Low-irritation transparent long-lasting sunscreen composition and use thereof

Abstract

The application discloses a low-irritation transparent long-acting sunscreen composition and application thereof, and a mass fraction composition of functional components of the low-irritation transparent long-acting sunscreen composition is as follows: 0.2-8 parts of acrylate polymer, 1-8 parts of water-soluble sunscreen agent, 15-30 parts of polyhydric alcohol and 1-15 parts of low-viscosity volatile silicone oil. The acrylate polymer containing zwitterions and the water-soluble sunscreen agent are combined together in the application, the respective advantages are exerted, the sunscreen product presents a stable and transparent appearance, meanwhile, the waterproofness and sweat resistance of the sunscreen product can be improved, the water-soluble sunscreen agent can be effectively fixed, the loss of the water-soluble sunscreen agent on the skin is reduced, the sunscreen effect is more durable, and thus the SPF value of the sunscreen product, i.e. the sunscreen effect, is stronger. The product of the application is completely transparent in appearance, is different from most sunscreen lotions on the market, and the product feels very fresh and non-greasy when used, and is suitable for various skin qualities.

Description

Technical Field

[0001] This invention relates to a cosmetic, specifically to a low-irritation, transparent, long-lasting sunscreen composition and its application. Background Technology

[0002] More and more consumers are using sunscreens to protect their skin from UV damage. Considering the feel of organic sunscreens, consumers tend to prefer combination and physical sunscreens for their smoother texture. However, high SPF is rarely necessary for children's products. Transparent sunscreens offer less UV protection and have weaker overall sun protection. To achieve better sun protection, most sunscreens contain a significant amount of inorganic sunscreen agents.

[0003] Transparent sunscreens perfectly meet consumers' desire for a simple and clear sunscreen, and significantly reduce skin irritation compared to water-based sunscreens. Generally, transparent sunscreen systems are common in oil-phase gel systems. However, when emulsification involves both oil and water phases, the presence of the phase interface makes it very difficult to achieve transparency. Firstly, different emulsion particle sizes result in different appearances; secondly, even slight changes in the refractive indices of the oil and water phases significantly affect the system's transparency. Therefore, developing a composition technology that can significantly increase the durability of transparent sunscreen systems is essential to meet user needs. Summary of the Invention

[0004] The purpose of this invention is to overcome at least one deficiency of the prior art and to provide a low-irritation, transparent, long-lasting sunscreen composition and its application.

[0005] The technical solution adopted in this invention is:

[0006] In a first aspect, the present invention provides a low-irritation, transparent, long-lasting sunscreen composition, wherein the effective ingredients are in the following proportions by weight: 0.2 to 8 parts of acrylate polymer, 1 to 8 parts of water-soluble sunscreen agent, 15 to 30 parts of polyol, and 1 to 15 parts of low-viscosity volatile silicone oil.

[0007] In some instances, the mass ratio of the acrylate polymer to the water-soluble sunscreen agent is 1:(1-40).

[0008] In some instances, the mass ratio of the acrylate polymer to the water-soluble sunscreen agent is 1:(3-20).

[0009] In some instances, the mass ratio of the acrylate polymer to the low-viscosity volatile silicone oil is 1:(0.5–40).

[0010] In some instances, the mass ratio of the low-viscosity volatile silicone oil to polyol is 1:(0.5-5).

[0011] In some instances, the low-viscosity volatile silicone oil is selected from at least one of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and alkyl polydimethylsiloxane copolyether.

[0012] In some instances, the water-soluble sunscreen agent is phenylbenzimidazole sulfonic acid.

[0013] In some instances, the polyol is selected from at least one of ethanol, glycerol, 1,2-propanediol, 1,3-butanediol, and methylpropanediol.

[0014] In some instances, the sunscreen composition also includes antioxidants, fragrances, preservatives, neutralizers, emollients, pH adjusters, free radical scavengers, and deodorants.

[0015] Secondly, the present invention provides a transparent, long-lasting sunscreen cosmetic, wherein the active ingredient is the low-irritation, transparent, long-lasting sunscreen composition described in any one of the first aspects.

[0016] The beneficial effects of this invention are:

[0017] The amphoteric acrylate polymer and water-soluble sunscreen agent exhibit strong compatibility: this means that these two ingredients can combine well, leveraging their respective advantages. The combination of the amphoteric acrylate polymer and the water-soluble sunscreen agent results in a stable, transparent appearance for the sunscreen product. It also enhances the sunscreen's water and sweat resistance, effectively fixing the water-soluble sunscreen agent and reducing its loss to the skin, thus making the sun protection effect longer-lasting and increasing the SPF value, i.e., stronger sun protection. The product of this invention is completely transparent in appearance, unlike most sunscreen lotions on the market, and feels refreshing and non-greasy during use, making it suitable for all skin types. Detailed Implementation

[0018] The inventors discovered that water-soluble acrylic film-forming agents play a crucial role in transparent sunscreen products. They not only reduce the irritation of water-soluble sunscreen agents but also improve their durability and SPF value. This film-forming agent is hydrophilic, allowing it to bind with water molecules, making the sunscreen ingredients more stable and forming a protective film on the skin surface for long-lasting, water- and sweat-resistant protection. Adding this film-forming agent to sunscreen products reduces skin irritation, making them gentler and suitable for all skin types. Furthermore, due to its film-forming properties, it adheres to the skin for extended periods, resulting in longer-lasting sun protection. In addition, this film-forming agent can increase the SPF value of sunscreen products, thus providing more comprehensive sun protection.

[0019] In general, by using this type of water-soluble acrylic film-forming agent, it is possible to manufacture gentler, longer-lasting sunscreens with higher SPF values, providing comprehensive protection for the skin.

[0020] The following disclosure provides many different implementations or examples for different ways of implementing the present invention.

[0021] The monomers of the zwitterionic acrylate polymers described in this invention include monomers containing acrylic groups and zwitterionic monomers.

[0022] The monomer containing the acrylic acid group is selected from at least one of acrylic acid, methacrylic acid, alkyl acrylate and alkyl methacrylate.

[0023] In an optional embodiment, the acrylic monomer includes a first monomer and a second monomer. The first monomer is selected from at least one of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, and isopropyl methacrylate. The second monomer is selected from at least one of octadecyl acrylate and octadecyl methacrylate. In an optional embodiment, the acrylic monomer further includes a third monomer, which is selected from at least one of lauryl acrylate and lauryl methacrylate.

[0024] The amphoteric monomer is selected from at least one of methacryloyl alkyl ammonium salt and methacryloyl alkyl amine oxide; in an optional embodiment, the monomers participating in the copolymerization to obtain the amphoteric copolymer also include pyrrolidone monomers.

[0025] In an optional embodiment, the structural formula of methacryloylalkylamine oxide is:

[0026]

[0027] In the formula, R1, R2 and R3 are all CH3 and n = 2.

[0028] In an optional embodiment, the amino-functionalized compound is selected from at least one of primary amines, secondary amines, and diamines.

[0029] In an optional embodiment, the amino-functionalized compound is selected from at least one of diamines.

[0030] The water-soluble sunscreen agent of the present invention is a UV-B type filter, and is particularly selected from phenylbenzimidazole sulfonic acid.

[0031] Phenylenic acid is one of the few effective UV absorbers that is water-soluble and prepared as a neutralizing salt using sodium hydroxide, triethanolamine, etc., making it suitable for use in water-containing cosmetics. It is commercially available, for example, as "Neo Heliopan Hydro" (Symrise Ltd.), "Eusolex 232" (Merck Ltd.), and "PARSOL HS" (DSM (China) Ltd.), and is a preferred choice for use.

[0032] The low-viscosity volatile silicone oil of the present invention can be selected from organosilicon oils. Usable volatile oils include volatile silicones, primarily cyclic silicone oils, especially those with a viscosity ≤ 8 centistokes (cSt) (8 × 10⁻⁶ m² / s), and silicone oils containing, in particular, 2 to 10 silicon atoms, especially 2 to 7 silicon atoms. These silicones optionally include alkyl or alkoxy groups containing 1 to 10 carbon atoms. Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, and mixtures thereof with viscosities of 5 cSt and 6 cSt are particularly mentioned.

[0033] In addition to organosilicon oils, the low-viscosity volatile silicone oils of this invention can also be selected from alkyl polydimethylsiloxane copolyethers. Examples include lauryl polymethylsiloxane copolyols sold by Dow Corning under the name Dow Corning 5200 Formulation Aid, cetyl PEG / PPG-10 / 1 polydimethylsiloxane sold by Evonik under the name Abil EM 90, or mixtures of polyglycerol-4 isostearate / cetyl PEG / PPG-10 / 1 polydimethylsiloxane / hexyl laurate sold by Evonik under the name Abil WE 09. Other types include PEG-10 polydimethylsiloxane, PEG / PPG-18 / 18 polydimethylsiloxane, lauryl PEG-9 polydimethylsiloxane-ethyl polydimethylsiloxane, cetyl PEG / PPG-10 / 1 polydimethylsiloxane, cyclopentamethoxysiloxane, bis-PEG / PPG-14 / 14 polydimethylsiloxane, and PEG / PPG-12 / 16 polydimethylsiloxane. The preferred material in this invention is KF6105 (lauryl polyglycerol-3-polydimethylsiloxane-ethyl polydimethylsiloxane) from Shin-Etsu Chemical Co., Ltd.

[0034] The compositions according to the invention may also contain any conventional cosmetic ingredients, particularly selected from antioxidants, fragrances, preservatives, neutralizers, surfactants, solar filters, vitamins, moisturizers, self-tanning compounds, anti-wrinkle active ingredients, emollients, hydrophilic or lipophilic active ingredients, free radical scavengers, deodorants, multivalent chelating agents, and mixtures thereof.

[0035] The technical solution of the present invention will be further illustrated below with examples.

[0036] All percentages in this invention are weight percentages and are based on 100% by weight of the cosmetic composition of this invention, unless otherwise stated.

[0037] All weights referred to in this invention are the weights of the effective substance. For substances in dispersion form, the weights referred to in this invention are the actual weights of the substance, excluding the weight of the carrier. That is, the weight of the substance in dispersion form as referred to in this invention = weight of the dispersion × content of solid components in the dispersion. For solid substances containing water of crystallization, the weights referred to in this invention are the weights after removing the water of crystallization.

[0038] Some of the raw materials and reagents are shown in Table 1:

[0039] Table 1

[0040]

[0041]

[0042] The preparation method includes mixing and homogenizing all raw materials. For ease of comparison, 0.5 parts of LEXGARD H (1,2-hexanediol) were added in each example. The addition amounts of each component are parts by weight. NaCl was selectively added as an isotonic adjuster, and water was added to a total of 100 parts. The composition of the components other than LEXGARD H in each example is shown in the tables below.

[0043] The compositions of Examples 1-12 are shown in Table 2 below, wherein the acrylate polymer is NZ631, the water-soluble sunscreen agent is PARSOL HS, the polyol is 1,3-butanediol, and the low-viscosity volatile silicone oils are F995 and 6105.

[0044] Table 2

[0045] serial number Sodium chloride 1,3-Butanediol PARSOL HS TEA F995 6105 NZ631 Example 1 1 18 8 9 9 1.9 0.3 Example 2 1 20 8 9 9 1.9 0.3 Example 3 1 20 8 9 12 2.2 0.3 Example 4 1 30 8 9 12 2.2 0.3 Example 5 1 18 8 9 9 1.9 1 Example 6 1 20 8 9 9 1.9 1 Example 7 1 20 8 9 12 2.2 1 Example 8 1 30 8 9 12 2.2 1 Example 9 1 18 8 9 9 1.9 3 Example 10 1 20 8 9 9 1.9 3 Example 11 1 20 8 9 12 2.2 3 Example 12 1 30 8 9 12 2.2 3

[0046] The compositions of Comparative Examples 1-15 are shown in Table 3 below. The difference between them and the Examples is that the isotonicity regulator sodium chloride and the acrylate polymer NZ631 were not added.

[0047] Table 3

[0048] serial number 1,3-Butanediol PARSOL HS TEA F995 6105 Comparative Example 1 0 4 4.5 9 1.9 Comparative Example 2 0 6 6.75 9 1.9 Comparative Example 3 0 8 9 9 1.9 Comparative Example 4 5 4 4.5 9 1.9 Comparative Example 5 5 6 6.75 9 1.9 Comparative Example 6 5 8 9 9 1.9 Comparative Example 7 10 4 4.5 9 1.9 Comparative Example 8 10 6 6.75 9 1.9 Comparative Example 9 10 8 9 9 1.9 Comparative Example 10 15 4 4.5 9 1.9 Comparative Example 11 15 6 6.75 9 1.9 Comparative Example 12 15 8 9 9 1.9 Comparative Example 13 18 4 4.5 9 1.9 Comparative Example 14 18 6 6.75 9 1.9 Comparative Example 15 18 8 9 9 1.9

[0049] The compositions of Comparative Examples 16-26 and 33-50 are shown in Table 4 below. The main difference lies in the addition of the isotonic conditioner sodium chloride.

[0050] Table 4

[0051]

[0052]

[0053] The composition of Comparative Examples 27-32 is shown in Table 5 below. The main difference is that the F995 component in the low-viscosity volatile silicone oil is replaced with GTCC or IP CLEAN HX, which have similar effects.

[0054] Table 5

[0055] serial number Sodium chloride 1,3-Butanediol PARSOL HS TEA F995 GTCC IP CLEAN HX 6105 Comparative Example 27 1 18 4 4.5 8.5 0.5 0 1.9 Comparative Example 28 1 18 6 6.75 8 1 0 1.9 Comparative Example 29 1 18 8 9 7.5 1.5 0 1.9 Comparative Example 30 1 18 4 4.5 8.5 0 0.5 1.9 Comparative Example 31 1 18 6 6.75 8 0 1 1.9 Comparative Example 32 1 18 8 9 7.5 0 1.5 1.9

[0056] The compositions of Comparative Examples 51-62 are shown in Table 6 below. The main difference is that the acrylate polymer NZ631 is replaced with C200, which has similar effects.

[0057] Table 6

[0058] serial number Sodium chloride 1,3-Butanediol PARSOL HS TEA F995 6105 C200 Comparative Example 51 1 18 8 9 9 1.9 0.1 Comparative Example 52 1 20 8 9 9 1.9 0.1 Comparative Example 53 1 20 8 9 12 2.2 0.1 Comparative Example 54 1 30 8 9 12 2.2 0.1 Comparative Example 55 1 18 8 9 9 1.9 1 Comparative Example 56 1 20 8 9 9 1.9 1 Comparative Example 57 1 20 8 9 12 2.2 1 Comparative Example 58 1 30 8 9 12 2.2 1 Comparative Example 59 1 18 8 9 9 1.9 2 Comparative Example 60 1 20 8 9 9 1.9 2 Comparative Example 61 1 20 8 9 12 2.2 2 Comparative Example 62 1 30 8 9 12 2.2 2

[0059] The composition of Comparative Examples 63-74 is shown in Table 7 below. The main difference is that the acrylate polymer NZ631 is replaced with LATMOISO, which has similar effects.

[0060] Table 7

[0061] serial number Sodium chloride 1,3-Butanediol PARSOL HS TEA F995 6105 LATMOISO Comparative Example 63 1 18 8 9 9 1.9 0.1 Comparative Example 64 1 20 8 9 9 1.9 0.1 Comparative Example 65 1 20 8 9 12 2.2 0.1 Comparative Example 66 1 30 8 9 12 2.2 0.1 Comparative Example 67 1 18 8 9 9 1.9 1 Comparative Example 68 1 20 8 9 9 1.9 1 Comparative Example 69 1 20 8 9 12 2.2 1 Comparative Example 70 1 30 8 9 12 2.2 1 Comparative Example 71 1 18 8 9 9 1.9 2 Comparative Example 72 1 20 8 9 9 1.9 2 Comparative Example 73 1 20 8 9 12 2.2 2 Comparative Example 74 1 30 8 9 12 2.2 2

[0062] The composition of Comparative Examples 75-86 is shown in Table 8 below. The main difference is that the acrylate polymer NZ631 is replaced with C200F, which has similar function.

[0063] Table 8

[0064] serial number Sodium chloride 1,3-Butanediol PARSOL HS TEA F995 6105 C200F Comparative Example 75 1 18 8 9 9 1.9 0.1 Comparative Example 76 1 20 8 9 9 1.9 0.1 Comparative Example 77 1 20 8 9 12 2.2 0.1 Comparative Example 78 1 30 8 9 12 2.2 0.1 Comparative Example 79 1 18 8 9 9 1.9 1 Comparative Example 80 1 20 8 9 9 1.9 1 Comparative Example 81 1 20 8 9 12 2.2 1 Comparative Example 82 1 30 8 9 12 2.2 1 Comparative Example 83 1 18 8 9 9 1.9 2 Comparative Example 84 1 20 8 9 9 1.9 2 Comparative Example 85 1 20 8 9 12 2.2 2 Comparative Example 86 1 30 8 9 12 2.2 2

[0065] The composition of Comparative Examples 87-94 is shown in Table 9 below. The main difference lies in the amount of acrylate polymer NZ631 added.

[0066] Table 9

[0067] serial number Sodium chloride 1,3-Butanediol PARSOL HS TEA F995 6105 NZ631 Comparative Example 87 1 18 8 9 9 1.9 0.1 Comparative Example 88 1 20 8 9 9 1.9 0.1 Comparative Example 89 1 20 8 9 12 2.2 0.1 Comparative Example 90 1 30 8 9 12 2.2 0.1 Comparative Example 91 1 18 8 9 9 1.9 10 Comparative Example 92 1 20 8 9 9 1.9 10 Comparative Example 93 1 20 8 9 12 2.2 10 Comparative Example 94 1 30 8 9 12 2.2 10

[0068] Evaluation Experiment 1: Formulation Transparency and Stability Test

[0069] The transparency of the formulation was tested by visual observation in cuvettes. The stability was tested at 48°C for 30 days. The results are shown in Tables 10 and 11, where Table 10 shows the results of Comparative Examples 1-50 without the addition of acrylate polymer NZ631, and Table 11 shows the results of the group with the addition of acrylate polymer NZ631.

[0070] Table 10

[0071]

[0072]

[0073] For formulations that do not contain sodium chloride (Comparative Examples 1-15), it is difficult for the formulation to appear transparent, and it has a greater impact on stability, which can easily lead to instability in the formulation.

[0074] Replacing the oils in the formula with other oils, such as GTCC (Comparative Examples 27-29) or IPCLEAN HX (Comparative Examples 30-32), did not result in a transparent appearance.

[0075] Table 11

[0076]

[0077]

[0078] In this set of tests, it was clearly observed that formulations containing polymers such as polyurethane-11 (C200) (Comparative Examples 51-62), polyurethane-7 (LATMOISO) (Comparative Examples 63-74), and polyurethane-1 (C200F) (Comparative Examples 75-86), even at a dosage of 0.1%, could not achieve a transparent appearance and all had an adverse effect on the stability of the formulation.

[0079] Formulations containing the polymer NZ631 of this invention (Comparative Examples 87-90, Examples 1-12) can achieve transparency even at a concentration of 3%. However, larger concentrations, such as 10%, reduce the transparency of the formulation. Therefore, formulations with good transparency and stability are achieved when the mass ratio of acrylate to water-soluble sunscreen agent is 1:(1-10), the mass ratio of low-viscosity volatile silicone oil to polyol is 1:(0.5-5), and the mass ratio of acrylate to low-viscosity volatile silicone oil is 1:(0.5-40).

[0080] Evaluation Experiment 2: Durability Evaluation

[0081] A suitable amount of the transparent and stable formula from Evaluation Experiment 1 was selected and weighed (0.05g) on ​​an analytical balance. This formula was then evenly spread onto a PMMA plate (2cm x 2cm). After the formula on the PMMA plate dried, it was placed on a UV transmittance analyzer to test its UVB transmittance. The lower the UV transmittance, the better the sun protection effect. For another group, the application and drying process was repeated, and the PMMA plate was placed in water for 20 minutes, then removed and allowed to dry again before undergoing the same test.

[0082]

[0083] In the formula, λ = wavelength, A = ultraviolet transmittance at a fixed wavelength, and h = test bandwidth (5nm for this test).

[0084] The permeability without water immersion is denoted as R0, and the permeability after immersion is denoted as R. The durability results of this test, calculated by R / R0, are shown in Table 12.

[0085] Table 12

[0086] serial number R0 R R0 / R serial number R0 R R0 / R Comparative Example 24 10.06％ 41.54％ 24.22％ Comparative Example 50 4.87％ 19.58％ 24.87％ Comparative Example 25 6.61％ 26.98％ 24.52％ Comparative Example 88 4.84％ 13.73％ 35.22％ Comparative Example 26 4.85％ 19.62％ 24.71％ Comparative Example 89 4.83％ 13.72％ 35.25％ Comparative Example 33 10.09％ 41.60％ 24.26％ Comparative Example 90 4.84％ 13.82％ 34.99％ Comparative Example 34 6.64％ 27.12％ 24.50％ Example 1 4.73％ 8.26％ 57.21％ Comparative Example 35 4.88％ 19.72％ 24.74％ Example 2 4.72％ 8.16％ 57.91％ Comparative Example 36 10.05％ 41.34％ 24.30％ Example 3 4.73％ 8.21％ 57.52％ Comparative Example 37 6.60％ 26.96％ 24.48％ Example 4 4.73％ 8.19％ 57.80％ Comparative Example 38 4.83％ 19.51％ 24.77％ Example 5 4.34％ 6.73％ 64.51％ Comparative Example 42 10.08％ 41.41％ 24.34％ Example 6 4.34％ 6.66％ 65.18％ Comparative Example 43 6.63％ 27.11％ 24.46％ Example 7 4.34％ 6.73％ 64.47％ Comparative Example 44 4.86％ 19.61％ 24.80％ Example 8 4.35％ 6.72％ 64.70％ Comparative Example 45 10.08％ 41.36％ 24.37％ Example 9 4.06％ 5.59％ 72.56％ Comparative Example 46 6.63％ 27.13％ 24.44％ Example 10 4.06％ 5.53％ 73.40％ Comparative Example 47 4.87％ 19.60％ 24.83％ Example 11 4.06％ 5.58％ 72.66％ Comparative Example 48 10.08％ 41.29％ 24.42％ Example 12 4.06％ 5.56％ 73.05％ Comparative Example 49 6.64％ 27.11％ 24.47％

[0087] For polymer-free formulations (Comparative Examples 24-26, 33-38, 42-50), the transmittance decreases with the increase of water-soluble sunscreen agents, but the retention rate is basically 24-25%. In contrast, adding a small amount of polymer NZ631 (Comparative Example 88-90) only slightly increases the retention rate by about 35%.

[0088] In this invention, when the mass ratio of acrylate to water-soluble sunscreen agent is 1:(1-10), the mass ratio of low-viscosity volatile silicone oil to polyol is 1:(0.5-5), and the mass ratio of acrylate to low-viscosity volatile silicone oil is 1:(0.5-40), i.e. (Examples 1-12), in addition to improving the efficiency of sun protection, it also improves the retention rate of water-soluble sunscreen agent, and this improvement is significant with the increase of polymer dosage.

[0089] The above is a further detailed description of the present invention and should not be considered as a limitation on the specific implementation of the present invention. For those skilled in the art, simple deductions or substitutions without departing from the concept of the present invention are all within the protection scope of the present invention.

Claims

1. A low-irritation, transparent, long-lasting sunscreen composition characterized in that, The composition comprises: 0.3-3 parts of acrylate polymer, 1-8 parts of water-soluble sunscreen agent, 18-30 parts of 1,3-butanediol, 0.5 parts of 1,2-hexanediol, 10.9-14.2 parts of low-viscosity volatile silicone oil, 1 part of sodium chloride, 9 parts of triethanolamine, water added to 100 parts, the mass ratio of the acrylate polymer and the water-soluble sunscreen agent is 1:(1-10), the low-viscosity volatile silicone oil is composed of decamethylcyclopentasiloxane and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, and the water-soluble sunscreen agent is phenyl benzimidazole sulfonic acid; The INCI name of the acrylate polymer is: water, acrylates / lauryl acrylate / stearo l acrylate / ethoxylamine oxide methacrylate copolymer, 1,2-hexanediol, and the model number is COTRUNE NZ631.

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