WO2021174714A1 - 一种基于黑色素的防晒组合物及其制备方法 - Google Patents

一种基于黑色素的防晒组合物及其制备方法 Download PDF

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WO2021174714A1
WO2021174714A1 PCT/CN2020/095256 CN2020095256W WO2021174714A1 WO 2021174714 A1 WO2021174714 A1 WO 2021174714A1 CN 2020095256 W CN2020095256 W CN 2020095256W WO 2021174714 A1 WO2021174714 A1 WO 2021174714A1
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melanin
weight
parts
titanium dioxide
sunscreen composition
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PCT/CN2020/095256
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English (en)
French (fr)
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东为富
李婷
黎赛瑶
汪洋
李广龙
张正
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江南大学
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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
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • 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
    • 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
    • A61Q19/08—Anti-ageing preparations
    • 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
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • 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
    • A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18

Definitions

  • the present invention relates to the technical field of sunscreen agents, and more specifically, to a melanin-based sunscreen composition, a preparation method and cosmetics.
  • UVA zone ultraviolet A zone
  • UVB zone ultraviolet B zone
  • oxygen free radicals increase.
  • the sun's damage to human skin mainly comes from the UVA area and UVB area.
  • UVA has strong penetrating power to the skin, can penetrate the skin and dermis, gradually destroy the elastic fibers, and make the muscles lose elasticity. Causes skin sagging, wrinkles, freckles and age spots. Excessive ultraviolet radiation can easily cause skin cancer.
  • UVB can reach the ground and can denature the nucleic acid or protein in the cells on the skin surface, the skin becomes red, erythema (sunburn) is formed, melanin is formed on the skin, and acute dermatitis occurs, which is often called sunburn. So ultraviolet rays are the enemy of skin health. There are nearly 500,000 new skin cancer patients in the United States each year, and the results of the study prove that more than 98% of these patients are affected by sunlight.
  • the sunscreens used in cosmetics on the market are mainly divided into organic small molecule ultraviolet absorbers and inorganic ultraviolet shielding agents.
  • the inorganic ultraviolet shielding agents approved by the national safety of various countries mainly include titanium dioxide and zinc oxide, and the types and maximum addition limits of organic small molecule ultraviolet absorbers are different in different countries.
  • Inorganic UV shielding agents are considered to be non-toxic and safe to the human body. It is not irritating to the skin and does not cause cancer; however, this type of sunscreen has no significant UV absorption and shielding effect.
  • Titanium dioxide absorbs UVB better than zinc oxide, but absorbs UVA weaker than zinc oxide; and when the content is small, sunscreen The sunscreen factor (SPF) of cosmetics is extremely low, and the dosage needs to be increased and used in combination with organic small-molecule ultraviolet absorbers.
  • SPF sunscreen factor
  • the present invention provides a melanin-based sunscreen composition and a preparation method.
  • the invention adopts the compound of melanin, titanium dioxide and zinc oxide, which can effectively increase the SPF value and the PA value, obtain a sunscreen composition with excellent protection effect in the full ultraviolet band, and is safe and effective, and has no side effects on the human body.
  • One of the objectives of the present invention is to provide a sunscreen composition based on melanin.
  • the sunscreen composition includes:
  • Inorganic components 100 parts by weight
  • Melanin 0.5-5 parts by weight; preferably 0.5-2 parts by weight;
  • the melanin particle size range is 50-400nm; preferably 80-250nm;
  • the inorganic component is titanium dioxide, or titanium dioxide and zinc oxide
  • the particle size of the inorganic component is in the range of 20-300 nm.
  • the crystal form of the titanium dioxide is preferably rutile type and anatase type
  • the particle size range of the titanium dioxide is preferably 20-200 nm, more preferably 30-100 nm.
  • the particle size range of the zinc oxide is preferably 30-300 nm, more preferably 50-100 nm.
  • the inorganic substance is titanium dioxide and zinc oxide
  • Titanium dioxide is 1-99 parts by weight
  • zinc oxide is 1-99 parts by weight
  • Titanium dioxide is 50-99 parts by weight
  • Zinc oxide is 1-50 parts by weight.
  • the second object of the present invention is to provide a method for preparing the sunscreen composition according to one of the objects of the present invention.
  • the method includes:
  • the sunscreen composition is prepared after the components are uniformly mixed according to the amount.
  • the main sunscreen principle of the melanin-based sunscreen composition of the present invention is to absorb and scatter ultraviolet rays.
  • melanin particles of suitable particle size are compounded with inorganic titanium dioxide and zinc oxide particles.
  • ultraviolet rays act on the particles in the medium, because the size of the nanoparticles is smaller than the wavelength of ultraviolet rays, or is equivalent to the wavelength of ultraviolet rays, the electrons in the particles Forced to vibrate (its vibration frequency is the same as that of the incident light wave), it becomes a secondary wave source, emitting electromagnetic waves in all directions, which can scatter ultraviolet light.
  • one or a combination of melanin, inorganic titanium dioxide and zinc oxide has a synergistic effect when absorbing ultraviolet rays, so that the final melanin-based sunscreen composition has an ultraviolet absorbing effect better than any one of the original components.
  • both inorganic titanium dioxide and zinc oxide are N-type semiconductors.
  • electrons in the valence band can absorb ultraviolet rays and be excited to the conduction band, and at the same time generate hole-electron pairs, so titanium dioxide and Zinc oxide has the function of absorbing ultraviolet rays.
  • pure titanium dioxide and zinc oxide can only absorb limited ultraviolet rays because the hole-electron pair has limited ability to absorb ultraviolet rays.
  • Titanium dioxide and zinc oxide cannot convert the absorbed ultraviolet rays into heat or electricity, so holes cannot be created- The electron pair then absorbs ultraviolet light.
  • Melanin can convert 99% of the proton absorption energy into thermal energy in a very short time (50ps) in a non-radiative form (Wavelength-dependent photoacoustic calorimetry study of melanin.Photochem Photobiol, 1998, 68(3): 296-298), However, large-scale use of melanin will result in darker cosmetics and lower consumer acceptance.
  • the present invention When the present invention combines a small amount of melanin with one or a combination of inorganic titanium dioxide and zinc oxide, while scattering ultraviolet rays, the ultraviolet rays that titanium dioxide and zinc oxide can absorb, the electrons in the valence band are excited to the conduction band, At the same time, hole-electron pairs are generated, and then transferred through the large ⁇ -conjugated system with the melanin itself, so that the photothermal conversion can be continuously carried out through the melanin, and the ultraviolet absorption capacity is greatly improved.
  • the melanin and melanin-like pigments used in the present invention are biological macromolecules, and have multiple properties of antioxidants, ultraviolet absorbers, and stable dispersants. They are different from other organic small molecular ultraviolet absorbers.
  • Melanin itself is a human metabolite and is safe. Toxic, does not cause skin allergic reactions and has multiple effects. Melanin is a peculiar biological macromolecule, which exists widely in animals and plants. It has superior properties such as ultraviolet light absorption, heat dissipation, metal ion chelation, temperature regulation, antibacterial properties and free radical scavenging (Journal of Physics.D: Applied Physics 2009, 42(3): 035502).
  • the particle size of melanin nanoparticles is about 100-200nm.
  • the Chinese patent publication number CN 103841947A mentions that a small amount of particles with a particle size of less than 500nm in cosmetics can inhibit the aggregation of emulsified particles over time and increase the formation of amphiphilic substances. Thickening effect, so the addition of melanin is conducive to the uniform mixing of the ingredients in the cosmetics. In addition, melanin almost completely absorbs ultraviolet rays in the UVA area and UVB area, and the transmittance of ultraviolet rays is about zero, and melanin captures and removes free radicals generated by the human body, and has an obvious antioxidant effect.
  • bio-melanin can be endocytosed like the melanin produced by the human body, forming a protective layer on human epidermal keratinocytes, reducing UV damage; at the same time, it can also metabolize cells and be excreted from the body (Mimicking Melanosomes: Polydopamine Nanoparticles as Artificial Microparasols, ACS Cent. Sci. 2017, 3, 564-569).
  • Titanium dioxide has a stronger effect on absorbing part of ultraviolet rays with wavelengths of 290-355nm.
  • Zinc oxide has a stronger effect on absorbing part of ultraviolet rays with wavelengths of 355-385nm than titanium dioxide, and melanin absorbs in the ultraviolet band. Therefore, melanin, titanium dioxide, and zinc oxide are compounded.
  • a personal care sunscreen composition with excellent protection effect in the full ultraviolet range can be obtained.
  • melanin-based sunscreen composition is formed, and it is incorporated into cosmetic components.
  • the sunscreen composition of the present application is not only suitable for cosmetics, but can also be applied to other fields, for example, it can be used in some transparent polymers to shield ultraviolet rays.
  • the melanin particles of suitable particle size are compounded with inorganic titanium dioxide and zinc oxide particles, when ultraviolet rays act on the particles in the medium, because the size of the nanoparticles is smaller than the wavelength of ultraviolet rays, they can scatter ultraviolet light.
  • Titanium dioxide and zinc oxide can continuously convert the absorbed ultraviolet rays through melanin for photothermal conversion, which greatly improves the ultraviolet absorption capacity.
  • a small amount of melanin can play multiple roles in cosmetics, such as scavenging free radicals, absorbing and scattering ultraviolet rays, and stabilizing dispersion; at the same time, it improves the color of cosmetics, makes cosmetics easy to spread and disperse, and reduce stickiness.
  • the combination of melanin, titanium dioxide and zinc oxide can effectively increase the SPF value and the PA value, and obtain a sunscreen composition with excellent protection effects in the full ultraviolet band.
  • melanin 1-2 Dissolve dopamine hydrochloride (provided by Shanghai Aladdin Biochemical Technology Co., Ltd., Specification: AR) in deionized water, stir, heat up, and then add a certain amount of alkaline substance, 4 After an hour, the reaction is over, and after centrifugation, melanin 1 with a particle size of 80 nm and melanin 2 with a particle size of 200 nm are obtained;
  • Titanium dioxide 1 has a particle size of 60nm, rutile type
  • Titanium dioxide 2 has a particle size of 100nm, rutile type
  • the particle size of zinc oxide 1 is 50nm;
  • the particle size of zinc oxide 2 is 100nm;
  • the formula is shown in Table 1.
  • the sunscreen composition is prepared after the components are evenly mixed
  • test sample after being stored at 25°C for one month was visually observed and evaluated according to the following criteria.
  • Comparative Examples 1-3 listed in Table 3 it can be seen that pure titanium dioxide has better UVB resistance than zinc oxide, and zinc oxide has better UVA protection effect than titanium dioxide, but the addition of 10% content has allowed Some consumers feel less use. Comparing Examples 13-15 with Comparative Example 1, it shows that the addition of melanin can greatly increase the SPF and PA values, and increase with the increase of melanin content; at the same time, the addition of a small amount of melanin can reduce the stickiness of cosmetics Sense, enhance the sense of experience.
  • Example 17 shows that under the same melanin content, the increase of the titanium dioxide content increases the SPF value of cosmetics, but too much titanium dioxide will make the overall color of the cosmetics too white, increase the stickiness, and consume The feeling of use decreases; in Example 17 and Comparative Examples 1-3, the content of titanium dioxide in the inorganic component is beneficial to increase the SPF value, the content of zinc oxide is beneficial to increase the PA value, and the addition of melanin can increase both values at the same time.
  • the present invention provides a sunscreen composition based on melanin and a preparation method thereof.
  • the sunscreen composition is formed by directly mixing a small amount of melanin, one or a combination of inorganic titanium dioxide and zinc oxide to form a sunscreen composition, which has a synergistic effect when scattering and absorbing ultraviolet rays.
  • the final melanin-based sunscreen composition has a UV protection effect superior to any of the original components.
  • melanin can better stabilize and disperse cosmetics, can effectively resist oxidation, is safe and non-toxic, adjusts the color of cosmetics, avoids various skin problems caused by ultraviolet radiation, and expands the application field of cosmetics.

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Abstract

一种基于黑色素的防晒组合物及其制备方法。所述组合物包括：无机物组分 100重量份；黑色素 0.5-5重量份；所述黑色素的粒径范围是50-400nm；所述无机物为二氧化钛、或二氧化钛和氧化锌；所述无机物组分的粒径范围是20-300nm。制备方法包括：将所述组分按所述用量混合均匀。所述组合物可以有效提高SPF值和PA值，获得防晒效果。

Description

[根据细则37.2由ISA制定的发明名称]　一种基于黑色素的防晒组合物及其制备方法 技术领域
本发明涉及防晒剂技术领域，进一步地说，是涉及一种基于黑色素防晒组合物、制备方法及化妆品。
背景技术
由于环境不断遭到破坏，大气臭氧层变稀、变薄，出现臭氧空洞，紫外线A区(即UVA区)和紫外线B区(即UVB区)照射强度增大，氧自由基增加。太阳光对人体皮肤的伤害主要来自于UVA区与UVB区。UVA对皮肤穿透力强，能够穿透皮肤和真皮层，逐渐破坏弹力纤维，使肌肉失去弹性。引起皮肤松弛，出现皱纹、雀斑和老年斑。若紫外线照射过量，还容易引起皮肤癌。UVB能够达到地面，能使皮肤表面细胞内的核酸或蛋白质变性，皮肤变红、产生红斑(晒斑)，在皮肤上形成黑色素，发生急性皮炎，常称为日光晒斑。所以说紫外线是皮肤健康的大敌。美国每年有近50万名皮肤癌新患者，而研究结果证明，在这些患者中受日光因素影响致癌的占98％以上。
现市面上化妆品中使用的防晒剂主要分为有机小分子类紫外线吸收剂与无机类紫外线屏蔽剂。通过各国国家安全认定的无机类紫外线屏蔽剂主要包括二氧化钛和氧化锌，而各国对有机小分子紫外线吸收剂的种类与最大添加量限定各不相同。无机类紫外线屏蔽剂被认为对人体是无毒安全的。对皮肤没有刺激性，不致癌；但是，此类防晒剂对紫外线的吸收屏蔽效果不显著，二氧化钛对UVB的吸收优于氧化锌，但对于UVA的吸收要弱于氧化锌；且含量少时，防晒化妆品防晒因子(SPF)极低，需要增大添加量并通过需要与有机小分子紫外线吸收剂复配使用。我国《化妆品安全技术规范》(IECIC 2015)中规定，二氧化钛 和氧化锌的最大添加量均为25％，但大量的添加二氧化钛和氧化锌会使得防晒化妆品发白且具厚重感，不易涂膜分散，消费者体验感差。
2019年5月，美国食品药品监督管理局(FDA)率先领导开展研究，比较了不同市售防晒产品中的4种常见活性成分在最大使用条件下的全身暴露情况，研究结果发表于JAMA(Effect of Sunscreen Application Under Maximal Use Conditions on Plasma Concentration of Sunscreen Active Ingredients,The Journal of the American Medical Association,321)。虽然市面上防晒产品的防晒剂成分种类与添加量均在规定内，但研究结果表示，志愿者使用防晒产品一天，其血液中阿伏苯宗(avobenzone)、氧苯酮(oxybenzone)、奥克立林(octocrylene)和依莰舒(ecamsule)等4种化学成分水平都超出当局所规定的每毫升0.5纳克的水平，而且随着防晒产品的重复使用，这些化学成分在血液中的浓度持续增加。可见，有机小分子类的紫外线吸收剂再人体使用过程中依然存在极大的安全隐患。
因此，开发安全无毒且防晒效果好的防晒组分极为迫切。
发明内容
为解决现有技术中出现的问题，本发明提供了一种基于黑色素防晒组合物及制备方法。本发明采用黑色素、二氧化钛、氧化锌复配，可以有效提高SPF值与PA值，获得全紫外波段防护效果优异的防晒组合物，并且安全有效，对人体没有副作用。
本发明的目的之一是提供一种基于黑色素防晒组合物。
所述防晒组合物包括：
无机物组分：100重量份；
黑色素：0.5-5重量份；优选0.5-2重量份；
所述黑色素粒径范围为50-400nm；优选为80-250nm；
所述无机物组分为二氧化钛、或二氧化钛和氧化锌；
所述无机物组分的粒径范围为20-300nm。
所述二氧化钛的晶型优选为金红石型和锐钛矿型；
所述二氧化钛粒径范围优选为20-200nm，更优选为30-100nm。
所述氧化锌粒径范围优选为30-300nm，更优选为50-100nm。
所述无机物为二氧化钛和氧化锌时；
无机物组分100重量份计，
二氧化钛为1-99重量份，氧化锌为1-99重量份，
优选：
二氧化钛为50-99重量份，
氧化锌为1-50重量份。
本发明的目的之二是提供一种本发明目的之一所述的防晒组合物的制备方法。
所述方法包括：
所述组分按所述用量混合均匀后制得所述防晒组合物。
本发明的基于黑色素防晒组合物主要防晒原理为吸收与散射紫外线。
本发明通过筛选合适粒径的黑色素粒子与无机物二氧化钛、氧化锌粒子进行复配，当紫外线作用到介质中粒子时，由于纳米粒子尺寸小于紫外线的波长，或者与紫外线波长相当，粒子中的电子被迫振动(其振动频率与入射光波的频率相同)，成为二次波源，向各个方向发射电磁波，可以散射紫外光。
本发明中黑色素与无机物二氧化钛与氧化锌其中的一种或组合在吸收紫外线时起到协同效果，使最终的基于黑色素防晒组合物具有优于任意一种原组成成分的紫外线吸收效果。这是因为，无机物二氧化钛与氧化锌均属于N型半导体，当受到紫外线的照射时，价带上的电子可吸收紫外线而被激发到导带上，同时产生空穴-电子对，因此二氧化钛与氧化锌具有吸收紫外线的功能。但单纯的二氧化钛与氧化锌只能吸收有限的紫外线，是因为空穴-电子对吸收紫外线能力有限，二氧化钛与氧化锌也无法将吸收到的紫外线转化成热或电能，所以无 法空出空穴-电子对再去吸收紫外线。黑色素可以在极短时间内(50ps)将99％的质子吸收能以非辐射的形式转化为热能(Wavelength-dependent photoacoustic calorimetry study of melanin.Photochem Photobiol,1998,68(3):296-298)，但大量使用黑色素会导致化妆品颜色较深，消费者接受能力降低。本发明将少量的黑色素与无机物二氧化钛与氧化锌其中的一种或组合复配时，在散射紫外线的同时，二氧化钛与氧化锌可以吸收的紫外线，价带上的电子被激发到导带上，同时产生空穴-电子对，再通过与黑色素自身的大π共轭体系转移，这样可以源源不断地通过黑色素进行光热转化，极大幅度的提高紫外线吸收能力。
本发明使用的黑色素及类黑色素为生物大分子，同时兼具抗氧化剂、紫外线吸收剂以及稳定分散剂多重性能，不同于其他有机小分子类的紫外线吸收剂，黑色素本身为人体代谢产物，安全无毒，不引起皮肤过敏反应且具有多重功效。黑色素是一种奇特的生物大分子，广泛存在于动植物体内。它具有紫外光吸收、热耗散、金属离子螯合、温度调节、抗菌性和自由基清除等优越性能(Journal of Physics.D:Applied Physics 2009,42(3):035502)。黑色素纳米颗粒粒径约为100～200nm，公开号为CN 103841947A的中国专利中提到，化妆品中配合少量粒径不足500nm的粒子可以抑制乳化粒子的经时性的聚集且配合双亲性物质形成增稠效果，所以黑色素的添加有利于化妆品中各成分的均匀混合。除此之外，黑色素几乎完全吸收UVA区以及UVB区紫外线，紫外线透过率约为零，且黑色素捕捉清除人体产生的自由基，抗氧化效果明显。且合成类的生物黑色素可以同人体自身产生的黑色素一样可以被内吞，在人表皮角质形成细胞形成保护层，减少紫外线损伤；同时还可以进行细胞代谢，排出体外(Mimicking Melanosomes:Polydopamine Nanoparticles as Artificial Microparasols,ACS Cent.Sci.2017,3,564-569)。
二氧化钛吸收波长290-355nm部分紫外线的作用较强，氧化锌在吸收波长355-385nm部分紫外线的作用要比二氧化钛强，而黑色素在紫外波段都有吸收，所以，将黑色素、二氧化钛、氧化锌复配加入化妆品，可以获得全紫外波段防 护效果优异的个人护理防晒组合物。通过将黑色素与无机防晒组分二氧化钛与氧化锌其中的一种或组合进行复配，形成基于黑色素防晒组合物，并将其掺入化妆品组分中，在不添加任何有机小分子紫外线吸收剂的同时，极大的提高SPF值、PA值与自由基清除能力，有效提高化妆品抗氧化和防紫外线性能，抵抗氧化，防止紫外线对人体损伤，避免因紫外线照射而引起的各类皮肤问题，扩大化妆品应用领域；在确保SPF值的同时，黑色素的加入可以降低二氧化钛与氧化锌的使用量，改善因大量使用无机防晒剂造成的化妆品发白且具厚重感、不易涂膜分散、消费者体验感差等问题。
本申请的防晒组合物不仅仅适用于化妆品，还可以应用于其他的领域，比如：可以使用在一些透明聚合物中用于屏蔽紫外线。
本发明有益的技术效果在于：
1.合适粒径的黑色素粒子与无机物二氧化钛、氧化锌粒子复配后，紫外线作用到介质中粒子时，由于纳米粒子尺寸小于紫外线的波长，可以散射紫外光。
2.少量的黑色素与无机物二氧化钛与氧化锌其中的一种或组合复配，二氧化钛与氧化锌可以将吸收的紫外线源源不断地通过黑色素进行光热转化，极大幅度的提高紫外线吸收能力。
3.少量的黑色素可以在化妆品中起到清除自由基、吸收与散射防紫外线及稳定分散等多重作用；同时改善化妆品颜色，使化妆品易涂抹分散，减小黏腻感。
4.黑色素、二氧化钛、氧化锌复配，可以有效提高SPF值与PA值，获得全紫外波段防护效果优异的防晒组合物。
具体实施方式
下面结合具体实施例对本发明进行具体的描述，有必要在此指出的是以下实施例只用于对本发明的进一步说明，不能理解为对本发明保护范围的限制，本领域技术人员根据本发明内容对本发明做出的一些非本质的改进和调整仍属 本发明的保护范围。
黑色素的制备
(1)黑色素1-2的制备：将多巴胺盐酸盐(上海阿拉丁生化科技股份有限公司提供，规格：AR)溶于去离子水中，搅拌，升温，再加入一定量的碱性物质，4个小时后，反应结束，经过离心，得到黑色素1，粒径为80nm；黑色素2，粒径为200nm；
(2)黑色素3的制备：将多巴(上海阿拉丁生化科技股份有限公司提供，规格：AR)、过氧化二苯甲酰(国药集团化学试剂有限公司，规格：AR)溶于二甲亚砜溶剂(国药集团化学试剂有限公司，规格：AR)中，调节溶液呈酸性，反应20时间后，经离心可到黑色素3，粒径为320nm；
(3)黑色素4的制备：从市场购买墨鱼(无锡南禅寺菜市场)，取墨鱼墨汁，经离心得到黑色素4，粒径为400nm。
二氧化钛1粒径为60nm，金红石型；
二氧化钛2粒径为100nm，金红石型；
氧化锌1粒径为50nm；
氧化锌2粒径为100nm；
实施例1～12
配方见表1，各组分混合均匀后制得防晒组合物
表1
Figure PCTCN2020095256-appb-000001
Figure PCTCN2020095256-appb-000002
试验：
化妆品基础配方见表2
表2
Figure PCTCN2020095256-appb-000003
方法步骤如下：
在一定温度下溶解油相和水相成分，制备亲油性、亲水性混合物并通过均质机混合均匀；冷却后，向其中加入适量pH稳定剂制备防晒组合物化妆品。
对比例1
以化妆品基础配方100重量份计，加入68重量份二氧化钛1，500重量份水；
对比例2
以化妆品基础配方100重量份计，加入68重量份氧化锌1，500重量份水；
对比例3
以化妆品基础配方100重量份计，加入34重量份二氧化钛1，34重量份氧化锌1，500重量份水；
实施例13
以化妆品基础配方100重量份计，加入68.34重量份(68重量份二氧化钛1，0.34重量份黑色素1)实施例1制得的防晒组合物；500重量份水；
实施例14
以化妆品基础配方100重量份计，加入68.68重量份(68重量份二氧化钛1，0.68重量份黑色素1)实施例2制得的防晒组合物；500重量份水；
实施例15
以化妆品基础配方100重量份计，加入69.36重量份(68重量份二氧化钛1，1.36重量份黑色素1)实施例3制得的防晒组合物；500重量份水；
实施例16
以化妆品基础配方100重量份计，加入100.68重量份(约100重量份二氧化钛1，0.68重量份黑色素1)实施例10制得的防晒组合物；500重量份水；
实施例17
以化妆品基础配方100重量份计，加入68.68重量份(34重量份二氧化钛1，34重量份氧化锌1，0.68重量份黑色素2)实施例11制得的防晒组合物；500重量份水；
评价项目
1、SPF测试
在石英玻璃板上均匀涂布各试样2mg/cm 2，自然干燥15分钟。之后，在距离玻璃板上方10mm处进行紫外线照射。紫外线透过率分析仪(美国Labsphere  Inc.)在280-400nm范围内在石英玻璃板上随机5处检测，得出SPF值，取五次平均值，记为SPF。
2、PA测试
在石英玻璃板上均匀涂布各试样2mg/cm 2，自然干燥15分钟。之后，在距离玻璃板上方10mm处进行紫外线照射。紫外线透过率分析仪(美国Labsphere Inc.)在280-400nm范围内在石英玻璃板上随机5处检测，得出PFA值，PFA在2-3记为PA+，PFA在4-7记为PA++，PFA在8-15记为PA+++，PFA大于等于16记为PA++++。
3、乳化稳定性
肉眼观察检测被测样品在25℃下保存一个月后的外观，按照以下基准评价。
◎：试样均匀稳定；
○：试样中观察到乳状液分离；
△：试样中观察到浮油；
×：试样完全分离。
4、使用感
选取10名志愿者，将各试样涂布于脸上，对吸收时的黏腻情况进行调查，按照以下基准评价。
◎：9-10人回答不黏腻；
○：6-8人回答不黏腻；
△：3-5人回答不黏腻；
×：0-2人回答不黏腻。
测试结果见表3
表3
Figure PCTCN2020095256-appb-000004
通过表3中所列的对比例1-3数据可以看出，单纯的二氧化钛对UVB的抵御效果优于氧化锌，而氧化锌对于UVA的防护效果优于二氧化钛，但10％含量的添加已经让部分消费者使用感下降。实施例13-15与对比例1相比，说明黑色素的添加，可以大幅度的提高SPF与PA值，且随着黑色素含量的增加而增加；同时，少量黑色素的添加即可减少化妆品的黏腻感，提升体验感。实施例16数据同实施例14比较说明，在相同的黑色素含量下，二氧化钛含量的增加，化妆品的SPF值增大，但是二氧化钛的过多，会使化妆品整体颜色过白，粘稠感增加，消费者使用感下降；实施例17与对比例1-3，无机物组分中二氧化钛的含量有利于提高SPF值，氧化锌的含量有利于提高PA值，而黑色素的加入可同时提高两者数值，形成紫外UVB-UVA全段防护。
本发明提供了一种基于黑色素防晒组合物及其制备方法，通过直接将少量黑色素与无机物二氧化钛与氧化锌一种或组合混合形成防晒组合物，在散射与吸收紫外线时起到协同效果，使最终的基于黑色素防晒组合物具有优于任意一种原组成成分的紫外线防护效果。同时，黑色素能更好的稳定分散化妆品，可有效抵抗氧化，安全无毒，调节化妆品颜色，避免因紫外线照射而引起的各类皮肤问题，扩大化妆品应用领域。
所属领域的普通技术人员应当理解：以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种基于黑色素的防晒组合物，其特征在于所述防晒组合物包括：
    无机物组分：100重量份；
    黑色素：0.5-5重量份；
    所述黑色素粒径范围为50-400nm；
    所述无机物组分为二氧化钛、或二氧化钛和氧化锌；
    所述无机物组分的粒径范围为20-300nm。
  2. 如权利要求1所述的防晒组合物，其特征在于：
    无机物组分：100重量份；
    黑色素：0.5-2重量份。
  3. 如权利要求1所述的防晒组合物，其特征在于：
    黑色素粒径范围为80-250nm。
  4. 如权利要求1所述的防晒组合物，其特征在于：
    所述二氧化钛的晶型为金红石型和锐钛矿型；
    所述二氧化钛粒径范围为20-200nm。
  5. 如权利要求4所述的防晒组合物，其特征在于：
    所述二氧化钛粒径范围为30-100nm。
  6. 如权利要求1所述的防晒组合物，其特征在于：
    所述氧化锌粒径范围为30-300nm。
  7. 如权利要求6所述的防晒组合物，其特征在于：
    所述氧化锌粒径范围为50-100nm。
  8. 如权利要求1所述的防晒组合物，其特征在于：
    所述无机物为二氧化钛和氧化锌；
    无机物组分 100重量份计，
    二氧化钛   1-99重量份；
    氧化锌     1-99重量份。
  9. 如权利要求8所述的防晒组合物，其特征在于：
    无机物组分 100重量份计，
    二氧化钛   50-99重量份；
    氧化锌     1-50重量份。
  10. 一种如权利要求1～9之一所述的防晒组合物的制备方法，其特征在于所述方法包括：
    所述组分按所述用量混合均匀后制得所述防晒组合物。
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CN108236600A (zh) * 2018-01-02 2018-07-03 刘莹艳 一种防晒霜

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