[해설논문] 한국재료학회지 https://doi.org/10.3740/MRSK.2023.33.3.

87
Korean J. Mater. Res.
Vol. 33, No. 3 (2023)

Component, Formulation and Regulatory of Sunscreen Materials:

A Brief Review
Firi Oktavia Hariani1, Mohammad Adam Jerusalem2, Iqmal Tahir3,
Maisari Utami4, Won-Chun Oh5, and Karna Wijaya3†
1
Department of Family Welfare Education, Faculty of Engineering, Universitas Negeri Yogyakarta,
Yogyakarta 55281, Indonesia
2
Department of Family Welfare Education and Department of Industrial Engineering, Faculty of Engineering,
Universitas Negeri Yogyakarta, Yogyakarta 55281, Indonesia
3
Department of Chemistry, Faculty of Mathematics and Natural Science, Universitas Gadjah Mada,
Yogyakarta 55281, Indonesia
4
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Islam Indonesia,
Yogyakarta 55584, Indonesia
5
Department of Advanced Materials and Engineering, Hanseo University, Seosan 31962, Republic of Korea

(Received January 25, 2023 : Revised February 25, 2023 : Accepted March 13, 2023)

Abstract Exposure to ultraviolet (UV) light is often associated with skin damage, sometimes very serious, and in recent times
has received particular attention as a health risk. As a result, the proper use of sunscreen has long been recommended to protect
against skin damage. The continued increase in the use of sunscreen may be linked to increased information about the risk of
melanoma and non-melanoma skin cancer caused by prolonged exposure to ultraviolet rays. Natural and harmless materials that
block and prevent UV light have emerged as essential household items in the field of skin beauty. New materials need to be
considered and evaluated in relation to ultraviolet rays and their harmful effects. This study aims to explain the effect of UV
exposure on human skin, the classification of sunscreens, the application of zeolite, nano clay, and LDH in sunscreen formu-
lations, as well as the regulation of this service in various countries around the world.
Key words sunscreen material, LDH, formulation, regulatory, ultraviolet.

1. Introduction human body can be caused by various factors, including du-

ration of sun exposure, geographic location, age, skin color,
Indonesia is located on the equator allow exposure to behavior, and activities.5-7)
sunlight with high intensity. Light exposure sun can cause Sunscreen is a topical product that consists of certain che-
damage to skin from ultraviolet (UV) radiation. In addition, micals that allow for its absorptive and reflective characte-
the resulting climate change by global warming can cause ristics on UV rays. UV rays are divided into UVA, UVB, and
increasing exposure to UV rays. Excessive exposure to ultra- UVC with wavelengths of 320~400 nm, 290~400 nm, and
violet (UV) radiation can cause redness (erythema) of the skin 200~290 nm, respectively.8) Sunscreens protect the skin from
as a result of an inflammatory response.1,2) In recent studies, UV radiation, which can cause cancer. Furthermore, it can
it has been discovered that long-term UV exposure can lead also prevent other effects, such as aging and pigmentation.9)
to the development of skin cancer, in which melanocytes Sunscreen is often used as a skin protector from UV radi-
transform into melanoma cells.3,4) Damages to this part of the ation, particularly during outdoor activities.10) Evidence of

†
Corresponding author
E-Mail : [email protected] (K. Wijaya, Univ. Gadjah Mada)

Materials Research Society of Korea, All rights reserved.

This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creative-
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original work is properly cited.

87
88 Firi Oktavia Hariani, Mohammad Adam Jerusalem, Iqmal Tahir, Maisari Utami, Won-Chun Oh, and Karna Wijaya

its protection from UV exposure has been reported.11) negative effects of this radiation. Using sunscreens to protect
Based on the formulation, sunscreens can be divided into the skin from harmful UVA and UVB rays have been shown
two categories, namely chemical-based and mineral-based. to provide long-term benefits in reducing the risk of cancer
Many materials have developed for its manufacturing, bring- and preventing signs of aging.23) Additionally, the literature
ing hybrid sunscreens. The safety and comfort of using this stated that regular use of this device can delay aging in human
device are critical. The products should meet testing stan- skin.24)
dards to ensure that it does not cause a burning sensation or Ultra Violet (UV) rays have many effects on the skin, ran-
irritation to the skin and cause pain to the eyes and skin.12) ging from mild to acute. Studies stated that exposure to UV
This article reviews the application of inorganic materials light without any protection for the skin can cause premature
in sunscreen formulations. The effect of UV rays and their aging. It also explains that this radiation is responsible for
potential exposure on human skin are also expanded along 80 % of the visible signs of facial aging.25) Exposure to UV
with the regulation, specifically in Indonesia. Mineral-based light can lead to the thickening of the epidermis, which can be
sunscreen was appointed because it minimizes irritating ef- called hyperkeratosis.26) Bright skin color is one of the most
fects, making it more suitable for sensitive skin, environmen- significant risk factors for melanoma development. Further-
tally friendly, and provides maximum SPF/PA scale protec- more, the rays can damage keratinocytes and melanocytes,
13)
tion. resulting in more disruption of the skin.26) Exposure to low-
intensity radiation can cause DNA damage in either light or
2. Effect of UV Exposure on the Skin dark skin.27)

UV rays have positive and negative effects on human skin. 3. Classification of Sunscreen Agents
Regarding the former, 90 % of vitamin D is produced by skin
exposed to this radiation over a certain period.14) The human Sunscreen is a product designed to protect human skin
epidermis has a natural photoprotection mechanism through from UV radiation. It can contain one or more UV filters and
the production of melanin and melanocytes. However, such a broadly be classified into tropical and systemic agents. Tro-
mechanism is insufficient when excessive and long-term sun pical sunscreen can be divided into three categories, namely
exposure is involved.9,15) UVA and UVB rays can cause organic, inorganic, and hybrid compound, as shown in Fig. 1.
premature aging to melanoma.16,17) UVA with a wavelength In general, sunscreen products are divided into inorganic and
of 320~400 nm has carcinogenic properties and can damage organic UV filters, each of which has a specific mechanism
DNA, hence, it plays an essential role in melanoma.18) Skin of action when exposed to sunlight. As opposed to organic
exposed to UVB rays for an extended period without any pro- blockers, which absorb high-energy UV radiation, inorganic
tection is susceptible to harmful effects, namely the damage substances reflect and scatter light. Scientists have recently
to cells and DNA in human keratinocytes that can cause can- become interested in hybrid materials that combine the qua-
cer.19) Excessive UV exposure can cause skin malignancies, lities of organic and inorganic substances as a potential sun-
and one of the most prominent groups are squamous cell car- screen ingredient.
cinoma (SCC), basal cell carcinoma (BCC), and malignant
melanoma.20) The ratio of UVA and UVB can be affected by 3.1. Organic compound based sunscreen
time, season, altitude, and latitude, hence, direct exposure to Organic compound-based sunscreens work by absorbing
the skin or through glass windows without any protection can UVA and UVB rays,29) as shown in Fig. 2. Table 1 present
cause damage and even melanoma.21) Ultraviolet radiation the organic based sunscreen filter/sunscreen agents and pro-
(UVR) is a risk factor that can lead to melanoma and non- tection against UV rays. The previous report stated that the
melanoma. This focuses on the need for public health action, organic filters supported in sunscreen could be classified as
understanding melanoma and its risks, and knowledge of photosensitive and photo-unstable. However, they can also
continuous exposure to UVA and UVB rays without any be photoreactive filters. These molecules can interact with
protection.22) Sun protection aims to minimize the unwanted
 Component, Formulation and Regulatory of Sunscreen Materials: A Brief Review 89

Fig. 1. Classification of sunscreen agents. Adapted from Ref. (28).

Table 1. UV filter compounds in sunscreens and the UV radiation they protect against.10,32,33)

UV filter compound UV radiation filtered Wavelength

PABA UVB λmax of 283 nm
Salicylates UVB 300~310 nm
Octisalate UVB λmax of 307 nm
Homosalate UVB λmax of 306 nm
Octinoxate (octyl methoxycinnamate or OMC or Parsol MCX) UVB λmax of 311 nm
Benzophenones UVA, UVB 360 nm, with a peak at 290 nm
Parsol 1789 or avobenzone or butyl methoxydibenzoylmethane UVA 290~400 nm
Terephthalydene-dicamphor sulphonic acid (mexoryl SX) UVA λmax of 345 nm
Drometriazole trisiloxane UVA, UVB λmax of 290~320 and 320~360 nm
Metilen-bis-benzotriazolil tetrametilbutilfenol UVA, UVB λmax of 360 and 303 nm
Bis-ethilhexyloxylphenol methoxyphenol triazine UVA, UVB λmax of 360 and 303 nm

other molecules, such as sunscreen ingredients, proteins, and

skin lipids, generating unwanted effects.30)

3.2. Inorganic compound based sunscreen

Inorganic compound-based sunscreens are agents that
scatter and reflect UV rays into the environment, providing
physical barriers.31) They contain for examples: zinc oxide
(ZnO) and titanium dioxide (TiO2). Furthermore, these com-
pounds offer UV protection mainly through radiation absorp-
tion, as shown in Fig. 3. Their average UV reflection range is
only 4~5 %, thereby providing minimal protection through
the reflection mechanisms.34)
Inorganic compound-based are less desirable because of
their opaque quality but could be accepted with improve-
ment.29) This can be achieved by adding iron oxide pigment
Fig. 2. Mechanism of protection of organic UV filter. Modified (Fe2O3) to impart a brown color to the sunscreen products.35)
from Ref. (31). Furthermore, micro-sized TiO2 and ZnO are increasingly be-
90 Firi Oktavia Hariani, Mohammad Adam Jerusalem, Iqmal Tahir, Maisari Utami, Won-Chun Oh, and Karna Wijaya

ing replaced by their nanoparticles to overcome sunscreens’ a UV filter with concentrations up to 25 % in cosmetic pro-
low opacity, making them appear more cosmetically plea- ducts can be considered safe for side effects. This was adopted
sing.36) by the Scientific Committee on Consumer Safety (SCCP).38)
TiO2 particles of 200~400 nm have useful properties for
catalysis applications, UV protectants, and photocatalysts 3.3. Hybrid compound based sunscreen
which can be required to scatter visible light to make it appear Hybrid compound-based sunscreens are developed as
white.37) Regardless of the particle size, the safety of TiO2 as multifunctional products that aim to produce specific bene-
fits and properties such as anti-pollution, anti-aging, and sun
protection.39) These hybrid products, which function as UV
filters, consist of organic mixed with inorganic compounds
on a nanoscale (Fig. 4).40) There are recent discoveries re-
garding hybrid UV filters. These include organic and mineral
UV filters that remain stable in various environments or
conditions with high UV protection, water resistance, and
broad-spectrum protection.41) A study showed that hybrid
nanoparticles consisting of lipids and silica increased sun-
screens’ SPF.42)

4. Zeolite Application in Sunscreen Formulation

Zeolite is a hydrated aluminosilicate compound found

naturally on the soil surface. It has a three-dimensional frame-

Fig. 3. Mechanism of protection of inorganic UV filter. Modified

from Ref. (31).

Fig. 5. Zeolite structure.43)

Fig. 4. Mechanism of protection of hybrid UV filter. Modified

from Ref. (31). Fig. 6. Dispersion of oxides, e.g., TiO2 on zeolite or clay.47)
 Component, Formulation and Regulatory of Sunscreen Materials: A Brief Review 91

work composed of tetrahedral SiO4 and AlO4 with oxygen in the pharmaceutical and cosmetic industries.58)
atoms linking these units.43) Furthermore, it has a porous alu- A detailed report has been prepared on kaolin, recommen-
mina silica tetrahydrate structure with the chemical formula ding and regulating it for medicinal and cosmetic purposes.
M8(Si40Al8O96)24H2O, where M is the balancing cation in the Its absorption properties and a large surface area made it
zeolite framework. Zeolites have been used for the encapsu- desirable and widely used as an agent in product formulation.
43-46)
lation and shielding of UV. Previous study showed that The literature stated that kaolin is used as a sunscreen agent
zinc and titanium zeolites are free radical neutralizers and because it has an adsorbent ability and can adhere to the skin
UV absorbers, hence, can be used in sunscreen applications to form a film.59)
for skin protection.44)
Many synthetic zeolites have been produced, but the na- 6. Application of Layered Double Hydroxide in
tural type still plays an essential role as they are abundant in Sunscreen Formulation
nature, specifically in Indonesia. Studies showed that zeolite
mineral has high UV absorption and has the same effective- Layered double hydroxide (LDH) is a class of inorganic
ness as other conventional sunscreens.45) Furthermore, 60~70 crystalline materials. It has the chemical formula: [(M²)1-x
% of zeolites in Indonesia are mostly modernite and clino- (M³)x (OH)2]x+(An- x/n) ‧ zH2O. M2+ is a divalent metal cation
ptilolite.46) The modernite type of natural zeolite is a micro- that M3+ partially replaces, and An represents inorganic
porous material that absorbs and diffuses radiations. They anions, as shown in Fig. 7.60)
explained that there was a strong bond between TiO2 and The encapsulation of sunscreen UV filters in LDH has
zeolite in the results of microscopic characterization, as been reported. The main aim of intercalation of sunscreens
shown in Figs. 5 and 6.47) into LDH nano galleries has been to enhance their photosta-
bility, to increase photoprotection, to prevent dermal contact
5. Application of Nanoclay on Sunscreen For- and impede dermal penetration.63-70)
mulation LDH is safe and provides a suitable matrix for use as a
face and body sunscreen formulation for photoprotection.71)
Two-dimensional (2D) nanoclay minerals, including mica, In addition, it has been proven that hydrotalcite-type double-
hydrotalcite, kaolinite, and montmorillonite, have been used coated hydroxide (HTlc) is often applied in cosmetics and a
in skin protection and against UVB-induced photodamage in good matrix for sunscreen formulations.72) LDH can be mixed
human skin due to chemical stability, biosecurity, breathabi- with organic filters or inorganic sunscreen agents such as
lity, water-barrier, and physical sun-blocking properties.48-52) TiO2 resulting in hybrid sunscreen materials.
The studies showed that nanoclays and lignin have nonflam-
mable UV-protective properties.53) It has been reported that 7. Sunscreen Regulation
creams containing nanoclays have different absorption levels
depending on the Fe2O3 content they contain, which deter-
mines their protection ability.54) Sunscreens that contain a
certain amount of the mineral bentonite have been shown to
absorb the highest levels of rays compared to other com-
mercial types.55) Furthermore, nano clay minerals commonly
used in pharmaceuticals and cosmetics are kaolinite, talc,
smectite (bentonite), and fibrous clays.56)
Kaolin is predominantly kaolinite, a rock composed of
nano clay material with low iron content with the chemical
formula Al2Si2O5(OH)4.57) It is soft, usually white or slightly
whitish, with a hardness of 2~2.5 on the Mohs scale. Further- Fig. 7. Structure scheme of Layered Double Hydroxides. Adapted
more, kaolin is highly abundant and a safe raw material used from Ref. (61, 62).
92 Firi Oktavia Hariani, Mohammad Adam Jerusalem, Iqmal Tahir, Maisari Utami, Won-Chun Oh, and Karna Wijaya

Table 2. Sun Protection Factor (SPF) values listed on Sunscreen 8. Conclusion

Cosmetics.78)

Level SPF value Sunscreen is an essential cosmetic product that protects

Low ≥6 ~ <15 the skin from exposure to harmful UV rays. The harmful
Medium ≥15 ~ <30 effects of long-term radiation are melanoma and non-mela-
High ≥30 ~ <50 noma cancers. Due to the harmful effects of UV rays, sun-
Very high ≥50 screen formulations must continue to evolve to give optimum
protection and an aesthetically pleasing finish to the skin
Sunscreen generally has cosmetic marking methods and upon which they are applied. Cosmetic marking methods and
regulations under state guidelines. The Food and Drug Ad- regulations that exist in each country are set based on guide-
ministration (FDA) has set the UVA regulation in the 2011 lines to regulate safety, use, and distribution.
FDA final rules, which mandates that sunscreen products Sunscreen formulation is evolving with ever more advan-
should protect with an average critical wavelength value of ced technological developments to improve product quality
370 nm or above.73) It has published final rules defining cri- and safety. Greater sunscreen products, both organic, inorga-
teria and procedures to standardize a drug that is generally nic, and hybrid, are continuously being developed to provide
recognized as safe and effective (GRASE) and not misbran- maximum UV protection. Therefore, this study discussed the
ded under the recommended conditions.74) Furthermore, the potential of zeolite, clay, kaolin, and LDH in sunscreen for-
FDA regulated that sunscreens need to pass an in vitro broad mulations due to their natural abundance.
spectrum test to demonstrate that the product can absorb
radiation and then include a numerical SPF value resulting Acknowledgement
from the test (Table 2). The waterproof sunscreen test should
also be clearly stated on the label to ensure protection and The author(s) would like to thank Dr. Nani Ratnaningsih
75)
effectiveness. STP., MP as the supervisor in the scientific writing course.
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