CN113332169B

CN113332169B - Personal care sunscreen composition, preparation method and application

Info

Publication number: CN113332169B
Application number: CN202010137491.XA
Authority: CN
Inventors: 东为富; 李婷; 黎赛瑶; 汪洋; 杨伟军
Original assignee: Jiangnan University
Current assignee: Jiangnan University
Priority date: 2020-03-02
Filing date: 2020-03-02
Publication date: 2022-03-08
Anticipated expiration: 2040-03-02
Also published as: CN113332169A; WO2021174715A1

Abstract

The invention discloses a personal care sunscreen composition, a preparation method and application thereof. The composition comprises: natural macromolecular additive, inorganic ultraviolet screening agent, water phase and/or oil phase; the natural macromolecular additive comprises the following components in parts by weight based on 100 parts by weight of the sun-screening composition: 0.01-5 parts by weight; inorganic ultraviolet screening agent: 4-25 parts by weight; water phase or oil phase ingredients: the balance; the natural macromolecular additive is melanin or the combination of the melanin and lignin compounds; the inorganic ultraviolet screening agent is titanium dioxide, or titanium dioxide and zinc oxide. A safe and excellent sunscreen effect melanin-containing personal care composition is prepared by using safe and non-toxic melanin, lignin compounds, inorganic ultraviolet screening agents and other cosmetically acceptable finished products without adding any ultraviolet absorbent with small molecular chemical components.

Description

Personal care sunscreen composition, preparation method and application

Technical Field

The invention relates to the field of daily necessities, in particular to a personal care sunscreen composition, a preparation method and application.

Background

Because the environment is continuously damaged, the atmospheric ozone layer becomes thin and thin, ozone holes appear, the irradiation intensity of an ultraviolet A region (namely UVA region) and an ultraviolet B region (namely UVB region) is increased, and oxygen free radicals are increased. The damage of sunlight to human skin mainly comes from UVA area and UVB area. UVA has strong penetrating power to skin, and can penetrate skin and dermis to gradually destroy elastic fibers and make muscles lose elasticity. Causing skin to relax, and wrinkles, freckles and age spots to appear. When the ultraviolet radiation is excessively applied, skin cancer is also easily caused. UVB reaches the ground and denatures nucleic acids or proteins in cells on the skin surface, causing redness of the skin, erythema (sunburn), melanin formation on the skin, and acute dermatitis, often referred to as sunburn. Therefore, ultraviolet rays are a big enemy of skin health. There are nearly 50 million new skin cancer patients in the united states each year, and the results of the study demonstrate that over 98% of these patients are carcinogenic by sun exposure.

The sunscreen agents used in the cosmetics on the market are mainly classified into organic small molecule ultraviolet absorbers and inorganic ultraviolet screening agents. The inorganic ultraviolet screening agent which is determined by the national safety of each country mainly comprises titanium dioxide and zinc oxide, and the limitation of each country to the type and the maximum addition amount of the organic micromolecular ultraviolet absorbent is different. Inorganic ultraviolet screening agents are considered to be non-toxic and safe to humans. No irritation to skin and no carcinogenesis; however, the sunscreen agent has no obvious effect of absorbing and shielding ultraviolet rays, and the titanium dioxide absorbs UVB due to zinc oxide, but absorbs UVA weaker than zinc oxide; when the content is small, the Sun Protection Factor (SPF) of the sun protection cosmetic is extremely low, and the addition amount needs to be increased and the sun protection cosmetic needs to be compounded with an organic small molecular ultraviolet absorbent for use. According to the regulations in the technical safety standards for cosmetics (IECIC2015) of China, the maximum addition amounts of titanium dioxide and zinc oxide are 25%, but the addition of a large amount of titanium dioxide and zinc oxide can make the sunscreen cosmetic whitish and thick, the sunscreen cosmetic is not easy to coat and disperse, and the experience of consumers is poor.

In 5 months 2019, The U.S. Food and Drug Administration (FDA) led to research, comparing The total exposure of 4 common Active Ingredients in different commercially available Sunscreen products Under The maximum Use condition, and The research results are reported in JAMA (Effect of Sun Application underlying Large Use Conditions on Plasma concentrationof Sun Active Ingredients, The Journal of The American Medical Association, 321). Although the types and the addition amounts of the sunscreen ingredients of the sunscreen products on the market are within the regulations, the research results show that 4 chemical ingredients such as avobenzone (avobenzone), oxybenzone (oxybenzone), octocrylene (octocrylene) and ecamsule (ecamsole) in the blood of a volunteer using the sunscreen product for one day exceed the 0.5 nanogram per milliliter level regulated by the authorities, and the concentrations of the chemical ingredients in the blood continuously increase along with the repeated use of the sunscreen product. Therefore, the organic micromolecule ultraviolet absorbent still has great potential safety hazard in the use process of human bodies.

Lignin is added in a microcapsule form in the research on the efficient construction and application of lignin/chemical sunscreen composite microcapsules, but the excellent sunscreen index can be shown only by compounding the lignin with a chemical free sunscreen; Lignin/TiO₂Preparation of composite nanoparticles and sunscreen application thereof, in the text, the lignin modified titanium dioxide composite nanoparticles are added into cosmetics, the SPF values of sunscreen cream after 10% and 20% of solvent type lignin modified titanium dioxide are added are respectively 43.88 and 72.83, but the early-stage modification is needed, the addition amount is large, and the lignin is not listed in technical safety and safety standards of cosmetics (IECIC 2015).

Therefore, the development of safe and nontoxic sunscreen cosmetics with good sunscreen effect is urgent.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a personal care sunscreen composition, a preparation method and application. The primary sunscreen principle of the personal care sunscreen composition of the present invention is the absorption and scattering of ultraviolet light. A safe and excellent sunscreen effect melanin-containing personal care composition is prepared by using safe and non-toxic melanin, lignin compounds, inorganic ultraviolet screening agents and other cosmetically acceptable finished products without adding any ultraviolet absorbent with small molecular chemical components.

It is an object of the present invention to provide a personal care sunscreen composition.

The composition comprises:

natural macromolecular additive, inorganic ultraviolet screening agent, water phase and/or oil phase;

based on 100 parts by weight of the total sunscreen composition,

natural macromolecular additive: 0.01-5 parts by weight; preferably 0.05 to 2.5 parts by weight;

inorganic ultraviolet screening agent: 4-25 parts by weight; preferably 8 to 15 parts by weight;

water phase or oil phase ingredients: the balance;

the natural macromolecular additive is melanin or the combination of the melanin and lignin compounds;

the melanin comprises melanin or melanoid prepared by natural extraction, chemical synthesis or biological fermentation;

the lignin compound can be dissolved in water, and is preferably lignosulfonate;

the water phase and/or oil phase is a permitted water phase or oil phase ingredient commonly used in cosmetics.

The inorganic ultraviolet screening agent is titanium dioxide, or titanium dioxide and zinc oxide;

the particle size range of the melanin is 50-400 nm; is 80-250 nm;

the particle size range of the inorganic ultraviolet screening agent is 20-300 nm.

Wherein the content of the first and second substances,

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.

When the natural macromolecular additive is the combination of melanin and lignin compounds, the melanin accounts for 10-50 parts by weight and the lignin compounds account for 50-90 parts by weight based on 100 parts by weight of the natural macromolecular additive.

When the inorganic ultraviolet screening agent is the combination of nano titanium dioxide and nano zinc oxide, the nano titanium dioxide accounts for 1-99 parts by weight, preferably 50-90 parts by weight, and the nano zinc oxide accounts for 1-99 parts by weight, preferably 10-50 parts by weight, based on 100 parts by weight of the inorganic ultraviolet screening agent.

In the invention, melanin substances and lignin compounds in a used cosmetic raw material name catalog (IECIC2015) are selected as components of the composition by screening, and melanin particles with proper particle size are selected to be compounded with inorganic ultraviolet screening agents, namely nano titanium dioxide and nano zinc oxide particles. When ultraviolet light is applied to particles in a medium, electrons in the particles are forcibly vibrated (the vibration frequency is the same as the frequency of incident light) by the size of the nanoparticles being smaller than or equal to the wavelength of the ultraviolet light, and become secondary wave sources, and electromagnetic waves are emitted in all directions to scatter the ultraviolet light.

The melanin and lignin compounds, and one or the combination of the nano titanium dioxide and the nano zinc oxide play a synergistic effect when absorbing ultraviolet rays, so that the final personal care sunscreen composition has an ultraviolet protection effect superior to that of any one of the original components. This is because titanium dioxide and zinc oxide are both N-type semiconductors, and when they are irradiated with ultraviolet rays, electrons in the valence band absorb the ultraviolet rays and are excited to the conduction band, and at the same time, hole-electron pairs are generated, and thus they have a function of absorbing ultraviolet rays. However, titanium dioxide and zinc oxide alone can only absorb limited ultraviolet rays and cannot convert the ultraviolet rays. Melanin can convert 99% of the proton absorption energy into heat energy in a non-radiative form in a very short time (50ps) (wavelet-dependent photo cosmetic study of skin. photo. biol, 1998, 68 (3): 296-298), but the use of melanin in large amounts leads to a darker color and a reduced consumer acceptance of the cosmetic. The lignin compound has a conjugated electron system such as an aromatic ring, a double bond, a carbonyl group, a phenolic hydroxyl group, etc., and can receive transferred electrons, etc. Therefore, when a small amount of melanin, lignin compounds and one or a combination of inorganic titanium dioxide and zinc oxide are compounded, ultraviolet rays can be absorbed by the titanium dioxide and the zinc oxide while the ultraviolet rays are scattered, electrons on a valence band are excited to a conduction band, hole-electron pairs are generated at the same time, and then the hole-electron pairs are transferred through a conjugated system such as large pi, n-pi and p-pi of the melanin and the lignin compounds, so that the photothermal conversion can be continuously carried out through the melanin, and the ultraviolet absorption capacity is greatly improved.

The melanin, the melanoid and the lignin compound used in the invention meet the requirements of the catalogue of names of used cosmetic raw materials (IECIC2015), the melanin has multiple performances of an antioxidant, an ultraviolet absorbent and a stabilizing dispersant, is different from other organic micromolecule ultraviolet absorbents, is a human body metabolite, is safe and non-toxic, does not cause skin anaphylaxis and has multiple effects. Melanin is a peculiar biological macromolecule and widely exists in animals and plants. It has excellent properties such as ultraviolet light absorption, heat dissipation, metal ion chelation, temperature regulation, antibacterial property and radical scavenging (Journal of Physics.D: Applied Physics 2009, 42 (3): 035502). The melanin nanoparticles have a particle size of about 100-200 nm, and it is mentioned in chinese patent publication No. CN 103841947 a that the addition of melanin facilitates the uniform mixing of the components in the cosmetic because the addition of melanin in the cosmetic can inhibit the aggregation of emulsified particles over time by adding a small amount of particles having a particle size of less than 500nm and form a thickening effect by adding an amphiphilic substance. In addition, the melanin almost completely absorbs ultraviolet rays in UVA and UVB regions, the ultraviolet transmittance is about zero, and the melanin captures and removes free radicals generated by a human body, so that the antioxidant effect is obvious. The synthesized biological melanin can be endocytosed like melanin generated by a human body, and a protective layer is formed on human epidermal keratinocytes, so that ultraviolet injury is reduced; at the same time, it can also be metabolized and excreted (Mimicking Melanosomes: Polydopamine Nanoparticles as Artificial Microparaols, ACS Cent. Sci.2017, 3, 564-569).

The titanium dioxide has stronger effect of absorbing the ultraviolet rays with the wavelength of 290-355nm, the zinc oxide has stronger effect of absorbing the ultraviolet rays with the wavelength of 355-385nm than the titanium dioxide, and the melanin and the lignin compounds can absorb the ultraviolet wave bands, so the melanin, the lignin compounds, the titanium dioxide and the zinc oxide are compounded and added into the cosmetics, and the personal care sunscreen composition with excellent protection effect on the whole ultraviolet wave bands can be obtained. Through compounding melanin, lignin compounds, one or a combination of inorganic ultraviolet screening agents titanium dioxide and zinc oxide, and adding the compound into cosmetic components, the SPF value, the PA value and the free radical scavenging capacity are greatly improved while no organic small-molecule ultraviolet absorbent is added, the oxidation resistance and the ultraviolet resistance of the cosmetic are effectively improved, the oxidation is resisted, the ultraviolet rays are prevented from damaging human bodies, various skin problems caused by ultraviolet irradiation are avoided, and the application field of the cosmetic is expanded; the addition of the melanin and lignin compounds can reduce the usage amount of titanium dioxide and zinc oxide while ensuring the SPF value, and solves the problems of whitening and heavy feeling of cosmetics, difficult film dispersion, poor experience of consumers and the like caused by using a large amount of inorganic sunscreen agents.

It is a further object of the present invention to provide a method for preparing a personal care sunscreen composition.

The method comprises the following steps:

firstly, dispersing or dissolving natural macromolecular additive and inorganic ultraviolet screening agent in water to form uniform water phase component, then mixing with oil phase to obtain the invented sunscreen composition.

It is a further object of the present invention to provide a personal care sunscreen composition for use in consumer products.

The personal care sunscreen composition of the present invention can be used in a variety of sunscreen and household products, such as: sunscreen lotion, sunscreen cream, sunscreen spray, sunscreen lotion, sunscreen liquid, sunscreen powder, sunscreen gel, isolation lotion, isolation cream, isolation lotion, BB cream, no-wash hair spray, shampoo, hair conditioner, toner and the like.

The beneficial technical effects of the invention are as follows:

1. the melanin and lignin compounds meet the catalogue of used cosmetic raw material names (IECIC2015), are natural macromolecules, are safe and non-toxic, are selected to be compounded with titanium dioxide and zinc oxide particles with proper particle sizes, and can scatter ultraviolet light to form physical sun protection when ultraviolet light acts on particles in a medium because the size of the nanoparticles is smaller than the wavelength of the ultraviolet light.

2. A small amount of melanin and lignin compounds are compounded with one or a combination of nano titanium dioxide and zinc oxide, and the titanium dioxide and the zinc oxide can continuously perform photothermal conversion on absorbed ultraviolet rays through the melanin and lignin compounds, so that the ultraviolet absorption capacity is greatly improved, and chemical sunscreen is formed.

3. A small amount of melanin can play multiple roles of eliminating free radicals, absorbing and scattering ultraviolet-proof, stably dispersing and the like in cosmetics; meanwhile, the color of the cosmetic is improved, the cosmetic is easy to apply and disperse, and the sticky feeling is reduced.

4. The melanin, the lignin compounds, the titanium dioxide and the zinc oxide are added into the cosmetics, so that the SPF value and the PA value can be effectively improved, and the personal care sunscreen composition with excellent full ultraviolet band protection effect is obtained.

Drawings

FIG. 1 is a comparative digital photograph of comparative example 1, example 7;

FIG. 2 is a comparative digital photograph of comparative example 1, examples 1-3;

fig. 3 is a comparative digital photograph of comparative example 4, comparative example 6, and example 14.

In FIG. 1, the color of the composition of comparative example 1 is white, the color of the composition of example 1 is lighter off-white, and the color of the composition of example 7 is gray, which illustrate that at the same content, the color of the cosmetic composition increases as the particle size of the melanin increases, and within certain limits, the selection of melanin having a smaller particle size is advantageous for the preparation of a cosmetic composition having a lighter color;

in FIG. 2, the composition of comparative example 1 is white, the compositions of examples 1 and 2 are lighter off-white, and the composition of example 3 is off-white, which shows that at the same particle size, the color of the cosmetic composition increases with the increase of the content of melanin, and within a certain range, the selection of the proper content of melanin is beneficial to prepare the cosmetic composition with lighter color;

in FIG. 3, the color of the composition of comparative example 4 is chocolate, the color of the composition of comparative example 6 is light curry, and the color of the composition of example 14 is light cream yellow, which shows that the addition of a certain content of inorganic ultraviolet screening agent is beneficial to preparing the cosmetic composition with lighter color, and meanwhile, the replacement of part of lignin compounds with the same content of small-particle-size melanin is beneficial to preparing the cosmetic composition with lighter color.

Detailed Description

While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.

Preparation of melanin

(1) Preparation of melanin 1-2: dissolving dopamine hydrochloride (specification: AR provided by Shanghai Aladdin Biotechnology Co., Ltd.) in deionized water, stirring, heating, adding a certain amount of alkaline substance, reacting for 4 hours, and centrifuging to obtain melanin 1 with particle size of 80 nm; melanin 2, particle size 200 nm;

(2) preparation of melanin 3: dissolving DOPA (specification: AR provided by Shanghai Aladdin Biotechnology Co., Ltd.) and dibenzoyl peroxide (specification: AR) in dimethyl sulfoxide solvent (specification: AR) to adjust the solution to be acidic, reacting for 20 hours, and centrifuging to obtain melanin 3 with particle size of 320 nm;

(3) preparation of melanin 4: cuttlefish (Wuxi Nanchan Temple vegetable market) is purchased from the market, and cuttlefish ink is taken and centrifuged to obtain melanin 4 with the particle size of 400 nm.

Preparing lignin compounds:

(1) preparing light-color lignosulfonate, which is marked as lignosulfonate 1, according to the method in the color reduction of lignin and the application of the lignosulfonate in lignin-based chemicals;

(2) the lignosulfonate is purchased from Chishiai (Shanghai) chemical industry development Co., Ltd and is marked as lignosulfonate 2.

The particle size of the titanium dioxide 1 is 60nm and rutile type, and the particle size of the titanium dioxide 2 is 100nm and rutile type;

the particle size of the zinc oxide 1 is 50nm, and the particle size of the zinc oxide 2 is 100 nm.

Examples 1 to 15 and comparative examples 1 to 9

The formulations of examples 1 to 15 and comparative examples 1 to 9 are shown in Table 1.

Comparative examples 1 to 9 and examples 1 to 15 were obtained based on the natural macromolecular additive sunscreen composition cosmetics by using the formulation of table 1 and the preparation method commonly used in the above field, based on 100 parts by weight of the total amount of the cosmetics. Wherein, no natural macromolecular additive is added in comparative examples 1-3; comparative examples 4-7 lignin-based compound was added only; the inorganic ultraviolet-screening agents in comparative examples 8 to 9 were added with zinc oxide. In examples 1 to 15, melanin and lignin compounds of different particle sizes and weight parts and titanium dioxide, titanium dioxide and zinc oxide of different particle sizes and weight parts were added.

Wherein, the comparative example 7 refers to chapter six in "color reduction of lignin and its application in lignin-based chemicals": preparation and evaluation of light-colored Lignin-based sunscreen preparation sample, the content of light-colored Lignin sulfonate, i.e., Lignin sulfonate 1, was 0.5%.

The method comprises the following steps:

dissolving oil phase and water phase components at a certain temperature, preparing a lipophilic and hydrophilic mixture, and uniformly mixing by a homogenizer; after cooling, a suitable amount of a pH stabilizer is added thereto to prepare a sunscreen composition cosmetic.

As can be seen from the data of comparative examples 1-3 listed in table 1, titanium dioxide alone is better at protecting UVB than zinc oxide, while zinc oxide is better at protecting UVA than titanium dioxide, but the addition of 10% level has reduced the consumer appeal in part. Examples 1-4 compared to comparative example 1, demonstrate that the addition of melanin can dramatically increase the SPF and PA values, and increases with the increase in melanin content; meanwhile, the addition of a small amount of melanin can reduce the sticky feeling of the cosmetics and improve the experience feeling. Examples 5-7 demonstrate that melanin has a small particle size and a high cosmetic SPF value. The data of example 2 and examples 8-11 show that the SPF value of the cosmetic is increased due to the increase of the content of titanium dioxide, but the use feeling of consumers is reduced due to the excessive content; comparing example 8 with comparative example 1, it can be seen that, after 0.1% of melanin is added, the titanium dioxide content in the cosmetic ingredients can be reduced to 4%, and the SPF value and the PA value are still superior to those of the comparative example, and meanwhile, the reduction of the titanium dioxide content can reduce the sticky feeling of the cosmetic and increase the experience feeling of consumers. Examples 12-13, in comparison with comparative example 3, show that the content of titanium dioxide in the mineral component contributes to an increase in the SPF value, the content of zinc oxide contributes to an increase in the PA value, and the addition of melanin increases both values simultaneously, resulting in full protection against uv UVB-UVA.

Comparative example 8 compared to example 1, it can be shown that the SPF sunscreen effect of titanium dioxide alone as an inorganic sunscreen is better than that of zinc oxide alone, but the PA value is slightly lower; comparative example 9 compares with examples 12-13, showing that the combined SPF sunscreen effect of titanium dioxide and zinc oxide is better than that of zinc oxide alone in inorganic sunscreens, but the PA value of the composition decreases when the zinc oxide component is reduced more in the ratio; comparative example 4 and comparative example 7 show that only the lignin compound is added, the sunscreen effect is achieved, but the SPF value and the PA value are extremely low, and the practical prospect is not achieved; the data of comparative examples 5 and 6 show that the sun-screening effect can be improved by compounding the lignin compound and the titanium dioxide. Compared with the comparative examples 1, 6 and 2 and the examples 14 to 15, the cosmetics prepared by compounding the melanin and the lignin compound have a sunscreen effect higher than that of any single component, so that the sunscreen composition prepared by compounding the melanin and the lignin compound with titanium dioxide and zinc oxide can better promote the conversion and absorption of ultraviolet rays, form a synergistic effect and form ultraviolet UVB-UVA full-section protection.

The invention provides a personal care sunscreen composition, which is formed by directly mixing one or a combination of melanin, lignin compounds, inorganic ultraviolet screening agent nano titanium dioxide and nano zinc oxide and other cosmetically acceptable components, is safe and nontoxic, and can perform photothermal conversion on absorbed ultraviolet rays while scattering the ultraviolet rays; in addition, the melanin can stably disperse the cosmetics better, can effectively resist oxidation, simultaneously improves the color of the cosmetics, enables the cosmetics to be easily smeared and dispersed, reduces the sticky feeling and expands the application field of the cosmetics.

Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.

Claims

1. A personal care sunscreen composition characterized in that said composition comprises:

based on 100 parts by weight of the total sunscreen composition,

natural macromolecular additive: 0.01-5 parts by weight;

inorganic ultraviolet screening agent: 4-25 parts by weight;

water phase or oil phase ingredients: the balance;

the particle size range of the melanin is 50-400 nm;

2. The personal care sunscreen composition of claim 1 wherein:

based on 100 parts by weight of the total sunscreen composition,

natural macromolecular additive: 0.05-2.5 parts by weight;

inorganic ultraviolet screening agent: 8-15 parts by weight;

water phase or oil phase ingredients: and (4) the balance.

3. The personal care sunscreen composition of claim 1 wherein:

the particle size range of the melanin is 80-250 nm; and/or the presence of a gas in the gas,

the crystal form of the titanium dioxide is rutile type and anatase type;

the particle size range of the titanium dioxide is 20-200 nm; and/or the presence of a gas in the gas,

the particle size range of the zinc oxide is 30-300 nm.

4. The personal care sunscreen composition of claim 3 wherein:

the particle size range of the titanium dioxide is 30-100 nm.

5. The sunscreen composition of claim 3 wherein:

the particle size range of the zinc oxide is 50-100 nm.

6. The personal care sunscreen composition of claim 1 wherein:

the lignin compound is lignosulfonate.

7. The personal care sunscreen composition of claim 1 wherein:

8. The personal care sunscreen composition of claim 1 wherein:

when the inorganic ultraviolet screening agent is the combination of nano titanium dioxide and nano zinc oxide, the weight of the nano titanium dioxide is 1 to 99 parts by weight and the weight of the nano zinc oxide is 1 to 99 parts by weight based on 100 parts by weight of the inorganic ultraviolet screening agent.

9. The personal care sunscreen composition of claim 8 wherein:

when the inorganic ultraviolet screening agent is the combination of nano titanium dioxide and nano zinc oxide, the weight of the nano titanium dioxide is 50-90 parts and the weight of the nano zinc oxide is 10-50 parts based on 100 parts of the inorganic ultraviolet screening agent.

10. A method of preparing a personal care sunscreen composition according to any of claims 1 to 9, characterized in that the method comprises:

11. Use of a personal care sunscreen composition according to any one of claims 1 to 9 in the manufacture of a commodity.