle size of 100-1000 nm, excellent ultraviolet absorption performance, good stability, and excellent water resistance and anti-penetration performance .
  • the invention provides the application of the light-colored catechol lignosulfonate sunscreen microcapsules in the chemical sunscreen field.
  • the chemical sunscreen does not take living organisms as sunscreen objects.
  • Lignin is a natural macromolecule UV protection agent in plants, which has good UV absorption and anti-oxidation functions, and also has good biocompatibility.
  • the delignified lignin after chemical modification contains more phenolic hydroxyl groups, and cross-linking reaction is more likely to occur when the chemical sunscreen is embedded in ultrasonic cavitation, and the added surfactant is beneficial to the oil-phase dispersion preparation of microparticles.
  • the size of the capsule will reach the nanometer level, which can strengthen the ultraviolet scattering effect.
  • the structure of catechol, resorcinol and other structures distributed on the surface of bioadhesive microcapsules of catechol lignosulfonate/chemical sunscreen endows the microcapsules with good water resistance and impermeability , improve efficiency and safety.
  • the preparation process of bioadhesive microcapsules of catechol lignosulfonate/chemical sunscreen is green and environmentally friendly, and the product is safe and efficient. It promotes the application of renewable resource lignin in the field of daily chemicals, and also solves the problem of lignosulfonate Insufficient cross-linking ability and other problems have broad application prospects.
  • the present invention has the following advantages and beneficial effects:
  • Lignosulfonate has good anti-ultraviolet and anti-oxidation properties and good biocompatibility. After chemical modification, there are many active sites of phenolic hydroxyl groups in the molecule, which can make use of free radical crosslinking in the process of ultrasonic cavitation , can effectively embed small-molecule chemical sunscreens in synergy with sun protection, improve the anti-photolysis performance of small-molecule chemical sunscreens, and achieve long-lasting sun protection.
  • the lignosulfonate demethylation process is green and environmentally friendly. The whole reaction is carried out in the water phase without using organic solvents. The reaction process is safe and environmentally friendly, and the reaction process is simple, easy to achieve large-scale preparation, and has good industrialization prospect.
  • reaction conditions used in this paper are milder and the preparation cost is lower.
  • the sulfide reagents used are all inorganic sulfides, which are more environmentally friendly and can realize wood The removal of the methyl group in the sulfonate effectively promoted the construction of the catechol-type lignosulfonate.
  • Bioadhesive microcapsules of catechol lignosulfonate/chemical sunscreen The structures of catechol and resorcinol distributed on the surface of the microcapsules endow the microcapsules with good adhesion and impermeability. Improve the efficiency and safety of use, solve the problems of poor water resistance of traditional sunscreens, easy penetration into the skin and harm the human body, etc., and achieve safe and efficient sun protection and skin care.
  • Fig. 1 is the bioadhesive microcapsule emulsion of catechol lignosulfonate/chemical sunscreen obtained by ultrasonic cavitation in step (2) of Example 1.
  • Figure 2 is a picture of the original sodium lignosulfonate (left) and catechol sodium lignosulfonate (right) prepared in Example 1 when they were tested for folinol.
  • Fig. 3 is the UV of the bioadhesive microcapsule sunscreen of catechol lignosulfonate/chemical sunscreen and lignosulfonate/chemical sunscreen microcapsule sunscreen of the obtained catechol lignosulfonate/chemical sunscreen in the range of 260 ⁇ 400nm Spectrum.
  • Fig. 4 is the laser confocal test figure of the bioadhesive microcapsule sunscreen of catechol lignosulfonate/chemical sunscreen and sodium lignosulfonate/chemical sunscreen microcapsule sunscreen of the obtained catechol lignosulfonate/chemical sunscreen .
  • Fig. 5 is the particle size test related data of the catechol lignosulfonate/chemical sunscreen agent bioadhesive microcapsules and sodium lignosulfonate/chemical sunscreen agent microcapsules obtained in Example 1.
  • Fig. 6 is the ultrasonic cavitation emulsion of catechol lignosulfonate obtained in Comparative Example 1.
  • microcapsules were mixed with a blank cream without sunscreen active ingredients (Nivea Deep Moisturizing Hand Cream, Nivea (Shanghai) Co., Ltd.) according to the mass ratio of 1:9 to prepare catechol lignosulfonate/ Bioadhesive microencapsulated sunscreens of chemical sunscreens.
  • Figure 1 is the ultrasonic cavitation emulsion of catechol lignosulfonate/chemical sunscreen prepared in step (2). It can be seen that the ultrasonic cavitation emulsion obtained after demethylation has good stability.
  • Figure 2 is a picture of the original sodium lignosulfonate and catechol lignosulfonate in step (1) when it was tested for folinol.
  • the absorption value of the original sodium lignosulfonate at 760nm on the left is 0.216, and the absorption value of the modified sodium lignosulfonate at 760nm has reached 0.3739, and the phenolic hydroxyl content has increased from the original 0.631mmol/g to 1.234 mmol/g, an increase of 95.5%.
  • the sodium lignosulfonate test solution after the demethylation reaction has a darker color, which also shows that the content of phenolic hydroxyl groups has increased.
  • Fig. 3 is the bioadhesive microcapsule sunscreen of the obtained catechol lignosulfonate/chemical sunscreen of the present embodiment 1 measured by the Shimadzu UV-2600 ultraviolet-visible spectrophotometer and the embodiment
  • step 1 catechol lignosulfonate is replaced by sodium lignosulfonate, the ultraviolet spectrum of the sodium lignosulfonate/chemical sunscreen agent microcapsule sunscreen in the range of 290-400nm can be seen from the figure It was found that the UV transmittance of the bioadhesive microcapsule sunscreen of catechol lignosulfonate/chemical sunscreen agent was significantly lower than that of sodium lignosulfonate/chemical sunscreen agent microcapsule sunscreen, It shows that it can block more ultraviolet rays.
  • the SPF value of catechol lignosulfonate/chemical sunscreen bioadhesive microcapsule sunscreen is 116, while sodium lignosulfonate/chemical sunscreen microcapsule sunscreen
  • the cream has an SPF of just 39.
  • Fig. 4 is the laser confocal test figure of the bioadhesive microcapsule sunscreen of catechol lignosulfonate/chemical sunscreen and sodium lignosulfonate/chemical sunscreen microcapsule sunscreen of the obtained catechol lignosulfonate/chemical sunscreen .
  • the adhesion properties of catechol lignosulfonate/chemical sunscreen bioadhesive microcapsule sunscreen and sodium lignosulfonate/chemical sunscreen microcapsule sunscreen to the skin were tested by laser confocal microscopy.
  • the blue fluorescence signal of surface lignin is weak, which proves that the microcapsules sticking to the skin surface are washed away, and the bioadhesive microcapsule sunscreen of catechol lignosulfonate/chemical sunscreen can be washed away Afterwards, the strong fluorescent signal was still maintained, which proved that the surface phenolic hydroxyl groups of sodium lignosulfonate after demethylation increased significantly compared with the original sodium lignosulfonate, and the adhesion performance was significantly improved.
  • Fig. 5 is the relevant data of the particle size test of the bioadhesive microcapsules of catechol lignosulfonate/chemical sunscreen obtained in Example 1 tested by a Malvern laser particle size analyzer.
  • the size of microcapsules has a great influence on its storage stability at room temperature, and the larger the particle size, the more difficult it is to store.
  • the average particle size of the bioadhesive microcapsules of catechol lignosulfonate/chemical sunscreen agent is about 300nm, while the median particle size of sodium lignosulfonate/chemical sunscreen agent microcapsules
  • the particle size is 350nm, and the particle size distribution of bioadhesive microcapsules of catechol lignosulfonate/chemical sunscreen is also narrower, which proves that the product uniformity obtained after demethylation treatment is better. Therefore, the preparation method of the present invention can significantly improve the storage time and stability of the microcapsules.
  • microcapsules were mixed with a blank cream without sunscreen active ingredients (Nivea Deep Moisturizing Hand Cream, Nivea (Shanghai) Co., Ltd.) according to the mass ratio of 1:9 to prepare catechol lignosulfonate/ Bioadhesive microencapsulated sunscreens of chemical sunscreens.
  • Example 1 The same microcapsule preparation process, ultraviolet-visible light spectrum analysis, laser confocal test, and particle size test were used as in Example 1. The results are basically the same as those in Figure 1, Figure 2, Figure 3, Figure 4, and Figure 5, respectively.
  • microcapsules were mixed with a blank cream without sunscreen active ingredients (Nivea Deep Moisturizing Hand Cream, Nivea (Shanghai) Co., Ltd.) according to the mass ratio of 1:9 to prepare catechol lignosulfonate/ Bioadhesive microencapsulated sunscreens of chemical sunscreens.
  • Example 1 The same microcapsule preparation process, ultraviolet-visible light spectrum analysis, laser confocal test, and particle size test were used as in Example 1. The results are basically the same as those in Figure 1, Figure 2, Figure 3, Figure 4, and Figure 5, respectively.
  • microcapsules were mixed with a blank cream without sunscreen active ingredients (Nivea Deep Moisturizing Hand Cream, Nivea (Shanghai) Co., Ltd.) in a mass ratio of 1:9 to prepare catechol lignosulfonate / Bioadhesive microencapsulated sunscreens of chemical sunscreens.
  • Example 1 The same microcapsule preparation process, ultraviolet-visible light spectrum analysis, laser confocal test, and particle size test were used as in Example 1. The results are basically the same as those in Figure 1, Figure 2, Figure 3, Figure 4, and Figure 5, respectively.
  • Fig. 6 is the ultrasonic cavitation emulsion of catechol lignosulfonate obtained in this comparative example. It can be seen from the figure that the resulting ultrasonic cavitation emulsion has a very obvious layering phenomenon. This is because an appropriate amount of surfactant will reduce the interfacial tension of water and oil, increase the specific surface area of oil droplets, and help the adsorption and crosslinking of sodium lignosulfonate on the surface of oil droplets. However, the addition of excessive surfactants will cause the excess surfactants to interact with themselves, resulting in droplet aggregation, so that the prepared microcapsules are too large in size, unstable and then demulsified.
  • microcapsules are prepared by adding chemical sunscreens and surfactants in the subsequent sequence, it is basically impossible to prepare microcapsules or the prepared microcapsules are very easy to break. It is also further explained that the demethylation treatment by the vulcanization method has significantly improved the stability of the modified lignosulfonate in the preparation of microcapsules. .

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Abstract

本发明公开了一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊及其制备与应用。本发明采用硫化法对木质素磺酸盐进行改性制备邻苯二酚木质素磺酸盐，再将邻苯二酚木质素磺酸盐与防晒剂、表面活性剂进行超声空化制备邻苯二酚木质素磺酸盐/化学防晒剂微胶囊乳液。本发明所述木质素/化学防晒剂微胶囊的制备过程绿色环保，成本低廉而且紫外吸收性能优异，相比于其他木质素基防晒剂颜色更浅，生物粘附性和抗渗透性能良好，解决传统防晒剂耐水性差、制备工艺污染较大、易渗入皮肤伤害人体等问题。

Description

一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊及其制备与应用 技术领域
本发明属于精细化学品领域，具体涉及一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊及其制备与应用。
 背景技术
国际上将波长在10～400nm之间的光照辐射叫做紫外线辐射。按照国际惯例紫外辐射可分为为UVA波段（320～400nm）、UVB波段(290～320nm)、UVC波段(200～290nm)、EUV（10-100 nm）。长时间暴露在紫外辐射下会导致皮肤晒伤、老化甚至会引起皮肤癌。EUV和UVC在高空中就已被臭氧层吸收，而1%～10%的UVB和大约90%以上的UVA仍然能够穿过大气层到达地球表面。UVB波段的紫外线的穿透性能较弱，照射到人体上时，多数都被人体的表皮细胞所吸收，但由于UVB段的紫外线能量相对较高，会对皮肤造成光损伤，使得皮肤出现泛红、水泡的现象。如果长时间的照射，还会导致皮肤出现炎症，老化等不良反应，严重者还会引起皮肤癌。UVA波段的紫外线具有很强的穿透性能，可以到达人体的真皮深处，进而会导致人体内的黑色素沉积，经过长期的累积会使得人体的皮肤老化和受损。UVA和UVB辐射诱导产生的活性氧簇（ROS）可损伤多种细胞成分，并诱导免疫抑制细胞因子的形成（The FASEB Journal, 2018, 32(7): 3700-3706）。所以，使用紫外防护剂来避免紫外线伤害是有必要的。
根据防护机理的不同，可以将防护剂分为两大类，分别为物理防晒剂和化学防晒剂。物理防晒剂相对来说比较厚重，使用感较差，同时容易发生光催化反应。因此市面上用到较多的是化学防晒剂，市面上常用的化学防晒添加物有二苯甲酮-3，二甲苯、阿伏苯宗、桂皮酸盐等。但是由于小分子反应之后会被皮肤吸收，进一步透过角质层，或者通过滤泡进入到表皮细胞，进而引起过敏反应甚至破坏DNA。且在紫外辐射下，即使少量化学、物理防晒剂渗入皮肤，也会生成活性氧簇（ROS）导致细胞和组织损伤，并且最终导致系列皮肤与系统疾病(Advanced Functional Materials,2018,28,1802127)。小分子防晒剂的渗透问题引起了人们的密切关注，Deng等利用具有生物粘附性能的醛基超支化聚缩水甘油醚作为壁材，包裹小分子防晒剂形成微胶囊，有效地阻止了防晒剂渗透问题（Nature Materials,2015,14,1278）。但是其抗紫外性能有限，且难以满足恶劣环境的使用条件。
自然界拥有储量丰富的的木质素，木质素在自然界中天然高分子化合物中含量位居第二，也是含量最高的含有苯环的天然高分子聚合物。它能够保护植物内部的组织免收紫外光照射的伤害。这是由于紫外线在照射植物后，植物中的木质素产生了苯丙烷偶联物，能够有效的屏蔽紫外线。木质素含有大量的酚羟基、苯环、羰基、甲氧基等结构，这些结构能够有效的吸收紫外线，并且还能够清除自由基起到抗氧化性的作用（Industrial crops and products,2011,33,259-276）。
虽然木质素自身防晒性能有限，但是与化学防晒剂存在协同效应，能够有效提升商品防晒霜的防晒性能，同时还能够提升化学防晒剂的抗光解性能（Green Chemistry, 2015, 17: 320-324）。因此，使用木质素包裹阿伏苯宗、桂皮酸盐来制备木质素/防晒剂复合纳米胶囊，并调控木质素与防晒剂比例，以强化木质素与防晒剂的协同效应，添加10 wt%木质素与空白护手霜混合得到的防晒霜SPF值最高可达到408，并且在8小时内都能呈现出良好的紫外防护性能 (ACS Applied Bio Materials,2018,1,1276)。
纳米级木质素胶囊因其优异、长效的紫外防护性能为天然高效防晒霜的开发提供了新的方向。但是木质素微胶囊的粒径相对较小而且几乎没有生物粘附性，所以仍然有着皮肤渗透的隐患。因此，需要通过对木质素进行改性，以增加木质素中的酚羟基含量，进而增强木质素以及木质素微胶囊的生物粘附能力，提升了木质素磺酸钠用于紫外防护剂的安全性和使用性能。
现有的木质素基防晒霜的制备主要是使用碱木质素以及酶解木质素作为原料，这两种木质素的颜色相对来说都比较深，木质素磺酸盐虽然相较于碱木质素和酶解木质素有着更浅的颜色，但是由于木质素磺酸盐自身容易导致霜体出现破乳的现象，从而使得所制备的防晒剂稳定性差于一般的木质素防晒剂，因而限制了其在防晒领域中的应用。另外木质素磺酸盐自身酚羟基含量较低，因而自由基清除能力较差，且在紫外区域的吸收能力有限。
 技术问题
为解决现有技术的缺点和不足之处，本发明的首要目的在于提供一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊的制备方法。
木质素分子中含有许多甲氧基基团，使用硫化法进行改性，能够将木质素磺酸盐中潜在的甲氧基与SO 3 2-发生亲核取代反应从而转变为羟基。本工艺中对硫化法的工艺进行了改进，反应的条件相对更加温和，使得在进行硫化法处理时，分子量不会出现明显的下降，证明木质素磺酸盐自身的分子结构并没有遭受明显的破坏。脱甲基处理后木质素磺酸盐中的酚羟基含量出现了明显的提升，使得木质素自身结构中出现了邻苯二酚和间苯二酚的结构，提高木质素磺酸盐的生物粘附能力，从而可以弥补木质素磺酸盐与霜体相容性较差的问题，因而能够形成稳定的木质素微胶囊，提升了木质素磺酸盐在紫外防护剂领域的应用可能性。采用本工艺进行脱甲基处理，反应在全水相体系中进行，反应过程相对来说更加环保和绿色，反应成本更加低廉，后续如果进行工业化生产有着更好的应用潜能。
本发明的另一目的在于提供上述方法制得的一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊。
本发明的再一目的在于提供上述一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊的应用。
 技术解决方案
本发明目的通过以下技术方案实现：
一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊的制备方法，包括以下步骤：
（1）将木质素磺酸盐与硫化试剂溶于碱溶液中，于40～160℃反应0.1～5小时，透析处理，浓缩和干燥，得到邻苯二酚木质素磺酸盐；
（2）将邻苯二酚木质素磺酸盐溶于pH=5～9的水溶液中，加入防晒剂和表面活性剂，超声空化，得到邻苯二酚木质素磺酸盐/化学防晒剂微胶囊乳液，离心后得到浅色化邻苯二酚木质素磺酸盐防晒微胶囊。
优选的，步骤（1）所述木质素磺酸盐与硫化试剂的重量比为1～10：0.2～2；更优选为10：0.7～2；最优选为8:1～5:1。
优选的，步骤（1）所述硫化试剂为亚硫酸盐、焦亚硫酸盐、硫代硫酸盐和亚硫酸氢盐中的至少一种。
优选的，步骤（1）所述木质素磺酸盐为木质素磺酸钠、木质素磺酸镁和木质素磺酸钙中的至少一种。
更优选的，所述木质素磺酸盐中的木质素为竹浆木质素磺酸盐、麦草浆木质素磺酸盐、芦苇木质素磺酸盐、蔗渣浆木质素磺酸盐、龙须草浆木质素磺酸盐和棉浆粕木质素磺酸盐中的至少一种。
在工业上使用不同的处理方式进行处理和分离所得到的木质素一般称为工业木质素。通常根据木质素的处理和分离方式的不同来进行划分和命名。不同的木质素在结构、活性官能团含量和种类上都有着很大的区别。工业木质素主要可以分为四个大类：①酶解木质素：酶解木质素是使用纤维素酶、半纤维素对木质素原料进行解聚和溶解处理后得到的一类木质素、②碱木质素：碱木质素主要来自于硫酸盐法、烷碱法等碱法制浆废液、③有机溶剂木质素：有机溶剂木质素是在高温环境下通过有机试剂例如甲醇、乙醇、丙酮等将植物中的木质素提取出来的一类木质素、④木质素磺酸盐：木质素磺酸盐来自于亚硫酸盐制浆废液，其具有很好的水溶性和广泛的应用前景。
优选的，步骤（1）所述碱溶液为1～20wt%的氢氧化钠溶液，更优选为1.5～15wt%的氢氧化钠溶液，最优选为5～15wt%的氢氧化钠溶液；所述木质素磺酸盐与碱溶液的重量比为1～10：30。
优选的，步骤（1）所述反应的温度为70～140℃，时间为1～2.5h。
优选的，步骤（1）所述透析处理的时间为2～8天，更优选为4～6天，透析液为水。
优选的，步骤（2）所述邻苯二酚木质素磺酸盐溶于pH=5～9的水溶液后所得溶液总重量与防晒剂重量比为1:1～10:1；更优选为1:1～4:1，最优选为7：3。
优选的，步骤（2）所述表面活性剂的添加量占邻苯二酚木质素磺酸盐、pH=5～9的水溶液与防晒剂总重量的1～10wt%；更优选为3～10 wt %。
优选的，步骤（2）所述邻苯二酚木质素磺酸盐与pH=5～9的水溶液的重量比为1～10：20～100；更优选为1：10～33。
优选的，步骤（2）所述邻苯二酚木质素磺酸盐溶于水溶液后所得溶液的pH范围应该在6～8。
优选的，步骤（2）所述防晒剂为UVA 和UVB型防晒剂中的至少一种；更优选为阿伏苯宗、甲氧基肉桂酸乙基己酯、胡莫柳酯和氧苯酮中的至少一种；所述防晒剂超过一种时，则需要其有良好的互溶性。
优选的，步骤（2）所述表面活性剂为吐温、烷基多苷和蔗糖酯中的至少一种。
优选的，步骤（2）所述超声空化的功率为200～1500 W，时间为1～20 min；更优选为400～1000W下超声空化3～10 min。
优选的，步骤（2）所述邻苯二酚木质素磺酸盐/化学防晒剂微胶囊乳液可通过离心水洗除去多余的邻苯二酚木质素磺酸盐，得到邻苯二酚木质素磺酸盐/化学防晒剂微胶囊。
更优选的，所述离心的速率为5000～15000 r/min，离心水洗的时间为20～40 min。
本发明提供上述方法制备得到的一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊。
本发明的浅色化邻苯二酚木质素磺酸盐防晒微胶囊为两亲球形结构，粒径100-1000 nm，紫外吸收性能优异，稳定性良好，同时具有优异的耐水性和防渗透性能。
本发明提供上述一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊在化学防晒领域中的应用。所述化学防晒不以生命体为防晒对象。
更优选在防晒品制备中的应用。
木质素是植物中天然大分子紫外防护剂，均有良好的紫外吸收和抗氧化功能，同时也具有良好的生物相容性。进行化学改性之后的脱甲基木质素含有更多的酚羟基，在超声空化包埋化学防晒剂时，更容易发生交联反应，而加入的表面活性剂有利于油相分散制备的微胶囊尺寸将至纳米级，可以强化紫外散射效应。在此基础上，邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊表面分布的邻苯二酚、间苯二酚等结构赋予微胶囊良好的耐水性和抗渗透性能，提升使用效率和安全性。邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊制备工艺绿色环保，产品安全高效推动了可再生资源木质素在日化领域的应用，也解决了木质素磺酸盐交联能力不足等问题，有广阔的应用前景。
 有益效果
与现有技术相比，本发明具有以下优点及有益效果：
（1）木质素磺酸盐，具有良好的抗紫外抗氧化性能，生物相容性良好，进行化学改性之后分子中酚羟基活性位点众多，有利用超声空化过程中的自由基交联，可以有效包埋小分子化学防晒剂协同防晒，提升小分子化学防晒剂抗光解性能，实现持久防晒。
（2）木质素磺酸盐脱甲基过程绿色环保，反应全程均在水相中进行，未使用有机溶剂，反应过程安全环保，且反应的流程简单，易实现大批量制备，有着良好的工业化前景。
（3）相比于以往的硫化脱甲基方法，本文使用的反应条件更加温和，制备成本更加低廉，使用的硫化试剂均为无机硫化物，更加绿色环保，在更低成本下就能实现木质素磺酸盐中甲基的去除，有效的促进了邻苯二酚型木质素磺酸盐的构建。
（4）邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊表面分布的邻苯二酚、间苯二酚等结构赋予微胶囊良好的粘附性能和抗渗透性能，提升使用效率和安全性，解决传统防晒剂耐水性差、易渗入皮肤伤害人体等问题，实现安全、高效防晒护肤。
 附图说明
图1为是实施例1步骤（2）超声空化所得邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊乳液。
图2是原始的木质素磺酸钠（左）以及实施例1制得的邻苯二酚木质素磺酸钠（右）进行福林酚测试时的图片。
图3是实施例1所得邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜和木质素磺酸盐/化学防晒剂微胶囊防晒霜在260～400nm范围的紫外光谱图。
图4是实施例1所得的邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜和木质素磺酸钠/化学防晒剂微胶囊防晒霜的激光共聚焦测试图。
图5是实施例1所得的邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊和木质素磺酸钠/化学防晒剂微胶囊的粒径测试相关数据。
图6是对比例1所得的邻苯二酚木质素磺酸盐超声空化乳液。
 本发明的实施方式
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
本发明实施例中未注明具体条件者，按照常规条件或者制造商建议的条件进行。所用未注明生产厂商者的原料、试剂等，均为可以通过市售购买获得的常规产品。
实施例1
（1）将10g木质素磺酸钠和1.5g亚硫酸钠溶于30ml、10wt%NaOH溶液中，90℃进行冷凝回流反应1小时，反应结束后冷却至室温，将反应液在纯水中进行透析提纯处理，透析结束后将样品溶液进行浓缩干燥得到邻苯二酚木质素磺酸盐固体粉末。
（2）将0.21g邻苯二酚木质素磺酸盐溶解于6.79g超纯水中，制备得到5wt%的溶液，加入3g甲氧基肉桂酸乙基己酯与阿伏苯宗（质量比为4:1）的混合物和0.7g吐温，在超声功率为400W状态下超声空化3min，得到邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊乳液，10000 r/min离心30min，得到邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊。将该微胶囊与没有防晒活性成分的空白乳霜（妮维雅深层滋润护手霜，妮维雅（上海）有限公司）按照质量比1:9的配比混合制得邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜。
图1是步骤（2）制备得到的邻苯二酚木质素磺酸盐/化学防晒剂的超声空化乳液。可以看到脱甲基后得到的超声空化乳液有着良好的稳定性。
图2是原始木质素磺酸钠以及步骤（1）中邻苯二酚木质素磺酸盐进行福林酚测试时的图片。左侧原始木质素磺酸钠在760nm处的吸收值为0.216，经过改性后的木质素磺酸钠在760nm处的吸收值达到了0.3739，酚羟基含量由原始的0.631mmol/g增加到了1.234mmol/g，提升了95.5%，从图中也可以看到进行脱甲基反应后的木质素磺酸钠测试溶液颜色更深，也可以说明其中酚羟基含量出现了提升。
图3是通过日本岛津UV-2600紫外-可见分光光度计测得的本实施例1所得邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜和将实施例1步骤2中邻苯二酚木质素磺酸盐换成木质素磺酸钠制备的木质素磺酸钠/化学防晒剂微胶囊防晒霜在290～400nm范围的紫外光谱图，从图中可以看出，邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜的紫外透过率明显小于木质素磺酸钠/化学防晒剂微胶囊防晒霜的紫外透过率，说明能够阻隔更多的紫外线。换算成紫外防护指数（SPF），邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜的SPF值为116，而木质素磺酸钠/化学防晒剂微胶囊防晒霜的SPF值仅为39。
图4是实施例1所得的邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜和木质素磺酸钠/化学防晒剂微胶囊防晒霜的激光共聚焦测试图。利用激光共聚焦显微镜来测试邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜和木质素磺酸钠/化学防晒剂微胶囊防晒霜与皮肤的粘附性能。将实施例1步骤2中的邻苯二酚木质素磺酸盐换成原始的木质素磺酸钠所制备的木质素磺酸钠/化学防晒剂微胶囊防晒霜与皮肤的粘附性能很差，表面木质素的蓝色荧光信号微弱，证明粘黏在皮肤表面的微胶囊被洗去，而邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜能够在洗涤之后仍然保持较强的荧光信号，证明与原始木质素磺酸钠相比脱甲基后木质素磺酸钠表面酚羟基变多，粘附性能出现了明显的提升。
图5是通过马尔文激光粒度仪测试的本实施例1所得的邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊的粒径测试相关数据。微胶囊的尺寸大小对其在常温下的储存稳定性有很大的影响，粒径越大越不易储存。从图中我们可以看到邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊的粒径平均在300nm左右，而木质素磺酸钠/化学防晒剂微胶囊的中位粒径在350nm，而且邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊的粒径分布也更窄，证明经过脱甲基处理后得到的产物均一性更好。所以本发明的制备方法能够明显提升微胶囊的储存时间和稳定性。
实施例2
（1）将10g木质素磺酸镁和2g亚硫酸钠溶于30mL的15wt%NaOH溶液中，120℃进行冷凝回流反应1小时，反应结束后冷却至室温，将反应液在纯水中进行透析提纯处理，透析结束后将样品溶液进行浓缩干燥得到邻苯二酚木质素磺酸盐固体粉末。
（2）将0.21g邻苯二酚木质素磺酸盐溶解于6.79g超纯水中，制备得到3wt%的溶液，加入4g胡莫柳酯与阿伏苯宗（质量比为4:1）的混合物和1g吐温，在超声功率为600W状态下超声空化5min，8000 r/min离心30min，得到邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊。将该微胶囊与没有防晒活性成分的空白乳霜（妮维雅深层滋润护手霜，妮维雅（上海）有限公司）按照质量比1:9的配比混合制得邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜。
采用与实施例1相同的微胶囊制备工艺、紫外—可见光光谱分析、激光共聚焦测试、粒径测试。结果分别与图1，图2，图3，图4，图5基本相同。邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜的SPF值为98。
实施例3
（1）将10g木质素磺酸钠和0.7g焦亚硫酸钠溶于40mL的5wt%NaOH溶液中，70℃进行冷凝回流反应2.5小时，反应结束后冷却至室温，将反应液在纯水中进行透析提纯处理，透析结束后将样品溶液进行浓缩干燥得到邻苯二酚木质素磺酸盐固体粉末。
（2）将0.6g邻苯二酚木质素磺酸盐溶解于6.4g超纯水中，制备得到3wt%的溶液，加入3g甲氧基肉桂酸乙基己酯与阿伏苯宗（质量比为4:1）的混合物和0.3g蔗糖酯，在超声功率为400W状态下超声空化3min，5000 r/min离心40min，得到邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊。将该微胶囊与没有防晒活性成分的空白乳霜（妮维雅深层滋润护手霜，妮维雅（上海）有限公司）按照质量比1:9的配比混合制得邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜。
采用与实施例1相同的微胶囊制备工艺、紫外—可见光光谱分析、激光共聚焦测试、粒径测试。结果分别与图1，图2，图3，图4，图5基本相同。邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜的SPF值为104。
实施例4
（1）将7g木质素磺酸钙和1.5g硫代硫酸钠溶于20mL的2.5wt%NaOH溶液中，140℃进行冷凝回流反应1.5小时，反应结束后冷却至室温，将反应液在纯水中进行透析提纯处理，透析结束后将样品溶液进行浓缩干燥得到邻苯二酚木质素磺酸盐固体粉末。
（2）将0.21g邻苯二酚木质素磺酸盐溶解于6.79g超纯水中，制备得到3wt%的溶液，加入3g胡莫柳酯与阿伏苯宗（质量比为4:1）的混合物和0.4g烷基多苷，在超声功率为700W状态下超声空化5min，10000 r/min离心30min，得到邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊。将该微胶囊与没有防晒活性成分的空白乳霜（妮维雅深层滋润护手霜，妮维雅（上海）有限公司）按照质量比1:9的配比混合，制得邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜。
采用与实施例1相同的微胶囊制备工艺、紫外—可见光光谱分析、激光共聚焦测试、粒径测试。结果分别与图1，图2，图3，图4，图5基本相同。邻苯二酚木质素磺酸盐/化学防晒剂的生物粘附型微胶囊防晒霜的SPF值为113。
对比例1
（1）将10g木质素磺酸钠溶于30ml、10wt%NaOH溶液中，在氮气氛围、90℃进行冷凝回流反应1小时，反应结束后冷却至室温，将反应液在纯水中进行透析提纯处理，透析结束后将样品溶液进行浓缩干燥得到邻苯二酚木质素磺酸盐固体粉末。
（2）将0.21g邻苯二酚木质素磺酸盐溶解于6.79g超纯水中，制备得到5wt%的溶液，加入3g甲氧基肉桂酸乙基己酯与阿伏苯宗（质量比为4:1）的混合物和0.7g吐温，在超声功率为400W状态下超声空化3min。得到木质素磺酸钠/化学防晒剂超声空化乳液。
图6是本对比例所得邻苯二酚木质素磺酸盐超声空化乳液。从图中可以看到所得超声空化乳液出现了非常明显的分层的现象。这是由于适量的表面活性剂会降低水油界面张力，增大油滴比表面积，有助于木质素磺酸钠在油滴表面吸附和交联。但是过量的表面活性剂的加入，会使得过量的表面活性剂自身发生相互作用，导致液滴聚合，从而使得制备的微胶囊粒径过大，不稳定然后出现破乳的现象。
经过在后序加入化学防晒剂和表面活性剂制备微胶囊的时候基本上无法制备微胶囊或者说制备得到的微胶囊极容易破乳。也进一步的说明了经过硫化法进行脱甲基的处理，使得改性后的木质素磺酸盐在微胶囊的制备中稳定性出现了明显的提升。。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (8)

  1. 一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊的制备方法，其特征在于，包括以下步骤：
    （1）将木质素磺酸盐与硫化试剂溶于碱溶液中，于40～160℃反应0.1～5小时，透析处理，浓缩和干燥，得到邻苯二酚木质素磺酸盐；
    （2）将邻苯二酚木质素磺酸盐溶于pH=5～9的水溶液中，加入防晒剂和表面活性剂，超声空化，得到邻苯二酚木质素磺酸盐/化学防晒剂微胶囊乳液，离心后得到浅色化邻苯二酚木质素磺酸盐防晒微胶囊；
    步骤（1）所述木质素磺酸盐与硫化试剂的重量比为1～10：0.2～2；所述硫化试剂为亚硫酸盐、焦亚硫酸盐、硫代硫酸盐和亚硫酸氢盐中的至少一种；
    步骤（2）所述邻苯二酚木质素磺酸盐溶于pH=5～9的水溶液后所得溶液总重量与防晒剂重量比为1:1～10:1；
    步骤（2）所述表面活性剂的添加量占邻苯二酚木质素磺酸盐、pH=5～9的水溶液与防晒剂总重量的1～10wt%；
    步骤（2）所述邻苯二酚木质素磺酸盐与pH=5～9的水溶液的重量比为1～10：20～100；
    步骤（2）所述防晒剂为阿伏苯宗、甲氧基肉桂酸乙基己酯、胡莫柳酯和氧苯酮中的至少一种；
    步骤（2）所述表面活性剂为吐温、烷基多苷和蔗糖酯中的至少一种。
  2. 根据权利要求1所述一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊的制备方法，其特征在于，步骤（1）所述木质素磺酸盐与硫化试剂的重量比为10：0.7～2。
  3. 根据权利要求1所述一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊的制备方法，其特征在于，步骤（2）所述邻苯二酚木质素磺酸盐溶于pH=5～9的水溶液后所得溶液总重量与防晒剂重量比为1:1～4:1；
    步骤（2）所述表面活性剂的添加量占邻苯二酚木质素磺酸盐、pH=5～9的水溶液与防晒剂总重量的3～10 wt %；
    步骤（2）所述邻苯二酚木质素磺酸盐与pH=5～9的水溶液的重量比为1：10～33。
  4. 根据权利要求1所述一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊的制备方法，其特征在于，步骤（1）所述木质素磺酸盐为木质素磺酸钠、木质素磺酸镁和木质素磺酸钙中的至少一种；所述木质素磺酸盐中的木质素为竹浆木质素磺酸盐、麦草浆木质素磺酸盐、芦苇木质素磺酸盐、蔗渣浆木质素磺酸盐、龙须草浆木质素磺酸盐和棉浆粕木质素磺酸盐中的至少一种。
  5. 根据权利要求1所述一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊的制备方法，其特征在于，步骤（1）所述反应的温度为70～140℃，时间为1～2.5h；
    步骤（2）所述超声空化的功率为200～1500 W，时间为1～20 min。
  6. 根据权利要求1所述一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊的制备方法，其特征在于，步骤（1）所述碱溶液为1～20wt%的氢氧化钠溶液，所述木质素磺酸盐与碱溶液的重量比为1～10：30；步骤（1）所述透析处理的时间为2～8天，透析液为水。
  7. 权利要求1～6任一项所述方法制得的一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊。
  8. 权利要求7所述一种浅色化邻苯二酚木质素磺酸盐防晒微胶囊在防晒品制备中的应用。
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CN120009213A (zh) * 2025-02-26 2025-05-16 武汉市皮肤病防治院 一种复方尿素乳膏中尿素含量测定方法

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