WO2018099297A1 - 一种高紫外吸收的木质素/化学防晒剂微胶囊及制备方法 - Google Patents

一种高紫外吸收的木质素/化学防晒剂微胶囊及制备方法 Download PDF

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WO2018099297A1
WO2018099297A1 PCT/CN2017/112098 CN2017112098W WO2018099297A1 WO 2018099297 A1 WO2018099297 A1 WO 2018099297A1 CN 2017112098 W CN2017112098 W CN 2017112098W WO 2018099297 A1 WO2018099297 A1 WO 2018099297A1
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lignin
chemical sunscreen
preparing
chemical
solution
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French (fr)
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邱学青
钱勇
李莹
杨东杰
楼宏铭
朱世平
刘伟峰
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华南理工大学
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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
    • A61K8/33—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
    • A61K8/33—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
    • A61K8/18—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
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • 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
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9789—Magnoliopsida [dicotyledons]
    • 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
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9794—Liliopsida [monocotyledons]
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
    • 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

Definitions

  • the invention belongs to the technical field of chemical sunscreen preparation, and particularly relates to a high ultraviolet absorption lignin/chemical sunscreen microcapsule prepared by using lignin as a wall material and a preparation method thereof.
  • Sun exposure is one of the important factors that cause skin aging. Intense ultraviolet radiation may cause skin cancer. Studies have shown that ultraviolet light in the UVB band (290-320 nm) can pass through the stratum corneum and epidermis, causing skin erythema, leading to DNA damage. Ultraviolet light in the UVA band (320-400 nm) can reach the dermis, which is an important factor in triggering melanoma. Therefore, effective sun protection is necessary. Sunscreens can effectively absorb or scatter ultraviolet light in the UVB and UVA bands of sunlight, and are generally classified into two major categories: physical and chemical.
  • Inorganic particles such as titanium dioxide and zinc oxide can reflect or scatter ultraviolet radiation, but have poor affinity with the skin, easily accumulate on the hair follicle, and have poor comfort, which makes certain limitations in practical applications. Therefore, the active ingredients in sunscreen skin care products are mainly chemical sunscreens.
  • the sunscreen skin care based on chemical sunscreen is relatively fine, the sunscreen spectrum is relatively wide, and the sunscreen ability is relatively strong, which is generally welcomed by consumers.
  • the chemical sunscreen itself can absorb ultraviolet rays, has photochemical activity or physical activity, and undergoes photodegradation after absorbing ultraviolet rays, resulting in a decrease in the ability of the sunscreen to absorb ultraviolet rays, a poor sunscreen effect for a long time, and irritating products of degradation products to the skin. Allergies will also increase.
  • chemical sunscreens are generally small molecule compounds that penetrate skin cells, trigger DNA variability, and are easily broken by molecular chains under illumination to produce highly active free radicals that can damage large macromolecules and multiple cells. Causes skin aging or causes skin cancer.
  • Chitosan gel is a preparation method of wall-coated chemical sunscreen agent. It is firstly emulsified by gelatin, chemical sunscreen and emulsifier, and then a mixed solution of chitosan and acetic acid is added to the primary emulsion, followed by chlorination.
  • the calcium is re-agglomerated and solidified with glutaraldehyde as a crosslinking agent to form a chemical sunscreen embedding body (CN1709219 [P].).
  • Zhang Yuping and Niu Wenxia effectively coated the octyl methoxycinnamate chemical sunscreen with solid lipid microparticles and inhibited the penetration of chemical sunscreen on the skin by controlling the particle size of the coated carrier (Zhang Yuping, Niu Wenxia. Preparation and properties of octyl octyl cinnamate solid lipid microparticles[J].Journal of Chemical Industry and Engineering(China),2011,62(10):2965-2968.). Deng et al.
  • Lignin is a natural polymer compound widely present in the cell wall of plants.
  • the functional structure of many benzene rings, double bonds, carbonyl groups and phenolic hydroxyl groups in the molecule determines that it can not only absorb ultraviolet rays, but also has the function of scavenging free radicals.
  • a natural UV absorber and antioxidant Because lignin has excellent UV and oxidation resistance and good dispersibility, Qian et al. mixed alkali lignin with a hand cream without sunscreen. When the lignin content is 10%, the sunscreen index of the mixed cream is used.
  • lignin can be developed into a natural polymer anti-UV wall material embedded chemical sunscreen to prepare composite nano-capsules for sunscreen skin care.
  • lignin/chemical sunscreen microcapsule prepared by using lignin as a wall material.
  • the lignin/chemical sunscreen microcapsule of the invention has the amphiphilic spherical structure, the ultraviolet absorption performance is superior to the chemical sunscreen agent and the lignin, and the chemical sunscreen agent can be prevented from photodegradation and the stability is good.
  • Another object of the present invention is to provide a method for preparing the above lignin/chemical sunscreen microcapsules.
  • Lignin has a large number of conjugated structures such as benzene ring and carbonyl group, as well as reactive functional groups with strong ultraviolet absorption such as phenolic hydroxyl group and methoxy group, and phenolic hydroxyl groups present in a large amount in lignin molecules can form phenolic type under ultrasonic irradiation.
  • the free radicals promote the intermolecular cross-linking polymerization of lignin.
  • the invention combines the chemical sunscreen agent with the lignin solution, and prepares the lignin/chemical sunscreen microcapsule by one-step emulsion crosslinking by ultrasonic irradiation, without adding an emulsifier and a crosslinking agent.
  • the preparation process is simple, the cost is low, the environment is green, and the high-end and high-value application fields of the natural polymer lignin are effectively expanded, and the chemical sunscreen agent is effectively prevented from contacting and hurting the skin, and has a great application prospect in the field of sunscreen skin care products.
  • a method for preparing a lignin/chemical sunscreen microcapsule comprises the following steps:
  • the lignin may be one or a mixture of industrial lignin such as solvent-type lignin, enzymatic lignin, alkali lignin, and lignosulfonate.
  • the alkali lignin comprises wood pulp alkali lignin, bamboo pulp alkali lignin, wheat straw alkali lignin, reed pulp alkali lignin, bagasse alkali lignin, alfalfa pulp alkali lignin, cotton pulp alkali wood Prime.
  • the lignosulfonate includes bamboo pulp lignosulfonate, wheat straw pulp lignosulfonate, reed lignosulfonate, bagasse pulp lignosulfonate, alfalfa pulp lignosulfonate, Cotton pulp lignin sulfonate.
  • Industrial lignin is mainly derived from the cooking wastewater of the paper pulping industry. Depending on the fiber raw materials, pulping process and extraction method, their physicochemical properties vary greatly, so their applications are also very diverse. Industrial lignin is generally divided into four categories: 1 Hydrolyzed lignin: Hydrolyzed lignin is a residue obtained by saccharification with an acid. It has poor solubility in water and solvent, and poor reaction performance. Most of the condensation has occurred. Therefore, it is mostly used as fuel. 2 alkali lignin: alkali lignin mainly comes from alkaline pulping waste liquid such as sulfate method and alkaloid method.
  • Lignosulfonate is derived from sulfite pulping waste liquid, which has good water solubility and wide application prospects.
  • 4 other lignin solvent-type lignin, enzymatic lignin and the like.
  • the chemical sunscreen agent may be at least one of chemical sunscreens such as isooctyl methoxycinnamate, avobenzone and humulizate.
  • the mass fraction of the lignin in the aqueous solution in the step (1) is preferably from 3 to 10%; and the pH of the conditioning solution is preferably adjusted to a pH of from 8.5 to 9.5.
  • the pH of the conditioning solution as described in step (1) is preferably adjusted using a dilute acid solution, more preferably with a dilute hydrochloric acid solution.
  • the weight ratio of the lignin solution to the chemical sunscreen agent in the step (2) is preferably from 1:1 to 10:1.
  • the power of the ultrasonic radiation in the step (2) is preferably controlled to be 600 to 1000 W, and the time of the ultrasonic irradiation is preferably controlled to be between 1 min and 12 min.
  • the obtained lignin/chemical sunscreen microcapsule emulsion can be removed by centrifugal washing to remove excess lignin to obtain a lignin/chemical sunscreen microcapsule.
  • the rate of centrifugation is preferably from 5,000 to 50,000 r/min, and the time of centrifugal water washing is preferably from 5 to 30 min.
  • the rate of centrifugation is more preferably 10,000 r/min, and the time of centrifugal water washing is preferably 10 to 20 min.
  • the invention provides a lignin/chemical sunscreen microcapsule prepared by the above method.
  • the lignin/chemical sunscreen microcapsule of the invention has the amphiphilic spherical structure, the ultraviolet absorption performance is superior to the chemical sunscreen agent and the lignin, and the chemical sunscreen agent can be prevented from photodegradation and the stability is good.
  • Lignin has a large number of conjugated structures such as benzene ring and carbonyl group, as well as reactive functional groups with strong ultraviolet absorption such as phenolic hydroxyl group and methoxy group, and phenolic hydroxyl groups present in a large amount in lignin molecules can be irradiated under ultrasonic radiation.
  • the phenolic radical is formed to promote the intermolecular cross-linking polymerization of the lignin.
  • the invention combines the chemical sunscreen agent with the lignin solution, and prepares the lignin/chemical sunscreen microcapsule by ultrasonic emulsification and cross-linking, without adding an emulsifier.
  • cross-linking agent simple preparation process, low cost, green and environmental protection, effectively expanding the high-end, high-value application field of natural polymer lignin, while effectively avoiding chemical sunscreen contact and skin damage, there is a huge field of sunscreen skin care products. Application prospects.
  • the present invention has the following advantages and beneficial effects:
  • the invention utilizes abundant lignin as a wall material to embed chemical sunscreen agent, without additional emulsifier and cross-linking agent, adopts ultrasonic radiation emulsification crosslinking, and obtains lignin/chemical sunscreen microcapsule in one step, and prepares
  • the process is simple, the process is green and environmentally friendly, and the cost is low, while retaining the functional structure of phenolic hydroxyl groups which can enhance the ultraviolet absorption and oxidation resistance of lignin.
  • the wall material of the lignin/chemical sunscreen microcapsule of the invention is amphiphilic lignin, and has good compatibility with the aqueous and oily cream system, and the synergistic effect produced by the lignin and the chemical sunscreen agent can Further enhancing the UV protection effect, the lignin microcapsules can well maintain the embedded chemical sunscreen for long-lasting sun protection, and have a good market potential in the field of sunscreen skin care.
  • the lignin used in the present invention is derived from plants and coexisted with human beings, and the natural molecular structure of the polymer makes it have good photostability.
  • chemical sunscreens can be prevented from being degraded by sunlight radiation, and It can avoid contact with chemical sunscreen and damage the skin, while lignin itself has no toxic side effects.
  • Example 1 is an optical micrograph of the lignin/chemical sunscreen microcapsule of Example 1.
  • Figure 2 is a graph of the sustained release of the lignin/chemical sunscreen microcapsules of Example 1 in artificial sweat.
  • Figure 3 is a UV spectrum of the lignin, chemical sunscreen, and lignin/chemical sunscreen microcapsules of Example 1 in the range of 260-400 nm.
  • FIG. 1 is an optical micrograph of a lignin/humulizate microcapsule of the product of Example 1 observed by an optical microscope, showing that the microcapsule is a spherical structure having a diameter of less than 5 ⁇ m.
  • the lignin/humulolate microcapsules obtained in the step (3) are uniformly dispersed in ultrapure water, and then placed in a 10,000 molecular weight microdialysis tube, and subjected to artificial sweat at a constant temperature of 35 ° C. Slow release test. The UV absorbance of the dispersion at 325 nm was measured by a Shimadzu UV-2450 UV-Vis spectrophotometer and the release amount of the sunscreen was calculated. 2 is a slow release curve of the product lignin/humulizate microcapsule of the first embodiment, and the product of the first embodiment of the product of the first embodiment is artificially sunscreened in the artificial sweat after 24 hours at 35 ° C. The release rate is only 15%, indicating that the lignin/humulizate microcapsules can well embed and maintain the chemical sunscreen, which can prolong the UV absorption time.
  • the lignin/humulolate microcapsule obtained in the step (3) is diluted to 0.01 mg/mL with ultrapure water, and the same concentration of the solvent-type lignin aqueous solution and the chemical sunscreen agent humulizate water are disposed.
  • the dispersion and the DMSO solution of humulizate were tested for UV absorbance.
  • Figure 3 is a UV spectrum of the product of Example 1 and the sample of lignin and chemical sunscreen measured by the Shimadzu UV-2450 UV-Vis spectrophotometer in the range of 260-400 nm, as can be seen from the figure,
  • the UV absorbance of the product lignin/humulizate microcapsules of Example 1 was 2 to 3 times higher than that of the aqueous solution of the same concentration of the aqueous solution of the enzymatic lignin solution and the sunscreen agent.
  • the synergistic sunscreen effect of lignin and chemical sunscreen is directly proportional to the contact rate between the two.
  • the lignin in the microcapsule system is completely in contact with the chemical sunscreen agent, and the synergistic effect is more significant, which makes the microcapsule product have a large UV absorption effect.

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Abstract

一种应用木质素为壁材制备的高紫外吸收的木质素/化学防晒剂微胶囊的制备方法，包括以下步骤：(1)将1～20重量份木质素溶解于100～200重量份的pH为12的水溶液中，调节溶液pH至7～10后滤除去不溶物，得到木质素溶液；(2)将10～50重量份步骤(1)的木质素溶液与1～10重量份的化学防晒剂混合，在200～1500W的功率下超声辐射10s～25min，得到木质素/化学防晒剂微胶囊乳液。

Description

一种高紫外吸收的木质素/化学防晒剂微胶囊及制备方法 技术领域
本发明属于化学防晒剂制备技术领域，特别涉及一种应用木质素为壁材制备的高紫外吸收的木质素/化学防晒剂微胶囊及制备方法。
背景技术
日光暴晒是使皮肤老化的重要因素之一，强烈的紫外线照射可能引起皮肤癌症。研究表明，UVB波段(290～320nm)的紫外线能穿过角质层和表皮，引起皮肤红斑，导致DNA损伤，UVA波段(320～400nm)的紫外线能到达真皮层，是引发黑色素瘤的重要因素。因此，有效的防晒非常必要。防晒剂能有效地吸收或散射太阳光中UVB和UVA波段的紫外线，一般分为物理和化学两大类。物理防晒剂如二氧化钛和氧化锌等无机颗粒能够反射或散射紫外辐射，但是与皮肤的亲和性不佳，容易在毛囊上堆积，舒适性较差，使得在实际应用有一定的局限。因此，目前防晒护肤品中活性成分是以化学防晒剂为主。
以化学防晒剂为主的防晒护肤品质地比较细腻，防晒波谱比较宽，防晒能力比较强，因而受到消费者的普遍欢迎。但是，化学防晒剂本身能够吸收紫外线，具有光化学活性或物理活性，吸收紫外线后会发生光降解作用，导致防晒剂吸收紫外线的能力降低，长时间防晒效果不好，降解产物对皮肤的刺激性和过敏性也会增加。
此外，化学防晒剂一般为小分子化合物，能够渗透皮肤细胞，引发DNA变异，在光照下也容易分子链断裂产生高活性的自由基，这些自由基能损坏生物体大分子和多种细胞，进而导致皮肤老化或引发皮肤癌。
为了解决上述问题，国内外的研究者开发脂质体、凝胶等多种基材体系包覆化学防晒剂。包覆后的化学防晒剂的稳定性得到很大提高，并且可以将化学防晒剂与皮肤隔离，降低了对皮肤的毒副作用。刘双喜和宋春津研发了一种以 壳聚糖凝胶为壁材包裹化学防晒剂的制备方法，先以明胶、化学防晒剂和乳化剂进行高速乳化，再将壳聚糖和乙酸的混合溶液加到初乳液中，接着以氯化钙进行复凝聚，以戊二醛作交联剂进行固化形成化学防晒剂包埋体(CN1709219[P].)。张婉萍和牛文霞利用固体脂质微粒对甲氧基肉桂酸辛酯化学防晒剂进行了有效包覆，并通过对包覆载体粒径的控制抑制化学防晒剂在皮肤上的渗透(张婉萍，牛文霞.包覆甲氧基肉桂酸辛酯固体脂质微粒的制备及性能[J].化工学报,2011,62(10):2965-2968.)。Deng等通过多步合成制备聚乳酸-聚甘油用于包埋化学防晒剂，进一步将聚甘油醛化改性，制备了具有生物吸附性能的聚合物/化学防晒剂微胶囊(Nature materials,2015,14:1278-1285)。无论是壳聚糖和脂质体，还是多步合成的聚乳酸-聚甘油，虽然可以通过化学交联包埋化学防晒剂，但是需要加入乳化剂、交联剂等多种助剂，这些助剂的加入不但增加制备和分离成本，而且还要考虑助剂残留对人体及皮肤的伤害。同时，以上壁材对化学防晒剂的包埋及保持性能也有待进一步评估。
木质素是广泛存在于植物细胞壁中的天然高分子化合物，分子中众多的苯环、双键、羰基、酚羟基等官能团结构决定其不但能够吸收紫外线，同时还具有清除自由基的功能，是一种天然的紫外线吸收剂和抗氧化剂。由于木质素抗紫外和抗氧化性能优异，同时具有良好的分散性，Qian等将碱木质素与没有防晒作用的护手霜混合，在木质素掺量为10％时，混合霜体的防晒指数(SPF值)达到5.72；将其与市售SPF值为15的防晒霜混合，碱木质素掺量为2％时混合霜体的SPF值已达到35.32，掺量在10％时SPF值更达到了89.58，说明木质素不但具有广谱紫外防护性能，而且与防晒霜中的化学防晒剂具有协同作用(Green Chemistry,2015,17:320-324)。
研究证明，即使是工业木质素经提纯后基本没有细胞毒性，具有很好的生理相容性，这些研究基本消除了木质素在化妆护肤甚至医药领域使用的安全忧虑。(Bioresources Technology,2008,99(14)：6683-6687)。无论从理论、实验还是生态、安全方面考虑，木质素均可以被开发成天然高分子抗紫外壁材包埋化学防晒剂制备复合纳米微胶囊应用于防晒护肤领域。
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种应用木质素为壁材制备的高紫外吸收的木质素/化学防晒剂微胶囊。本发明的木质素/化学防晒剂微胶囊为两亲球形结构，紫外吸收性能优于化学防晒剂和木质素，同时可以避免化学防晒剂光降解，稳定性良好。
本发明另一目的在于提供一种上述木质素/化学防晒剂微胶囊的制备方法。
木质素具有大量的苯环、羰基等共轭结构，还有酚羟基、甲氧基等具有较强紫外吸收的活性官能团，而木质素分子中大量存在的酚羟基在超声辐射下能够形成酚型自由基，促使木质素发生分子间交联聚合，本发明将化学防晒剂与木质素溶液混合，通过超声辐射一步乳化交联制备木质素/化学防晒剂微胶囊，无需添加乳化剂和交联剂，制备过程简单，成本低，绿色环保，有效拓展了天然高分子木质素的高端、高值化应用领域，同时有效避免化学防晒剂接触、伤害皮肤，在防晒护肤品领域有着巨大的应用前景。
本发明的目的通过下述方案实现：
一种木质素/化学防晒剂微胶囊的制备方法，包括以下步骤：
(1)将1～20重量份木质素溶解于100～200重量份的pH为12的水溶液中，调节溶液pH至7～10后滤除去不溶物，得到木质素溶液；
(2)将10～50重量份步骤(1)的木质素溶液与1～10重量份的化学防晒剂混合，在200～1500W的功率下超声辐射10s～25min，得到木质素/化学防晒剂微胶囊乳液。
所述木质素可为溶剂型木质素、酶解木质素、碱木质素以及木质素磺酸盐等工业木质素中的一种或几种混合物。
所述的碱木质素包括木浆碱木质素、竹浆碱木质素、麦草浆碱木质素、芦苇浆碱木质素、蔗渣浆碱木质素、龙须草浆碱木质素、棉浆粕碱木质素。
所述的木质素磺酸盐包括竹浆木质素磺酸盐、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、棉浆粕木质素磺酸盐。
工业木质素主要来源于造纸制浆工业的蒸煮废水，根据纤维原料、制浆工艺以及提取方法等的不同，它们的物理化学性质相差很大，因此其应用也是非常多样化的。工业木质素通常分为四类：①水解木质素：水解木质素是用酸进行糖化后得到的残渣，它对水和溶剂的溶解性都很差，反应性能也很差，大部分已经发生缩合，因此多用作燃料。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。④其他木质素：溶剂型木质素、酶解木质素等。
所述的化学防晒剂可为甲氧基肉桂酸异辛酯、阿伏苯宗和胡莫柳酯等化学防晒剂中的至少一种。
为了进一步更好地实现本发明目的，步骤(1)中所述木质素在水溶液中质量分数优选为3～10％；所述调节溶液pH优选调节pH为8.5～9.5。
为了进一步更好地实现本发明目的，步骤(1)所述调节溶液pH优选使用稀酸溶液调节，更优选使用稀盐酸溶液调节。
为了进一步更好地实现本发明目的，步骤(2)中所述木质素溶液与化学防晒剂的重量比优选为1:1～10:1。
为了进一步更好地实现本发明目的，步骤(2)中所述超声辐射的功率优选控制在600～1000W，所述超声辐射的时间优选控制在1min～12min。
为了进一步更好地实现本发明目的，所述得到的木质素/化学防晒剂微胶囊乳液可通过离心水洗除去多余的木质素，得到木质素/化学防晒剂微胶囊。
所述离心的速率优选为5000～50000r/min，离心水洗的时间优选为5～30min。
所述离心的速率更优选为10000r/min，离心水洗的时间优选为10～20min。
本发明提供上述方法制备得到的木质素/化学防晒剂微胶囊。本发明的木质素/化学防晒剂微胶囊为两亲球形结构，紫外吸收性能优于化学防晒剂和木质素，同时可以避免化学防晒剂光降解，稳定性良好。
木质素具有大量的苯环、羰基等共轭结构，还有酚羟基、甲氧基等具有较强紫外吸收的活性官能团，而木质素分子中大量存在的酚羟基在超声辐射下能 够形成酚型自由基，促使木质素发生分子间交联聚合，本发明将化学防晒剂与木质素溶液混合，通过超声辐射一步乳化交联制备木质素/化学防晒剂微胶囊，无需添加乳化剂和交联剂，制备过程简单，成本低，绿色环保，有效拓展了天然高分子木质素的高端、高值化应用领域，同时有效避免化学防晒剂接触、伤害皮肤，在防晒护肤品领域有着巨大的应用前景。
本发明相对于现有技术，具有如下的优点及有益效果：
1、本发明以来源丰富的木质素直接作为壁材包埋化学防晒剂，无需额外添加乳化剂和交联剂，采用超声辐射乳化交联，一步制得木质素/化学防晒剂微胶囊，制备工艺简单，过程绿色环保、成本低廉，同时保留了木质素能够强化紫外吸收和抗氧化的酚羟基等官能结构。
2、本发明木质素/化学防晒剂微胶囊的壁材为两亲性的木质素，与水性和油性的乳霜体系均具有良好的相容性，木质素和化学防晒剂产生的协同效应能够进一步强化紫外防护效果，木质素微胶囊能够很好地保持包埋的化学防晒剂实现持久防晒，在防晒护肤领域有着很好的市场潜力。
3、本发明使用的木质素来源于植物，与人类共生共长，而天然的高分子分子结构使其具有良好的光稳定性，作为壁材不但可以避免化学防晒剂受阳光辐照降解，而且可以避免化学防晒剂接触、伤害皮肤，而木质素本身没有毒副作用。
附图说明
图1是实施例1木质素/化学防晒剂微胶囊的光学显微镜图。
图2是实施例1木质素/化学防晒剂微胶囊在人工汗液中的缓释曲线。
图3是实施例1木质素、化学防晒剂和木质素/化学防晒剂微胶囊在260～400nm范围的紫外光谱图。
具体实施方式
下面结合实施例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。
下列实施例中使用的试剂均可从商业渠道获得。
实施例1
(1)将20g溶剂型木质素置于500mL烧杯中，加入180g pH12的水溶液溶解木质素，再加入稀盐酸调节溶液pH至8.5后，滤除不溶物，得到质量分数为10％的溶剂型木质素水溶液。
(2)将步骤(1)所得的木质素溶液取100g与100g化学防晒剂胡莫柳酯加入到中，水油比为1:1，利用600W功率的超声波超声辐射处理12min，得到含有木质素/胡莫柳酯微胶囊乳液。
(3)将步骤(2)中得到乳液以10000r/min的速度离心水洗20min，得到木质素/胡莫柳酯微胶囊膏体。图1是通过光学显微镜观察到的本实施例1产品木质素/胡莫柳酯微胶囊的光学显微镜图，表明该微胶囊是直径小于5μm的球形结构。
(4)将步骤(3)中得到的木质素/胡莫柳酯微胶囊用超纯水分散均匀后，装入10000分子量的微量透析管中，35℃的恒温条件下，在人工汗液中进行缓释测试。通过日本岛津UV-2450紫外-可见分光光度计测量不同时间分散液在325nm处的紫外吸光度并计算出防晒剂的释放量。图2是本实施例1的产品木质素/胡莫柳酯微胶囊的缓释曲线，在35℃条件下，24h后本实施例1的产品在人工汗液中化学防晒剂胡莫柳酯的累计释放量仅为15％，表明木质素/胡莫柳酯微胶囊可以很好的包埋和保持化学防晒剂，进而可以延长紫外吸收时间。
(5)将步骤(3)中得到的木质素/胡莫柳酯微胶囊用超纯水稀释至0.01mg/mL，并配置相同浓度的溶剂型木质素水溶液、化学防晒剂胡莫柳酯水分散液、胡莫柳酯DMSO溶液，进行紫外吸光度测试。图3是通过日本岛津UV-2450紫外-可见分光光度计测得的本实施例1产品及木质素、化学防晒剂样品在260～400nm范围的紫外光谱图，从图中可以看出，本实施例1产品木质素/胡莫柳酯微胶囊的紫外吸光度与相同浓度的酶解木质素水溶液、防晒剂胡莫柳酯的水溶液的紫外吸光度相比，分别高出其2到3倍。木质素与化学防晒剂的协同防晒效应与二者的接触率成正比，微胶囊体系中木质素与化学防晒剂胡莫柳酯完全接触，协同效应更加显著，使得微胶囊产品的紫外吸收效果大 大提高。
实施例2
(1)将6g酶解木质素置于500mL烧杯中，加入194g pH12的水溶液溶解木质素，再加入稀盐酸调节溶液pH至9.5后，滤除不溶物，得到质量分数为3％的酶解木质素水溶液。
(2)将步骤(1)所得的木质素溶液取50g与5g化学防晒剂甲氧基肉桂酸异辛酯入到中，水油比为10:1，利用1000W功率的超声波超声辐射处理1min，得到含有木质素/甲氧基肉桂酸异辛酯微胶囊乳液。
(3)将步骤(2)中得到乳液以10000r/min的速度离心水洗10min，得到木质素/甲氧基肉桂酸异辛酯微胶囊膏体。
(4)采用与实施例1相同的光学显微镜测定、缓释分析、紫外光谱测定，结果分别与图1，图2，图3基本相同。
实施例3
(1)将10g碱木质素置于500mL烧杯中，加入190g pH12的水溶液溶解木质素，再加入稀盐酸调节溶液pH至9.0后，滤除不溶物，得到质量分数为5％的碱木质素水溶液。
(2)将步骤(1)所得的木质素溶液取50g与25g化学防晒剂胡莫柳酯和阿伏苯宗的混合物加入到中，水油比为2:1，利用800W功率超声波超声辐射处理8min，得到含有木质素/(胡莫柳酯和阿伏苯宗)化学防晒剂微胶囊乳液。
(3)将步骤(2)中得到乳液以10000r/min的速度离心水洗10min，得到木质素/化学防晒剂微胶囊膏体。
(4)采用与实施例1相同的光学显微镜测定、缓释分析、紫外光谱测定，结果分别与图1，图2，图3基本相同。
实施例4
(1)将15g木质素磺酸盐置于500mL烧杯中，加入185g pH12的水溶液 溶解木质素，再加入稀盐酸调节溶液pH至9.0后，滤除不溶物，得到质量分数为7.5％的碱木质素水溶液。
(2)将步骤(1)所得的木质素溶液取75g与25g化学防晒剂甲氧基肉桂酸辛酯和阿伏苯宗的混合物加入到中，水油比为3:1，利用900W功率的超声波超声辐射处理6min，得到含有木质素/(甲氧基肉桂酸辛酯和阿伏苯宗)化学防晒剂微胶囊乳液。
(3)将步骤(2)中得到乳液以10000r/min的速度离心水洗10min，得到木质素/化学防晒剂微胶囊膏体。
(4)采用与实施例1相同的光学显微镜测定、缓释分析、紫外光谱测定，结果分别与图1，图2，图3基本相同。
实施例5
(1)将8g木质素磺酸盐置于250mL烧杯中，加入192g pH12的水溶液溶解木质素，再加入稀盐酸调节溶液pH至9.1后，滤除不溶物，得到质量分数为4％的碱木质素水溶液。
(2)将步骤(1)所得的木质素溶液取80g与40g化学防晒剂甲氧基肉桂酸辛酯、胡莫柳酯和阿伏苯宗的混合物加入到中，水油比为4:1，利用700W功率的超声波超声辐射处理9min，得到含有木质素/(甲氧基肉桂酸辛酯、胡莫柳酯和阿伏苯宗)化学防晒剂微胶囊乳液。
(3)将步骤(2)中得到乳液以10000r/min的速度离心水洗10min，得到木质素/化学防晒剂微胶囊膏体。
(4)采用与实施例1相同的光学显微镜测定、缓释分析、紫外光谱测定，结果分别与图1，图2，图3基本相同。
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 (10)

  1. 一种木质素/化学防晒剂微胶囊的制备方法，其特征在于包括以下步骤：
    (1)将1～20重量份木质素溶解于100～200重量份的pH为12的水溶液中，调节溶液pH至7～10后滤除去不溶物，得到木质素溶液；
    (2)将10～50重量份步骤(1)的木质素溶液与1～10重量份的化学防晒剂混合，在200～1500W的功率下超声辐射10s～25min，得到木质素/化学防晒剂微胶囊乳液。
  2. 根据权利要求1所述的木质素/化学防晒剂微胶囊的制备方法，其特征在于：所述木质素为溶剂型木质素、酶解木质素、碱木质素以及木质素磺酸盐中的一种或几种混合物。
  3. 根据权利要求2所述的木质素/化学防晒剂微胶囊的制备方法，其特征在于：所述的碱木质素包括木浆碱木质素、竹浆碱木质素、麦草浆碱木质素、芦苇浆碱木质素、蔗渣浆碱木质素、龙须草浆碱木质素或棉浆粕碱木质素；
    所述的木质素磺酸盐包括竹浆木质素磺酸盐、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或棉浆粕木质素磺酸盐。
  4. 根据权利要求1所述的木质素/化学防晒剂微胶囊的制备方法，其特征在于：所述的化学防晒剂为甲氧基肉桂酸异辛酯、阿伏苯宗和胡莫柳酯化学防晒剂中的至少一种。
  5. 根据权利要求1所述的木质素/化学防晒剂微胶囊的制备方法，其特征在于：步骤(1)中所述木质素在水溶液中质量分数为3～10％。
  6. 根据权利要求1所述的木质素/化学防晒剂微胶囊的制备方法，其特征在于：步骤(1)中所述调节溶液pH指调节pH为8.5～9.5。
  7. 根据权利要求1所述的木质素/化学防晒剂微胶囊的制备方法，其特征在于：步骤(2)中所述木质素溶液与化学防晒剂的重量比为1:1～10:1。
  8. 根据权利要求1所述的木质素/化学防晒剂微胶囊的制备方法，其特征在于：步骤(2)中所述超声辐射的功率为600～1000W。
  9. 根据权利要求1所述的木质素/化学防晒剂微胶囊的制备方法，其特征在于：步骤(2)中所述超声辐射的时间为1min～12min。
  10. 一种木质素/化学防晒剂微胶囊，其特征在于根据权利要求1～9任一项所述的制备方法得到。
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