KR102424847B1 - Dispersion Composition For UV Blocking - Google Patents

Abstract

[상기 화학식1에서,
Ar₁ 및 Ar₂는 각각 독립적으로 C6-C20의 아릴이고, 상기 Ar₁ 및 Ar₂의 아릴은 각각 독립적으로 C1-C20의 알콕시로 치환될 수 있고;
R₁, R₂, R₃, R₅ 및 R₈은 각각 독립적으로 C1-C20의 알콕시이고;
R₄, R₆ 및 R₇은 각각 독립적으로 C1-C20의 알킬이고;
L₁ 및 L₂는 각각 독립적으로 2가의 연결기이고;
w, x, y 및 z는 몰분율로 0<w<1, 0<x<1, 0<y<1, 0<z<1을 만족하는 실수이고, w+x+y+z=1이다.]The dispersion composition for blocking ultraviolet rays according to the present invention includes silsesquioxane-based polymer particles including a structural unit represented by the following formula (1) and oil.
[Formula 1]

[In Formula 1,
Ar ₁ and Ar ₂ are each independently C6-C20 aryl, wherein Ar ₁ and Ar ₂ aryl may be each independently substituted with C1-C20 alkoxy;
R ₁ , R ₂ , R ₃ , R ₅ and R ₈ are each independently C1-C20 alkoxy;
R ₄ , R ₆ and R ₇ are each independently C1-C20 alkyl;
L ₁ and L ₂ are each independently a divalent linking group;
w, x, y and z are real numbers satisfying 0<w<1, 0<x<1, 0<y<1, 0<z<1 in mole fraction, and w+x+y+z=1. ]

Description

Dispersion Composition For UV Blocking

The present invention relates to a dispersion composition for blocking UV rays, and more particularly, to a dispersion composition for blocking UV rays having improved dispersibility and a cosmetic composition comprising the same.

Sunscreens are classified into organic sunblocks and inorganic sunblocks according to the sunblock principle. When irradiated with ultraviolet rays, organic sunscreen absorbs ultraviolet rays by a chemical principle by molecular bonding, and has a transparent appearance and soft feeling, but may cause skin irritation or eye irritation depending on the mechanism of chemical blocking on the skin surface. Reported hazards tend to be avoided in the current market. Accordingly, recently, a technology for blocking ultraviolet rays by physically reflecting ultraviolet rays irradiated to the skin using titanium oxide and zinc oxide, which are inorganic sunscreens, has been meeting the needs of consumers.

As described above, inorganic sunscreens such as zinc oxide and titanium oxide have excellent ultraviolet blocking effects and are widely used as materials for sunscreens. However, these inorganic sunscreens have a high refractive index, making it difficult to maintain transparency in formulation . In order to solve this problem, Patent Document 1 proposes an inorganic sunscreen of fine particles having an average particle size of less than 100 nm. However, in the case of a sunscreen containing an inorganic sunscreen with a size of less than 100 nm, the surface area of the inorganic sunscreen increases and it is difficult to maintain dispersibility over time, which causes problems in formulation and remains on the skin. It clogs pores and causes skin problems. Therefore, there is still a need for research on materials that can maximize UV protection while avoiding the nano-size and without the risk of skin residue and penetration.

In addition, when the amount of the inorganic sunscreen is high, white turbidity occurs, which is not aesthetically pleasing and forms a cosmetically unsatisfactory formulation due to a stiff feeling of use. In order to solve this problem, research on organic-inorganic hybrid type composite materials or research on modifying the surface of an inorganic sunscreen is being conducted, but it has not yet shown a sufficient effect.

Therefore, as another method that can meet these needs, a UV protection booster is required.

KR 10-1158806 B1

An object of the present invention is to provide a dispersion composition for UV protection with improved dispersibility and improved storage stability by supplementing the UV blocking ability of the UV blocking agent when mixed with an existing inorganic UV blocking agent to realize a synergistic effect.

Another object of the present invention is to provide a dispersion composition for UV protection that does not cause cloudiness even when included in a high content in a cosmetic composition, and is harmless to the human body.

In order to achieve the above object, in the present invention, there is provided a dispersion composition for blocking ultraviolet rays comprising silsesquioxane-based polymer particles including a structural unit represented by the following formula (1) and an oil.

[Formula 1]

[In Formula 1,

Ar ₁ and Ar ₂ are each independently C6-C20 aryl, wherein Ar ₁ and Ar ₂ aryl may be each independently substituted with C1-C20 alkoxy;

R ₁ , R ₂ , R ₃ , R ₅ and R ₈ are each independently C1-C20 alkoxy;

R ₄ , R ₆ and R ₇ are each independently C1-C20 alkyl;

L ₁ and L ₂ are each independently a divalent linking group;

w, x, y and z are real numbers satisfying 0<w<1, 0<x<1, 0<y<1, 0<z<1 as mole fractions, and w+x+y+z=1. ]

In the dispersion composition for sunscreen according to an embodiment of the present invention, Ar ₁ of the structural unit represented by Formula 1 is C1-C7 alkoxy-substituted C6-C12 aryl, and Ar ₂ is C6-C12 aryl of; wherein R ₁ , R ₂ , R ₃ , R ₅ and R ₈ are each independently C1-C7 alkoxy; wherein R ₄ , R ₆ and R ₇ are each independently C1-C7 alkyl; Each of L ₁ and L ₂ may independently be a divalent linking group including an amide group or an ester group.

In the dispersion composition for sunscreen according to an embodiment of the present invention, it may include one or more selected from ester-based oils and plant-based oils.

The dispersion composition for sunscreen according to an embodiment of the present invention may include 20 to 70% by weight of the silsesquioxane-based polymer particles and 20 to 70% by weight of the oil, based on the total weight.

In the dispersion composition for blocking ultraviolet rays according to an embodiment of the present invention, the average particle size of the silsesquioxane-based polymer particles may be in the range of 1 to 10 μm.

In the dispersion composition for blocking ultraviolet rays according to an embodiment of the present invention, it may further include one or more compounds selected from polyhydroxy fatty acid-based compounds and siloxane-based compounds to which polyethylene glycol is bonded.

In the dispersion composition for blocking ultraviolet rays according to an embodiment of the present invention, the viscosity of the dispersion composition for blocking ultraviolet rays may be in the range of 400 to 10000 cps.

In the dispersion composition for blocking ultraviolet rays according to an embodiment of the present invention, the dispersion composition for blocking ultraviolet rays may block UV-A and UV-B at the same time.

In addition, in the present invention, there is provided a cosmetic composition for sunscreen comprising the above-described dispersion composition for sunscreen.

The cosmetic composition according to an embodiment of the present invention may further include an inorganic sunscreen.

In the cosmetic composition according to an embodiment of the present invention, the dispersion composition for sunscreen may exhibit a boosting effect with the inorganic sunscreen to increase the sunscreen index of the cosmetic composition.

The dispersion composition for sunscreen according to the present invention has improved dispersibility and has the advantage of having storage stability by suppressing the sedimentation of the dispersoid despite the passage of time.

The dispersion composition for blocking ultraviolet rays according to the present invention can implement a critical wavelength of 370 nm or more even though it is not a sunscreen agent. This means the UV-A wavelength value that the sunscreen can block to the maximum. Accordingly, the dispersion composition for blocking UV rays according to the present invention can block UV-B as well as UV-A region, and thus can exhibit an effective effect as a UV blocking booster material for excellent UV blocking ability.

The dispersion composition for UV protection according to the present invention can provide a significantly improved UV blocking effect when mixed with a conventional inorganic UV blocking agent.

The dispersion composition for sunscreen according to the present invention has improved safety as it contains silsesquioxane-based polymer particles and oil that do not penetrate into the human body.

1 is a digital photograph showing the dispersibility of Example 1. FIG.

Hereinafter, the dispersion composition for blocking ultraviolet rays of the present invention will be described in detail with reference to the accompanying drawings. The drawings introduced below are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

The singular forms used in the specification may also be intended to include the plural forms unless the context specifically dictates otherwise. In this specification, the units used without special mention are based on the weight, for example, the unit of % or ratio means weight % or weight ratio.

As used herein, the terms “alkyl,” “alkoxy,” and other substituents comprising an “alkyl” moiety include both straight-chain and comminuted forms.

In addition, the term "aryl" as used herein is an organic radical derived from an aromatic ring by removal of one hydrogen, and a monocyclic ring containing 4 to 7, specifically 5 or 6 ring atoms in each ring, as appropriate. Or it may include a polycyclic ring system, and includes a form in which a plurality of aryls are connected by a single bond.

Under the above-mentioned background technology, the present inventors have intensified research on new materials capable of boosting the UV blocking ability of inorganic UV blocking agents while solving the problems of the prior art. As a result, it was confirmed that when the silsesquioxane-based polymer particles according to the present invention form a stable dispersed phase, a critical wavelength of 370 nm or more can be implemented even though it is not a UV blocker. In addition, the present inventors intend to propose the present invention by confirming that the dispersion composition including the silsesquioxane-based polymer particles according to the present invention can implement a UV blocking boosting effect as well as a high UV blocking effect. It is noteworthy that there has been no report of verification of such an effect through silsesquioxane-based polymer particles to date.

Hereinafter, the present invention will be specifically described.

The present invention provides a dispersion composition for blocking ultraviolet rays comprising silsesquioxane-based polymer particles. Specifically, the dispersion composition for blocking ultraviolet rays according to the present invention includes silsesquioxane-based polymer particles including a structural unit represented by the following Chemical Formula 1 and oil.

[Formula 1]

[In Formula 1,

Ar ₁ and Ar ₂ are each independently C6-C20 aryl, wherein Ar ₁ and Ar ₂ aryl may be each independently substituted with C1-C20 alkoxy;

R ₁ , R ₂ , R ₃ , R ₅ and R ₈ are each independently C1-C20 alkoxy;

R ₄ , R ₆ and R ₇ are each independently C1-C20 alkyl;

L ₁ and L ₂ are each independently a divalent linking group;

w, x, y and z are real numbers satisfying 0<w<1, 0<x<1, 0<y<1, 0<z<1 as mole fractions, and w+x+y+z=1. ]

In the dispersion composition for sunscreen according to an embodiment of the present invention, Ar ₁ of the structural unit represented by Formula 1 is C1-C7 alkoxy-substituted C6-C12 aryl, and Ar ₂ is C6-C12 aryl of; wherein R ₁ , R ₂ , R ₃ , R ₅ and R ₈ are each independently C1-C7 alkoxy; wherein R ₄ , R ₆ and R ₇ are each independently C1-C7 alkyl; Each of L ₁ and L ₂ may independently be a divalent linking group including an amide group or an ester group.

In the dispersion composition for sunscreen according to an embodiment of the present invention, Ar ₁ of the structural unit represented by Formula 1 is C1-C3 alkoxy-substituted C6-C12 aryl, and Ar ₂ is C6-C12 aryl of; wherein R ₁ , R ₂ , R ₃ , R ₅ and R ₈ are each independently C1-C3 alkoxy; wherein R ₄ , R ₆ and R ₇ are each independently C1-C3 alkyl; Each of L ₁ and L ₂ may independently be a divalent linking group including an amide group or an ester group.

For example, in Formula 1, Ar ₁ may be C1-C3 alkoxy-substituted phenyl or C1-C3 alkoxy-substituted naphthyl, and Ar ₂ may be phenyl or naphthyl.

For example, in Formula 1, R ₁ , R ₂ , R ₃ , R ₅ and R ₈ are each independently methoxy or ethoxy; The R ₄ , R ₆ and R ₇ may each independently be methyl or ethyl.

For example, L ₁ and L ₂ may each independently be a divalent linking group including an amide group, which may be a functional group represented by Formula 2 below.

[Formula 2]

[In Formula 2,

R is hydrogen, methyl or ethyl

n is an integer selected from 1 to 5,

* may be a position bonding with Si in Formula 1]

For example, in Formula 2, n is an integer selected from 1 to 3.

The silsesquioxane-based polymer particles including the structural unit represented by Formula 1 are water-insoluble particles having an average particle size of 100 nm or more, but in the dispersion composition mixed with oil, they have an average particle size of 1 μm or more, so they are absorbed through the skin Since the possibility of contamination is very low, the harmfulness of nanoparticles, which has recently been a problem, can be excluded. That is, the dispersion composition for blocking ultraviolet rays according to the present invention is a material that does not penetrate into the human body, and thus has excellent safety. In addition, since the silsesquioxane-based polymer particles contain a functional group capable of absorbing ultraviolet rays, it is expected that the silsesquioxane-based polymer particles can exhibit a UV-blocking effect. In addition, the silsesquioxane-based polymer particles have an excellent boosting effect when combined with an organic/inorganic sunscreen.

Silsesquioxane-based polymer particles containing an aromatic ring group and a silicone group simultaneously have excellent compatibility with oils commonly used in cosmetic compositions, and at the same time provide a silky and matte feeling that is difficult to provide with organic sunscreens. good to have

The dispersion composition for sunscreen according to the present invention may include at least one selected from ester-based oils and plant-based oils in terms of implementing more improved dispersibility.

Non-limiting examples of the ester oil may be selected from C12-15 alkyl benzoate, hexyl laurate, ethylhexyl stearate, ethylhexyl palmitate, isotridecyl isononanoate, cetylethylhexanoate, and the like. and may preferably include C12-15 alkyl benzoate.

Non-limiting examples of the vegetable oil include squalane, castor oil, coconut oil, palm oil, tamanu oil, macadamia nut oil, sunflower seed oil, olive oil, evening primrose oil, argan oil, apricot seed oil, bergamot oil, Camellia oil, tea tree oil, jojoba oil and citron seed oil, etc.; and alkanes or esters derived therefrom, and may preferably include coconut alkanes, which are alkanes or esters of the vegetable oil having solubilizing ability.

The dispersion composition for sunscreen according to the present invention may further include one or more oils selected from hydrocarbon-based oil, triglyceride-based oil, carbonate-based oil, alcohol-based oil, fluorine-based oil, and silicone-based oil.

The dispersion composition for sunscreen according to the present invention has storage stability by effectively inhibiting the sedimentation of the dispersoid (silsesquioxane-based polymer particles) despite the passage of time by forming a dispersed phase with improved dispersion stability. and can provide a remarkably improved UV blocking effect even when mixed with conventional organic/inorganic sunscreens. Accordingly, the dispersion composition for UV protection according to the present invention may have an equivalent meaning to the UV protection index booster composition capable of improving the UV blocking effect.

The dispersion composition for sunscreen according to an embodiment of the present invention may include 20 to 70% by weight of the silsesquioxane-based polymer particles and 20 to 70% by weight of the oil, based on the total weight, If it satisfies the content range, it can be mixed and used in various amounts.

For example, the dispersion composition for blocking ultraviolet rays may have a solid content of 25 to 60% by weight, or 30 to 50% by weight, or 35 to 45% by weight. At this time, when the solid content of the dispersion composition for UV blocking satisfies 35 to 45 wt%, it is preferable to have a high UV protection index compared to the amount used.

The dispersion composition for blocking ultraviolet rays according to the present invention has improved dispersibility even if it contains silsesquioxane-based polymer particles of very fine size, and can suppress aggregation of silsesquioxane-based polymer particles in the dispersion composition. It may have an improved UV blocking ability.

For example, the average particle size of the silsesquioxane-based polymer particles in the dispersion composition for blocking ultraviolet rays may be 1 to 10 μm, specifically 3 to 7 μm, and more specifically 4 to 6 μm.

The dispersion composition for blocking ultraviolet rays according to an embodiment of the present invention can block ultraviolet A (320 to 400 nm) and ultraviolet B (280 to 320 nm) at the same time. Specifically, the dispersion composition for blocking ultraviolet rays according to an embodiment of the present invention has a maximum absorption wavelength in the region of 320 nm or less, and its main absorption region is the UV-B region, and has a critical wavelength of 370 nm or more. Area A can be blocked at the same time.

For example, when the solid content of the dispersion composition for UV protection satisfies 40% by weight, the UV-B region UV protection factor (Sun Protection Factor, SPF) may be 30 to 80, preferably 40 to 75 , more preferably, the range of 45 to 70 may be satisfied. Furthermore, the UV-blocking index (Protection grade of UV-A, PA, UVA-PF) in the UV-A region may be triple plus (PA+++). However, in Korea, since the UV-blocking index of 16 and above in the UV-A region is all indicated as triple plus (PA+++), the UV-blocking index of the UV-A region, which will be described later, is expressed as a numerical value.

As described above, the dispersion composition for UV protection according to the present invention can exhibit a high UV protection index by implementing improved dispersion stability and can impart synergy to the boosting effect with the inorganic UV blocking agent. Accordingly, the dispersion composition for blocking ultraviolet rays may further include an additive to further improve dispersion stability.

In the dispersion composition for sunscreen according to the present invention, the additive may be one or two or more compounds selected from polyhydroxy fatty acid-based compounds and siloxane-based compounds to which polyethylene glycol is bonded. These compounds can improve dispersibility by controlling the viscosity of the final dispersion composition by dissociating the agglomerated particles by generating steric or electrostatic repulsion between the silsesquioxane-based polymer particles in the dispersion composition. .

The polyhydroxy fatty acid-based compound may serve as a dispersant, and may be a compound derived from a fatty acid having 10 to 50 carbon atoms. Non-limiting examples thereof include, but are not limited to, polyhydroxystearic acid.

The siloxane-based compound to which polyethylene glycol (PEG) is bound may act as a phase stabilizer, and may include PEG to which 5 to 50 moles of ethylene glycol are added. Non-limiting examples thereof, PEG-10 dimethicone (PEG-10 Dimethicone), cetyl PEG/PPG-10/1 dimethicone (Cetyl PEG/PPG-10/1 Dimethicone), lauryl PEG-9 polydimethylsilox Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone, Cyclopentasiloxane/PEG.PPG-19.19 Dimethicone and Lauryl PEG.PPG-18.18 Methicone (Lauryl PEG.PPG-) 18.18 Methicone), but is not limited thereto.

For example, the dispersion composition for sunscreen according to the present invention may contain the dispersant in an amount of 0.1 to 5.0% by weight. In addition, it may be included in an amount of 0.1 to 3.0% by weight, and also 0.5 to 2.0% by weight.

For example, the dispersion composition for blocking ultraviolet rays according to the present invention may contain the phase stabilizer in an amount of 0.5 to 2.5% by weight. In addition, it may be included in an amount of 1.0 to 2.0% by weight, and also 1.5 to 2.0% by weight.

For example, the dispersion composition for blocking ultraviolet rays according to the present invention may contain the dispersant and the phase stabilizer at the same time, and it is of course that the content can be variously adjusted within the above-described content range. In this case, the dispersion composition for blocking ultraviolet rays may contain 1 to 2 parts by weight of the phase stabilizer based on 1 part by weight of the dispersant.

When the dispersion composition for UV protection according to the present invention includes an additive within the above numerical range, the viscosity of the dispersion composition for UV protection in the dispersion composition is not too low and the silsesquioxane-based polymer particles in the dispersion composition may not settle, and the viscosity of the dispersion composition may be properly maintained. Accordingly, even if a thixotropic reaction is involved, the fluidity of the dispersion composition can be stably maintained, and a rapid change in viscosity over time can be prevented.

For example, the viscosity of the dispersion composition for sunscreen according to the present invention may be in the range of 400 to 10000 cps. In addition, it may be one that satisfies the range of 1000 to 7500 cps, and also 3000 to 7000 cps.

For example, the viscosity range of the dispersion composition for blocking ultraviolet rays according to the present invention may satisfy the above-described range when the silsesquioxane-based polymer particles are included in an amount of 30 to 50% by weight. Specifically, the dispersion composition for sunscreen according to the present invention preferably satisfies the range of 3000 to 7000 cps, and in order to satisfy such a viscosity range, it may further include one or more additives selected from dispersants and phase stabilizers. have.

When the viscosity of the dispersion composition for UV protection according to the present invention satisfies the above range, the dispersion composition for UV protection is excellent in dispersibility to suppress sedimentation of the silsesquioxane-based polymer particles despite the passage of time nice to be able to

In addition, the present invention provides a cosmetic composition for blocking ultraviolet rays comprising the above-described dispersion composition for blocking ultraviolet rays. In this case, the dispersion composition for blocking UV rays serves as a UV blocking index booster capable of improving UV blocking efficacy.

In the cosmetic composition according to an embodiment of the present invention, the dispersion composition for blocking ultraviolet rays may be included in an amount of 1 to 50% based on the solid content. In addition, 5 to 30%, and may also be included in 8 to 20%.

Specifically, the cosmetic composition according to the present invention may further include an inorganic sunscreen. In general, it is difficult to satisfy the UV protection factor (SPF) of 50 or more and to simultaneously satisfy the feeling of use such as the application of the skin only by using an inorganic sunscreen. However, by including the dispersion composition for sunscreen according to the present invention, it can be satisfied at the same time. That is, the cosmetic composition according to the present invention further includes the dispersion composition for blocking ultraviolet rays and the inorganic sunscreen, so that the sunscreen effect can be further improved. On the other hand, the UV blocking boosting effect is insignificant only by mixing the inorganic UV blocking agent.

The inorganic sunscreen is not limited as long as it is a conventional inorganic sunscreen nanoparticle used for blocking ultraviolet rays, and metal oxide nanoparticles including metals such as titanium, zinc, copper, aluminum, cesium, iron and zirconium may be mentioned. have. Non-limiting examples thereof include TiO ₂ , ZnO, ZnO ₂ , CuO, CuO ₂ , Al ₂ O ₃ , Al(OH) ₃ , CeO ₂ , Ce ₂ O ₃ , Fe ₂ O ₃ , ZrO ₂ , and the like. However, the present invention is not limited thereto.

For example, the inorganic sunscreen agent may be included in an amount of 5 to 30% by weight based on the total weight of the cosmetic composition. In addition, 5 to 25% by weight, and may be included in 8 to 20% by weight.

In the cosmetic composition according to an embodiment of the present invention, when the inorganic sunscreen agent and the silsesquioxane-based polymer particles are included in a weight ratio of 100:20 to 100:65, a more improved sunscreen index can be implemented. That is, when the above-described weight ratio is satisfied, synergy can be imparted to the UV protection index boosting effect. More preferably, the weight ratio may satisfy 100:35 to 100:65 weight ratio.

For example, since the dispersion composition for blocking ultraviolet rays mainly blocks the UV-B region, it is preferable to include a concentration of zinc oxide that blocks the UV-A region in an amount of 10% by weight or more.

For example, when the cosmetic composition contains ultrafine titanium dioxide and zinc oxide in concentrations of 3.50% and 10.56%, the sunscreen index (SPF) of the cosmetic composition is a control (dispersion composition for sunscreen according to the present invention) It can have an improved value of up to 195% or more compared to samples that do not contain In addition, the UV protection factor (UVA-PF) may also satisfy double plus (PA++) or triple plus (PA+++) by implementing an improved value.

The cosmetic composition according to an embodiment of the present invention is a makeup primer, makeup base, liquid or solid foundation, concealer, lipstick, lip gloss, powder, lip liner, eyeliner, mascara, eyebrow, eye shadow, blusher, twin cake, ultraviolet rays. It may be formulated as a blocker, lotion, cream or essence, but is not limited thereto.

Hereinafter, examples using the silsesquioxane-based polymer particles represented by the following Chemical Formula 3 are presented. However, the following examples are provided for easier understanding of the present invention, and the following examples are merely illustrative and not intended to limit the scope of the present invention in any way.

[Formula 3]

[In Formula 3,

w, x, y and z are real numbers satisfying 0<w<1, 0<x<1, 0<y<1, 0<z<1 as mole fractions, and w+x+y+z=1. ]

(Example 1) Selection of dispersion medium

Silsesquioxane-based polymer particles (average particle size = 2 μm) including the structural unit represented by Formula 3 as a dispersoid were dispersed and dissolved in oil as a dispersion medium. Specifically, the dispersion medium, C12-15 alkyl benzoate (C12-15 Alkyl benzoate); Coconut Alkanes; cyclopentasiloxane; Castor oil; and capric triglyceride (Caprylic/Capric Triglyceride) were used. Dispersion A (C12-15 alkyl benzoate), dispersion B (coconut alkane), dispersion C (cyclopentasiloxane), dispersion D (castor oil), and dispersion E (caprylic/capric triglyceride), depending on the type of the dispersion medium ) was obtained. The concentrations of the silsesquioxane-based polymer particles (Polysilicone-24, PS-24) of the sample were all 50%, and a separate dispersant was not added.

The shape according to the dispersion medium, that is, the dispersibility was visually confirmed, and the results are shown in FIG. 1 below. 1, it was confirmed that the dispersion A and the dispersion B prepared in Example 1 can evenly disperse the silsesquioxane-based polymer particles. This is expected because, in the case of an ester-based oil such as C12-15 alkyl benzoate, it contains an aromatic ring group like the silsesquioxane-based polymer particles, and thus has excellent compatibility between the two components, and vegetable oils such as coconut alkanes. In the case of oil, it is expected because it has excellent solubilization ability. Although it was confirmed that both oils (C12-15 alkyl benzoate and coconut alkane) had dispersibility, C12-15 alkyl benzoate, which is more commonly used in cosmetic compositions, was added to the silsesquioxane-based polymer particles. It was selected as a dispersion medium for

(Example 2) Dispersoid concentration selection

To satisfy the composition of Table 1 below, the silsesquioxane-based polymer particles represented by Formula 3 as a dispersant, C12-15 alkyl benzoate as a dispersion medium, Polyhydroxystearic Acid as a dispersant, and PEG-10 as a phase stabilizer After mixing dimethicone (PEG-10 Dimethicone) and stirring with a stirrer to prepare a primary dispersion, the primary dispersion is put into a bead mill and dispersion is completed to complete the secondary dispersion (dispersion for UV protection) composition) was prepared.

In order to determine the optimal concentration of the silsesquioxane-based polymer particles as a dispersoid, the viscosities of the primary and secondary dispersions of Example 2 were measured. The UV-A and B UV protection indices of the secondary dispersion of Example 2 and the diluted solution (diluted solution of the secondary dispersion) diluted by 30% in C12-15 alkyl benzoate were checked, and using a particle size analyzer The average particle size of each dispersion was confirmed.

The results are shown in Table 2. Example 2-1 showed the lowest UV-A and B UV protection factor (SPF). This is because the concentration of the added dispersoid was the lowest. In the case of Example 2-2, it had the smallest average particle size and the least amount of agglomeration of the dispersoid occurred. However, in the case of Example 2-2, it exhibited a low viscosity as in Example 2-1. In the case of Examples 2-3 to 2-5, the viscosity of both the primary and secondary dispersions was 1,000 cps or more. In particular, in the case of Example 2-3, the SPF for the stock solution and the 30% dilution of the secondary dispersion showed the highest range among the five samples tested. In addition, in the case of Examples 2-4 to 2-5, despite having a higher dispersoid concentration compared to Example 2-3, the UV blocking index was lower than that of Example 2-3. This result means that, when the dispersoid concentration exceeds 40% by weight, the dispersion of the silsesquioxane-based polymer particles is not well achieved despite the dispersion through the dispersion equipment. Therefore, when preparing a dispersion composition for UV protection comprising the silsesquioxane-based polymer particles and C12-15 alkyl benzoate, it can be seen that the optimal concentration of the dispersoid is 40% by weight (Example 2-3). have.

(Example 3) Dispersant concentration selection

To satisfy the composition of Table 3 below, silsesquioxane-based polymer particles represented by Formula 3 as a dispersant, C12-15 alkyl benzoate as a dispersion medium, Polyhydroxystearic Acid as a dispersant, and PEG-10 as a phase stabilizer After mixing dimethicone (PEG-10 Dimethicone) and stirring with a stirrer to prepare a primary dispersion, the primary dispersion is put into a bead mill and dispersion is completed to complete the secondary dispersion (dispersion for UV protection) composition) was prepared.

In order to determine the optimal concentration of polyhydroxystearic acid as a dispersant, the viscosities of the primary and secondary dispersions of Example 3 were measured.

The results are shown in Table 4. In the case of the primary dispersion, the viscosity decreases as the concentration of the dispersant increases, whereas in the case of the secondary dispersion, the viscosity decreases as the concentration of the dispersant increases when the dispersant is 1.5% by weight, and the dispersant is 1.5% by weight When it is exceeded, it can be seen that the viscosity increases again as the concentration of the dispersant increases. On the other hand, for dispersion stability of the secondary dispersion, it is preferable to adjust its viscosity to 3,000 cps or more. Therefore, when preparing a dispersion composition for UV protection comprising the silsesquioxane-based polymer particles and C12-15 alkyl benzoate, it can be seen that the optimal concentration of the dispersant is 1.0% by weight (Example 3-1). .

(Example 4) Phase stabilizer concentration selection

To satisfy the composition of Table 5 below, silsesquioxane-based polymer particles as a dispersant, C12-15 alkyl benzoate as a dispersion medium, Polyhydroxystearic Acid as a dispersant, and PEG-10 dimethicone as a phase stabilizer (PEG-10) Dimethicone) was mixed and stirred with a stirrer to prepare a primary dispersion, and then the primary dispersion was put into a bead mill and dispersion was completed to prepare a secondary dispersion (dispersion composition for UV protection).

In order to determine the optimal concentration of PEG-10 dimethicone as a phase stabilizer, the viscosities of the primary and secondary dispersions of Example 4 were measured.

The results are shown in Table 6. As a result, in proportion to the concentration of the phase stabilizer, the viscosity of both the primary and secondary dispersions tended to increase, and in particular, it was confirmed that the increase in the secondary dispersion was higher than that of the primary dispersion. In addition, when the viscosity of the secondary dispersion is very high, 8000 cps or more, there is a possibility that the viscosity increases rapidly over time due to a thixotropic reaction. Therefore, it can be seen that when preparing a dispersion composition for UV protection comprising the silsesquioxane-based polymer particles and C12-15 alkyl benzoate, the optimal concentration of the phase stabilizer is 1.5 wt% (Example 4-2). have.

(Example 5) Confirmation of UV protection index of dispersion composition for blocking UV rays

Based on the results of Examples 1 to 4, 57.5% by weight of C12-15 alkyl benzoate, 40.0% by weight of silsesquioxane-based polymer particles, and 1.0% by weight of polyhydroxystearic acid And 1.5 wt% of PEG-10 dimethicone (PEG-10 Dimethicone) was mixed and stirred with a stirrer to prepare a first dispersion, and then the first dispersion was put into a bead mill and dispersion was completed. A tea dispersion (dispersion composition for UV protection) was prepared.

Check the viscosity of the primary dispersion and secondary dispersion of Example 5, and UV-A and B ultraviolet rays of the stock solution of the secondary dispersion of Example 5 and the dilution of the secondary dispersion diluted 30% in C12-15 alkyl benzoate The blocking index was checked.

The results are shown in Table 7. The viscosity of the primary dispersion and the secondary dispersion of Example 5 were 1,720 and 3,700 cps, respectively, indicating that the viscosity of the secondary dispersion was higher than that of the primary dispersion. It is considered that when the primary dispersion is further dispersed through the dispersion preparation equipment, the activity of the phase stabilizer is more increased than the dispersant, and the viscosity is improved. In addition, as the viscosity of the secondary dispersion was confirmed to be 3,000 cps or more, it is judged to have the most ideal physical properties of the dispersion for long-term storage.

On the other hand, it can be confirmed that the UV A blocking index and the UV B blocking index of the secondary dispersion of Example 5 are at a level of 60 to 80. Through this, it can be seen that the silsesquioxane-based polymer particles included in the dispersion composition for UV blocking have a UV blocking effect. Therefore, when used in combination with the dispersion composition for sunscreen of the present invention and a conventional sunscreen agent, it is considered that it can help to increase the sunscreen index.

(Example 6) Confirmation of change over time of dispersion composition for UV protection-1

With the composition of Example 5, the viscosity change of the secondary dispersion through the preparation of the primary dispersion and then mechanical dispersion treatment was confirmed for a total of 6 weeks. In addition, the viscosity of each dispersion was measured at intervals of one week to determine the change in viscosity over time.

The results are shown in Table 8. The lowest viscosity of Example 5 was confirmed to be about 2,700 cps, and the highest viscosity was about 3,500 cps, among the confirmation of changes over time. There was no thixotropy phenomenon over time. Thixotropy phenomenon refers to a phenomenon in which a sol is initially formed in a liquid phase with strong interparticle bonding, but is converted to a gel when left alone. In other words, when a liquid having an increased viscosity is dispersed with a strong force, it returns to the previous viscosity, and when it is left standing without dispersing with an additional force, the viscosity increases again. This is a typical phenomenon occurring in a dispersion in which ultrafine titanium dioxide is dispersed, but in the case of Example 5, no thixotropy phenomenon was found.

(Example 7) Confirmation of change over time of dispersion composition for UV protection-2

With the composition of Example 5, the particle size change of the secondary dispersion through the preparation of the primary dispersion and then mechanical dispersion treatment was confirmed for a total of 6 weeks. In addition, the change in particle size of each dispersion was measured at intervals of one week to determine the average particle size over time.

The results are shown in Table 8. The average particle size of Example 5 for a total of 6 weeks was 6.06 μm. The lowest average particle size was confirmed to be 5.90 μm after 3 weeks of measurement, and their average value and standard deviation were found to be 6.06 ± 0.08. Accordingly, it was confirmed that the average particle size of the dispersion composition for blocking ultraviolet rays according to the present invention was also kept constant during the measurement period.

(Example 8) Confirmation of change over time of dispersion composition for UV protection-3

With the composition of Example 5, the change in the UV protection index of the secondary dispersion through the preparation of the primary dispersion and then mechanical dispersion treatment was confirmed for a total of 7 weeks. In addition, the UV protection index of each dispersion was measured at intervals of one week to determine the value over time.

The results are shown in Table 9. As a result of checking the UV protection index for Example 5 for a total of 7 weeks, the average value of the SPF was 62 and the UVA PF was 71. Overall, the fact that the UV-A blocking index, UVA PF, was higher than the UV-B blocking index, SPF, suggests that 40% of the dispersed silsesquioxane-based polymer particles were at a high concentration. In addition, it was confirmed that a high concentration of silsesquioxane-based polymer particles were present in the dispersion, and thus had UV blocking ability by itself.

Example 9) Confirmation of UV protection boosting effect of dispersion composition for blocking UV rays

With the composition of Example 5, the UV blocking booster effect of the secondary dispersion through the preparation of the primary dispersion and then mechanical dispersion treatment was confirmed. This is an essential item for the development of sunscreen cosmetics consisting only of inorganic sunscreens. It is necessary to develop a product that can block SPF 50 or higher by using an inorganic sunscreen alone and satisfy the feeling of use such as spreadability on the skin.

First, the ultraviolet blocking ability of the inorganic sunscreen was confirmed. After selecting the appropriate concentration for the ultrafine titanium dioxide and zinc oxide currently in general use, the UV protection index was confirmed. Then, the UV blocking boosting effect of the present invention was confirmed. The inorganic sunscreen combination applied for this purpose was ultrafine titanium dioxide and zinc oxide, and the concentrations were 3.50% and 10.56%, respectively. Before examining the UV protection booster effect, the UV protection index at each concentration and a mixture of the two blocking agents was checked.

In addition, after diluting the dispersion composition for UV protection prepared with the composition of Example 5 to the concentration shown in Table 10 below, the UV blocking index was checked, and the results are shown in Table 10. As shown in Table 10 below, the UV blocking index was also constantly increased in proportion to the solid content of the dispersion composition for UV blocking according to the present invention.

In order to confirm the UV protection boosting effect of the present invention, the dispersion composition for UV protection according to the present invention was applied at different concentrations to the inorganic UV blocking agent combination derived above, and the UV protection index was measured, and the result is shown below. Table 11 shows.

As shown in Table 11 above, when the dispersion composition for sunscreen according to the present invention was added to the inorganic sunscreen agent at a final concentration of 1%, the measured SPF showed a lower negative increase rate compared to the theoretical SPF. However, it showed a positive increase rate from 3% to 9%. In particular, the measured SPF of the sample applied 9% showed an SPF increase of more than 195% compared to the theoretical SPF. As a result, it was confirmed that the dispersion composition for UV blocking according to the present invention exhibits a UV blocking boosting effect in the UV-B region when applied together with an inorganic UV blocking agent.

For the sample at the time of confirming the SPF boosting effect, the UV-blocking index boosting effect of UV-A PF was confirmed, and the results are shown in Table 12 below.

As shown in Table 12, the actual UV-A PF showed a negative increase rate compared to the theoretical UV-A PF up to the 3% concentration of the dispersion composition for UV protection according to the present invention, but the positive increase rate from the 5% increase showed When 9% of the dispersion composition for UV protection according to the present invention was added, an increase rate of about 50% or more was shown, and a high boosting effect was exhibited according to the increase in the treatment concentration of the dispersion composition for UV protection according to the present invention. Therefore, it was confirmed that the dispersion composition for UV protection according to the present invention exhibits a UV blocking boosting effect in the UV-A region when applied together with an inorganic UV blocking agent.

(Example 10) Clinical trial

A skin irritation test was performed on the dispersion composition for sunscreen according to the present invention. The sample was used after diluting the dispersion composition for UV protection prepared in Example 5 to a solids concentration of 10%. After the patch test on the back of 32 general subjects, skin reactions were observed under a magnifying glass (SK101-3X, Seki optical, Korea). The skin reaction evaluation criteria are shown in Table 13 below, and based on the results, skin irritation was evaluated through Equation 1 below (0.00 to 0.87 mild irritation; 0.88 to 2.42 mild irritation; 2.43 to 3.44 moderate irritation; 3.45 or more strong stimulation). ).

(Formula 1)

As a result, the dispersion composition for sunscreen according to the present invention was evaluated as a product without skin irritation because no skin reactivity was observed.

In addition, the UV protection index for the cosmetic composition comprising the dispersion composition for blocking UV according to the present invention was confirmed. A sample was prepared by adding 8.0% of ultrafine titanium dioxide and 9.62% of zinc oxide to the dispersion composition for UV protection according to the present invention prepared in the composition of Example 5. Specifically, UVA PF evaluation is based on the 「Regulations on the Review of Functional Cosmetics」 for 'functional cosmetics that help to brighten the skin or protect the skin from UV rays' prescribed in Article 9 of the Cosmetics Act (Food and Drug Administration). It was carried out in accordance with 'Method and Standards for Measuring UV Protection Effect' of Ministry of Safety and Health Notice No. 2019-47).

As a result, it was found that the UV A blocking index of the cosmetic composition comprising the dispersion composition for blocking UV according to the present invention was 9.15±0.99 and the UV blocking index was 51.4±3.0, which is a product having UV blocking power of SPF 50+ and PA+++ was evaluated as

As described above, the present invention has been described with specific matters and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (11)

Dispersion composition for UV protection comprising silsesquioxane-based polymer particles and oil comprising a structural unit represented by the following formula (1):
[Formula 1]

In Formula 1,
Ar ₁ is C1-C3 alkoxy-substituted C6-C12 aryl, Ar ₂ is C6-C12 aryl;
R ₁ , R ₂ , R ₃ , R ₅ and R ₈ are each independently C1-C3 alkoxy;
R ₄ , R ₆ and R ₇ are each independently C1-C3 alkyl;
L ₁ and L ₂ are each independently a divalent linking group including an amide group or an ester group;
w, x, y and z are real numbers satisfying 0<w<1, 0<x<1, 0<y<1, 0<z<1 as mole fractions, and w+x+y+z=1. The method of claim 1,
Ar ₁ of the structural unit represented by Formula 1 is C1-C3 alkoxy-substituted phenyl or C1-C3 alkoxy-substituted naphthyl, and Ar ₂ is phenyl or naphthyl; wherein R ₁ , R ₂ , R ₃ , R ₅ and R ₈ are each independently methoxy or ethoxy; wherein R ₄ , R ₆ and R ₇ are each independently methyl or ethyl; Wherein L ₁ and L ₂ are each independently a divalent linking group including an amide group. The method of claim 1,
The oil is
A dispersion composition for UV protection comprising an ester-based oil, a plant-based oil, or a combination thereof. The method of claim 1,
Based on the total weight, the dispersion composition for UV protection comprising 20 to 70% by weight of the silsesquioxane-based polymer particles and 20 to 70% by weight of the oil. The method of claim 1,
In the dispersion composition for sunscreen,
The average particle size of the silsesquioxane-based polymer particles is 1 to 10 μm, a dispersion composition for UV protection. The method of claim 1,
A dispersion composition for UV blocking, further comprising one or more compounds selected from polyhydroxy fatty acid-based compounds and siloxane-based compounds to which polyethylene glycol is bonded. The method of claim 1,
The viscosity of the dispersion composition for sunscreen is,
400 to 10000 cps, a dispersion composition for blocking ultraviolet rays. The method of claim 1,
The dispersion composition for blocking ultraviolet rays,
A dispersion composition for blocking UV-A and UV-B at the same time. A cosmetic composition for sunscreen comprising the dispersion composition for sunscreen according to any one of claims 1 to 8. 10. The method of claim 9,
A cosmetic composition for sunscreen, further comprising an inorganic sunscreen. 11. The method of claim 10,
The cosmetic composition exhibits a boosting effect with the inorganic sunscreen to increase the sunscreen index of the cosmetic composition, a cosmetic composition for sunscreen.

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