KR101000275B1 - Booster for blocking ultraviolet light - Google Patents

Abstract

PURPOSE: A booster for blocking ultraviolet light is provided to improve UVB and UVA shield effects, water resistance, adhesion, and convenience. CONSTITUTION: A booster for blocking ultraviolet light includes emulsion consisting of a water-phase medium and an acrylic copolymer. The acrylic copolymer is a block copolymer including two kinds of monomers selected from the group consisting of alkyl ester of acrylic acid and alkyl ester of methacrylic acid. The alkyl ester of acrylic acid is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. The alkyl ester of methacrylic acid is selected from the group consisting of methyl methacrylate or butyl methacrylate.

Description

Booster for blocking ultraviolet light}

The present invention relates to a sunscreen breaker. In particular, the present invention relates to a methacrylate-based polymer emulsion that imparts a sun protection factor (SPF) and a protective (PA) boosting effect to a sunscreen personal care article.

UV rays included in sunlight can be divided into UVA (400-320nm), UVB (320-280nm) and UVC (280-200nm). UVC, the strongest ultraviolet rays passing through the atmosphere, is absorbed in the ozone layer and UVA and UVB Is reached to the surface. When irradiated with ultraviolet UVB waves on the skin, the energy of the ultraviolet wavelength penetrates the epidermis and causes inflammation around the capillaries, so short-term irradiation can cause skin erythema or edema. In this case, it may be accompanied by fever or pain. If there is no proper measure, pigmentation may occur over time and skin peeling may occur. On the other hand, in the case of irradiating the skin with UVA, which is a long-wavelength ultraviolet rays, since the irradiation energy reaches the dermal layer and damages the collagen elastic fibers, recent research results indicate that skin wrinkles and elasticity are reduced.

The effects of ultraviolet radiation are not limited to skin. When the human body is exposed to ultraviolet rays for a long time, it is reported that the risk of skin cancer due to decreased immune function or DNA damage is increased. Therefore, to reduce the risk of ultraviolet irradiation to the human body technology for sunscreen is constantly being studied.

Sunscreens are basically divided into UV absorbers and UV scatterers. Early ultraviolet absorbers were mainly those in which only organic ultraviolet absorbers were dissolved in liquid oil, or simply emulsified them. As an organic ultraviolet absorber, organic compounds, such as a salicylic acid derivative, a cinnamic acid derivative, or a benzophenone derivative, are mentioned. They absorb ultraviolet light and become an excited state, and the energy is converted into heat or light energy that is less irritating to the skin and released, thereby returning to the ground state.

However, these early organic UV absorbers are poor in use, such as stickiness persists when applying the skin, there was a limit to the technology for compounding a large amount effective in the nature of the emulsification. In order to overcome this problem, research has been conducted in the direction of formulating an inorganic ultraviolet scattering agent. The metal oxide of zinc oxide or titanium oxide has a band structure in the energy state in which electrons exist due to the periodic potential field, and the energy difference between the upper end of the valence band and the lower end of the conduction band is called band gap energy. do. Zinc oxide has a bandgap energy of 3.2 eV, and when more energy is irradiated, electrons are excited, and the electrons are indirectly transitioned and photoexcitation occurs below 320 nm, which is used as UVB and UVA wave blockers. Titanium oxide has the same effect and is used as a UVB wave blocker.

However, the fine particle powder of titanium oxide used as an inorganic UV scattering agent has a high blocking effect of UVB waves, but when combined with a sunscreen agent, a metallic blue film is formed on the skin, making it difficult to be used in cosmetic personal care products. Catalytic activity is strong enough to decompose organic matter into hydrogen and oxygen, and tends to deteriorate the performance of other components of the sunscreen. This tendency also applies to zinc oxide, which can be used as a UVB and UVA wave blocker. To solve this problem, a technique for blocking catalytic activity by coating the surface of the fast particulate powder with an emulsion or silicon has been established. Moreover, the effect of controlling cohesion was also obtained by performing such fine particle powder coating.

However, recent studies have shown that the sunscreen index SPF (UVB) and PA (UVA) are largely dependent on the uniform dispersion of the sunscreen, and the development of the blocker itself and the method of maintaining the dispersion of the blocker particles. It is being studied.

Methods of dispersing the sunscreen agent include a method using a dispersant and a method using SPF / PA booster (Booster). In the case of using a dispersant, silicone oil is generally used to form the W / O emulsion of the sunscreen particles, and these have low viscosity and light skin spreadability and feel. In this method, control of the phase separation of the sunscreen fine particles in the oil-based component is very important for maintaining the function and storage stability of the sunscreen. However, there is a disadvantage in that the usability is excellent while the lasting effect of the sunscreen effect is rapidly lowered over time.

As an alternative to this problem, a method using SPF / PA boosters has been developed. International patent application WO2006 / 028931 discloses an SPF / PA booster having a structure in which a methacrylate monomer is graft polymerized on a basic skeleton of vinyl acetate to form a side chain. They serve to double the sunscreen effect as the sunscreen particles are placed between the polyacrylic side chains and applied to the skin in a dense and uniformly distributed state. In addition, the polymer booster itself and the sunscreen particles by the physical combination of the role of preventing the sunscreen penetrates into the skin has the property of continuing the sunscreen effect.

As mentioned above, the acrylic SPF / PA booster proposed for the uniform dispersion of the sunscreen acts as an excellent sunscreen aid by itself. However, despite the excellent UV protection effect, SPF / PA booster has a specific odor of the raw material itself and emulsifiers, there is a limit to commercialization, there is also room for improvement of the sun protection effect by the structural modification of the SPF / PA booster. Therefore, there is a need to develop a structure that enables a more compact distribution of the sunscreen in order to enhance the sunscreen effect. There is also a need to develop a process for removing specific odors prior to formulation.

The inventors of the present invention carried out a study to give new properties to the SPF / PA booster to solve the conventional problems. As a result, the addition of new monomers and crosslinkers increased the particle dispersion performance of the SPF / PA booster.

As one feature of the present invention, the SPF / PA booster of the present invention forms a crosslink between the booster side chain and the side chain, and the side chain and the main chain by adding a crosslinking agent. This makes it possible to achieve a denser and more uniform distribution than when the polymer itself forms a network to distribute the sunscreen only on the side chains of the linear polymer.

In one embodiment of the present invention, the polymer emulsion for SPF / PA booster of the present invention comprises (1) a semicrystalline polymer, (2) a polymer of acrylic acid and / or methacrylic acid and / or unsaturated monomers, (3) one or Optionally comprising (4) one or more phase stable emulsifiers, (5) one or more thickeners, (6) acrylic or styrene-acrylic resins having an average molecular weight of 2,000 to 15,000 Daltons, and (7) tallow alkyls. Polypropylene polymers or polyethylene oxides prepared with cationic functional groups such as amines. In this case, most of the graft polymers have a semicrystalline polymer as a main chain, and a polymer of a plurality of acrylic acid and / or methacrylic acid and / or unsaturated monomers has a side chain grafted copolymer, and the side chain and side chain or Crosslinks are formed between the side chain and the main chain.

The polymer emulsion for SPF / PA booster of the present invention contains the following components.

(1) semicrystalline polymer

Semicrystalline polymers include ethylene, propylene, acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, vinyl acetate, At least one monomer, including but not limited to ethyl acrylate and similar lower (C ₁ -C ₈ ) esters of acrylic acid and methacrylic acid, and preferably at least two. In the case of containing two or more types of monomers, the semicrystalline polymer has the form of a copolymer.

(2) polymers of acrylic acid and / or methacrylic acid and / or unsaturated monomers

The polymer of the unsaturated monomer is ethyl acrylate (ethyl acrylate), butyl acrylate (butyl acrylate), 2-ethyl hexyl acrylate (2-ethyl hexyl acrylate), butyl methacrylate (butyl methacrylate), methyl methacrylate ( methyl methacrylate, styrene, ethoxylated C ₁ -C ₆ esters of acrylic acid and methacrylic acid, such as hydroxypropyl methacrylate, hydroxyethyl methacrylate, Polyethylene glycol (PEG) and polypropylene glycol (PPG) modified acrylates and meta with hydroxyethyl acrylate, and 1-10 moles of ethylene oxide or propylene oxide or combinations thereof One or more monomers, including but not limited to acrylates, preferably two or more. When two or more types of monomers are included, the polymer of unsaturated monomers has the form of a copolymer. These polymers of acrylic acid are lower amino alkyl (C ₁ -C ₆ ) esters of acrylic acid and methacrylic acid, such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, t- The monomer may include one or two or more monomers including but not limited to butylaminoethyl methacrylate, dimethyldiallyl methacrylate and quaternary adducts thereof.

In addition, the monomer may include acryloxyacetic acid, acryloxypropionic acid, methacrylicoxyacetic acid, methacrylicoxypropionic acid or one or two or more thereof. .

(3) one or more crosslinking agents

The crosslinker includes ethylene glycol dimethacrylate, allyl methacrylate, 1,3-butanediol dimethacrylate, diethylene glycol dimethacrylate, and the like. (diethylene glycol dimethacrylate) and divinylbenzene, but are not limited thereto.

The emulsion composition of the present invention may optionally contain the following components:

(4) one or more phase stable emulsifiers

Phase stable emulsifiers suitable for the present invention contain a combination of lipophilic and hydrophilic segments capable of forming an oil-in-water emulsion, and include all emulsifiers that retain the phase stability of long-term emulsions. In addition, all anionic surfactants suitable for emulsion polymerization techniques can be included.

Examples of phase stable emulsifiers include sodium lauryl sulfate, sodium lauryl ether sulfate, sulfonated mono and dialkyl esters of succinic acid and their salts, alkyl esters of diphenyl oxide. Including but not limited to. Phase stability emulsifiers are nonionic surfactants, for example, acrylate and ethylene oxide ethoxylate C _lO -C ₃₀ alkyl alcohols may be selected from propylene oxide block copolymer.

(5) one or more thickeners

Examples of the thickener include, but are not limited to, cellulose derivatives, polyacrylic acid derivatives, guar gum, and the like. This component serves to prevent the precipitation of the emulsion of the present invention to impart emulsion stability.

(6) acrylic or styrene-acrylic resins having an average molecular weight of 2,000 to 15,000 daltons

The monomer of the resin may be selected from acrylic monomers listed in (1) or (2). This component serves to improve the physical properties of the present invention.

(7) oxidized polyethylene or polypropylene polymers made of cationic functional groups, such as tallow, i.e. animal fat

As an example of the said component, the cation emulsion of a high density polyethylene oxide wax is preferable. These improve the hydrophobic / hydrophilic balance and the affinity between each component.

Looking at the composition ratio of the polymer emulsion for SPF / PA booster of the present invention, when the present invention consists of components (1) to (3) component (1) is 29% to 98.99 based on the total weight of the components excluding the aqueous phase medium %; Component (2) 1% to 70%; Component (3) is 0.01 to 1%. Further, when the present invention optionally further comprises components (4) to (7) as components, component (4) is 0.01 to 1%, preferably 1 to 1, based on the total weight of the components excluding the aqueous medium. 15%; Component (5) is 0.01 to 5%, preferably 1 to 3%; Component (6) from 0.01 to 20%, preferably from 0.2% to 20%; Or component (7) is contained in an amount of 0 to 5%, preferably 0.5% to 1.5%, wherein the content of components (1) to (3) is suitably adjusted according to the content of additionally selected components. In addition, the average molecular weight of the polymer emulsion for SPF / PA booster of the present invention is preferably 500 to 1,000,000 daltons.

In the polymer emulsion for SPF / PA booster according to the present invention, when the crosslinking agent content is less than 0.01%, the network formation effect due to the crosslinking is insignificant and does not affect the SPF / PA value. As a result, the structure of the side chain in which the particles are trapped is destroyed, so that the SPF / PA boosting effect is not exerted.

As used herein, the term “semicrystalline polymer” means a polymer that exists in the form of a viscous liquid at a temperature above the melting point of the crystal. In the case of cooling, crystals aggregate and grow to increase in volume. These materials are referred to as “semicrystalline” because, when cooled at room temperature, a portion of the polymer remains microcrystalline or amorphous. Amorphous polymers are trapped between growing crystals. Due to the highly entangled structural properties of the polymer chains, the movement of the amorphous polymer is limited.

As used herein, the term "olefin" means an alkene. By "alkene" is meant herein all aliphatic hydrocarbons containing at least one carbon-carbon double bond. As used herein, the term "alkyl group" is a hydrocarbon in a molecule that bonds to another functional group in the molecule via a single covalent bond of one of the carbon atoms. Alkyl groups are cyclic, branched or unbranched, substituted or unsubstituted and / or saturated or unsaturated forms. Alkyl groups are, for example, from 1 to about 24 carbons, from 1 to about 12 carbons or from 1 to about 4 carbons, ie methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert -Butyl.

<Graft polymer emulsion polymerization>

The preparation of the polymer emulsion according to the invention is by the following method. Semicrystalline olefin polymers are obtained from various manufacturers such as Honeywell, Dupont or Sud-Chemie. This type of polymer is provided in pellet or flake form and must be emulsified before use. Depending on the function of the base olefin, it is carried out at pressurized or atmospheric pressure. High temperature and pressure resistant vessels are required to emulsify hot melt olefins and low functional polymers. Specific emulsification processes for such polymers are provided by the manufacturer and are readily understood by those skilled in the art. In general, this process relates to the melting of polymer pellets at temperatures above softening point / melting point in the presence of a neutralizing base to provide adequate emulsion stability in the water phase. Graft polymerization of the invention is by physical bonding of polymer chains and covalent graft bonds. Graft polymerization results in a uniform polymer emulsion with a single glass transition temperature (Tg) and the ability to not degrade to thermal, chemical attack.

As a feature of the present invention, the polymer emulsion for SPF / PA booster of the present invention is characterized in that it undergoes a deodorization process to remove the specific odor after the preparation. The deodorization process includes a vacuum deodorization method applying temperature and pressure, an osmosis method using the size and osmotic pressure of a dialysis vessel made of a regeneration membrane, and a diafiltration method using a regeneration membrane and pressure having various pore sizes. It is preferable to use the diafiltration method for deodorization of the polymer emulsion for SPF / PA boosters of the present invention. After deodorization by diafiltration, the content of impurities is reduced from about 350 ppm to 0 ppm (gas chromatograph FID Agilent-7890A).

The polymer emulsion for SPF / PA booster according to the present invention includes a graft polymer having a structure in which side chains and side chains or cross-links between side chains and main chains are formed by a crosslinking agent, whereby the polymer itself forms a network to form a linear A denser and more uniform distribution is achieved than if the sunscreen was distributed only on the side chains of the polymer. Therefore, when the graft polymer emulsion according to the present invention is used as a booster of the sunscreen, the UVB blocking effect and the UVA blocking effect are dramatically improved, and further, the water resistance, adhesion and spreadability are improved to maximize the user's convenience. In addition, the polymer emulsion for SPF / PA booster according to the present invention is removed by the deodorizing process to minimize the discomfort felt by the user.

Hereinafter, the content of the present invention will be described in more detail by the following examples. However, the protection scope of the present invention is not limited by the following examples.

1. Copolymer Emulsion  Produce

Comparative Example 1.

900 g of ion-exchanged water, 20.22 g of polysorbate 80 (trade name Tween 80) and 25.75 g of sorbitan oleate (trade name Span 80), 1.0 g of ammonium persulfate, ethyl acrylate 880.5 g was added in this order and stirred (20-25 ° C., 500 rpm, 30 minutes) to prepare a first reaction medium.

990 g of ion-exchanged water in a secondary emulsion mixer, 35.05 g of sodium dioctyl sulfosuccinate (trade name OT-75), 12.7 g of polysorbate 80 (trade name Tween 80), 1.7 g of ammonium persulfate , 660 g of methyl methacrylate were added in this order and stirred (20-25 ° C., 500 rpm, 30 minutes or less) to prepare a second reaction medium.

1510 g of ion-exchanged water was added to the polymerization reactor, and the mixture was stirred while starting nitrogen filling. Thereafter, the polymerization reactor was heated to 70 ° C., and a first reaction medium was added (loading rate of 50 kg / min). After the first reaction medium was added, the reaction conditions were maintained at 70 to 75 ° C and 200 rpm for 3 hours, and after 3 hours, the reaction conditions were maintained at 90 ° C and 200 rpm. Then, after slowly adding the second reaction medium, the reaction conditions were maintained at 70 ~ 75 ℃, 200rpm for 3 hours, and aged for 5 hours. After completion of the reaction aging, the polymer solution was contacted with regenerated cellulose membranes of various sizes and the polymer was pressed to isolate and deodorize the material of interest.

The obtained acrylic copolymer emulsion had a solids content of 30% by weight, a pH of about 7.5, and a viscosity of 20 cps. A white fluid emulsion solution having a size range of 10 to 500 nm was obtained.

Comparative Example 2

It was prepared in the same manner as in Comparative Example 1 except for further adding an acryloxyacetic acid to the second reaction medium.

The obtained acrylic copolymer emulsion had a solid content of 30% by weight, a pH of about 7.5, and a viscosity of 32 cps. A white fluid emulsion solution having a size range of 10 to 500 nm was obtained.

Example 1.

Comparison was made except that an additional 0.3 g of divinyl benzene was added as a crosslinking agent to the primary emulsion mixer and an additional 0.3 g of diallyl phthalate was added as the crosslinking agent to the secondary emulsion mixer. Prepared in the same manner as in Example 1.

The obtained acrylic copolymer emulsion had a solid content of 30% by weight, a pH of about 7.5, and a viscosity of 560 cps. A white flowable emulsion solution having a size range of 10 to 350 nm was obtained.

Example 2.

Comparison was made except that an additional 0.5 g of divinyl benzene was added to the primary emulsion mixer as a crosslinking agent, and 0.5 g of diallyl phthalate was further added to the secondary emulsion mixer as a crosslinking agent. Prepared in the same manner as in Example 2.

The obtained acrylic copolymer emulsion had a solid content of 30% by weight, a pH of about 7.5, and a viscosity of 778 cps. A white fluid emulsion solution having a size range of 10 to 300 nm was obtained.

2. Copolymer Emulsion  UV protection Sunscreen  Produce

Using the copolymer emulsion prepared in Comparative Examples 1 to 2 and Examples 1 to 2 was prepared as a sunscreen for sun protection as shown in Table 1 below.

Main Phase Ingredient Control Comparative Preparation Example 1 Comparative Production Example 2 Preparation Example 1 Production Example 2 A Distilled water 70 65 65 65 65 Dissolvine Na2-S 0.05 0.05 0.05 0.05 0.05 Propylene glycol 2.0 2.0 2.0 2.0 2.0 Copolymer emulsion - 5.0 5.0 5.0 5.0 B Finsolv TN 3.0 3.0 3.0 3.0 3.0 Protachem SMO 0.2 0.2 0.2 0.2 0.2 Escalol 557 Octinoxate 7.5 7.5 7.5 7.5 7.5 Escalol 567 Oxybenzone 3.0 3.0 3.0 3.0 3.0 Escalol 587 3.0 3.0 3.0 3.0 3.0 Crodafos ces 4.0 4.0 4.0 4.0 4.0 Ceterayl Alcohol 50/50 4.0 4.0 4.0 4.0 4.0 Crodafos C320 Acid 1.33 1.33 1.33 1.33 1.33 C Liquid Germall Plus 0.6 0.6 0.6 0.6 0.6 Frangrance 0.15 0.15 0.15 0.15 0.15 TEA 99% 0.1 0.1 0.1 0.1 0.1 D TiO ₂ 4.0 4.0 4.0 4.0 4.0 ZnO 2.0 2.0 2.0 2.0 2.0 DC 345 8.0 8.0 8.0 8.0 8.0

In Table 1, the units of the components are all "g", Comparative Preparation Example 1 is a copolymer emulsion prepared in Comparative Example 1, Comparative Preparation Example 2 is a copolymer emulsion prepared in Comparative Example 2 In Preparation Example 1, a copolymer prepared in Example 1 was used as a copolymer emulsion, and Preparation Example 2 used a copolymer prepared in Example 2 as a copolymer emulsion.

3. Copolymer Emulsion  UV protection In sunscreen  About SPF Boosting  effect

(1) test method

Among healthy healthy men and women between the ages of 18 and 60 years with no skin disease, 10 or more persons with skin types of Fitzpatrick optical skin type I to III with a minimum erythema of 20mJ / cm 2 to 50mJ / cm 2 were selected. It was carried out according to the method and criteria for measuring the sunscreen effect according to Article 9 of the Cosmetic Act.

After sectioning the product-free area at the back of the subject, the subject is allowed to take a comfortable position and irradiates with UVB to determine the subject's erythema state at a predetermined time within the range of 16 to 24 hours. Erythema is judged by two or more skilled people under sufficiently bright light sources. The minimum amount of UVB light irradiated to the erythema appeared on the front surface is the minimum amount of erythema (MED). Based on the minimum amount of erythema of each subject, the range of light is determined based on the expected blocking index of the standard sample and the test product, and then the standard sample application site and the test product application site are divided on the subject's back. Put a rubber thimble on your finger and apply the appropriate amount of standard sample and test product. After drying at room temperature for 15 minutes, measure the same amount as the minimum erythema of the product-free area. The erythema determination is made by the same person at the same time as the minimum erythema measurement time of the product-free area.

The light source has a continuous emission spectrum similar to sunlight and uses a solar simulator or similar light source equipped with a Xenon arc lamp that does not exhibit a specific peak. At this time, the wavelength of less than 290nm should be removed using a suitable filter, and maintain a constant amount of light for the test time.

As the standard sample, a high UV blocking index (SPF20 or higher) standard sample was used, and the UV blocking index was 15.5 ± 3.0. The product application amount is 2.0 mg / cm 2 or 2.0 μL / cm 2, and the product application area is 24 cm 2 (6 cm × 4 cm = 24 cm 2) or more and five or more irradiation sites having an area of 0.5 cm 2 or more are divided. The amount of light at each irradiation site is adjusted so that the area where minimal erythema is expected is medium (eg 3 or 4 positions) and accordingly equal to 25% or less when the estimated UVF is less than 20 and less than 20 or less than 30 If less than 15%, if more than 30 less than 10%) increase the amount of light at intervals.

The UV protection index (SPF) is obtained by calculating the minimum amount of erythema (MEDu) of the product-free area and the minimum amount of erythema (MEDp) of the product application area, and calculating the UV-protection index (SPFi) of each subject according to the following equation. It is done. The 95% confidence interval of the sunscreen index should be within ± 20% of the sunscreen index. However, if this condition is not met, test again by increasing the number of samples or by resetting the test conditions.

The sunscreen index (SPF) is expressed as an integer after the decimal point of the sunscreen index (SPF) value obtained according to the sunscreen index calculation method is discarded.

The standard samples used in the test were prepared and used as shown in Table 2 below according to the method for measuring the UV blocking effect according to 2008-60 No. 2008-60, and the high SPF standard sample preparation method presented in the standards.

Main Phase ingredient amount(%) A Cetostearyl alcohol (and) PEG-40 caster oil (and) Sodium cetearyl sulphate 3.15 Decyl oleate 15.0 Octyl methoxycinnamate 3.0 Butyl methoxydibenzoylmethane 0.5 Propyl hydroxybenzoate 0.1 B Purified water 53.57 Phenylbenzimidazole sulphonic acid 2.78 Sodium hydroxide (45% solution) 0.9 Methyl hydroxybenzoate 0.3 Disodium edetate 0.1 C Purified water 20.0 Carbomer 0.3 Sodium hydroxide (45% solution) 0.3

(2) test result

The SPF boosting test results for 10 subjects are shown in Table 3 below.

Subject age Control Comparative Preparation Example 1 Comparative Production Example 2 Preparation Example 1 Production Example 2 KWK 39 30.3 35.0 39.5 43.7 48.5 PYS 25 35.3 37.2 38.2 48.9 53.3 KJH 20 27.2 32.1 36.8 38.4 38.3 LSJ 21 33.5 30.7 33.8 37.3 46.8 KBS 25 38.1 43.9 45.3 48.2 45.5 CKS 25 26.0 31.6 37.5 40.0 49.9 LTU 23 29.9 30.2 39.0 39.1 44.3 LJS 22 30.2 30.3 38.6 44.2 47.5 JYK 22 32.5 36.6 35.4 40.8 48.0 CES 25 25.1 32.9 43.8 41.3 39.1 Average 24.7 30 34 38 42 46

4. Copolymer Emulsion  UV protection In sunscreen  About PA Boosting  effect

(1) test method

Ten healthy males and females aged 18-60 years without skin disease were selected as subjects and were performed according to the method and criteria for measuring the effect of sunscreen according to Article 9 of the Cosmetic Act. After sectioning the uncoated test site on the subject's back, the subject is placed in a comfortable position and irradiated with UVA. Do not move the subject while irradiating ultraviolet light. The blackening state of the subject is determined at a fixed time within 2 to 4 hours after the investigation is completed. Two or more skilled people will judge under a sufficiently bright light source. The minimum amount of UVA light irradiated to the site where blackening appears on the entire surface is the minimum sustained instant blackening amount (MPPD).

After determining the range of irradiated light based on the minimum sustained instantaneous blackening amount of each subject, the standard sample application site and the product application site are divided on the subject's back. Put a rubber thimble on your finger and apply the standard sample and product as appropriate. After drying for 15 minutes at room temperature, measure the same as the minimum continuous instantaneous blackening (MPPD) measurement of the product uncoated area. The judgment is made by the same person at the same time as the minimum continuous instantaneous blackening measurement time of the product-free area.

The light source uses an artificial light source that satisfies the following and maintain and check that the following conditions are always satisfied. The light source should have a continuous spectrum similar to sunlight in the UVA range. In addition, the ratio of UVA I (340-400 nm) and UVA II (320-340 nm) should be similar to the ratio of sunlight (ultraviolet A II / total UV A = 8-20%). To avoid excessive sun burn, ultraviolet rays below wavelength 320 nm are removed using an appropriate filter. The standard sample used the standard sample of Table 4, and the ultraviolet-ray A blocking index was 3.75 +/- 1.

Main Phase ingredient amount (%) A Purified water 57.13 Dipropylene glycol 5.00 Potassium Hydroxide 0.12 Trisodium EDTA 0.05 Phenoxyethanol 0.30 B Stearic acid 3.00 Glyceryl Monostearate, selfemulsifying 3.00 Cetearyl Alcohol 5.00 Petrolatum 3.00 Triethylhexanoin 15.0 Ethylhexylmethoxycinnamate 3.00 (Ethylhexyl Methoxycinnamate) 5.00 Butylmethoxydibenzoylmethane 0.20 Ethylparaben Methylparaben 0.20

The product application amount is 2 mg / cm 2 or 2 μL / cm 2, and the product application area is 24 cm 2 or more, and five or more irradiation sites having an area of 0.5 cm 2 or more are partitioned. The partitioning method is the same as the UV blocking index measurement method. The amount of light at each irradiation site is adjusted so that the minimum sustained instantaneous blackening is expected to be in the middle (eg, 3 or 4 positions) and accordingly increases the amount of light at equal intervals. The rate of increase is up to 25%.

The UVA blocking index (PFA) is obtained by determining the minimum sustained instantaneous blackening amount (MPPDu) of the product-free coating site and the minimum sustained instantaneous blackening amount (MPPDp) of the product coating site, and according to the following equation, Calculate (PFAi) and use the arithmetic mean value. In this case, the standard error of the UVA blocking index (PFA) should be within ± 10% of the obtained UVA blocking index (PFA) value. However, if this condition is not met, test again by increasing the number of samples or by resetting the test conditions.

(2) test result

The PA test results for ten subjects are shown in Table 5 below.

Subject age Control Comparative Preparation Example 1 Comparative Production Example 2 Preparation Example 1 Production Example 2 KWK 39 5.01 5.66 6.06 7.05 7.78 PYS 25 5.65 5.87 6.24 6.86 7.62 KJH 20 5.87 5.85 6.97 8.24 8.47 LSJ 21 5.16 5.55 6.02 6.77 6.98 KBS 25 5.54 5.91 6.83 7.54 8.29 CKS 25 5.98 6.78 6.75 7.37 8.51 LTU 23 6.23 6.99 6.84 8.05 8.25 LJS 22 6.39 6.27 6.94 8.27 8.18 JYK 22 4.91 5.45 6.37 7.01 7.85 CES 25 6.55 7.02 7.58 7.47 8.24 Average 24.7 5.73 6.14 6.66 7.46 8.02

5. UV protection Sunscreen  Water resistance

(1) test method

The water resistance test is a comparison between the UV protection index and the water resistance UV protection index after conducting the test according to the water resistance test method below. The water resistance test is divided into a water resistant product and a durable water resistant product according to the water resistance test method. The test shall be made indoors which may block direct sunlight which may affect the test, and the water temperature shall be between 23 and 32 ° C.

The tub should be fully submerged in the test area of the subject and should be comfortable sitting on the subject's back without touching the tub wall. At this time, do not directly touch the subject's back during water circulation or air ejection.

The UV protection index and the UV resistance index according to the water resistance test method shall be measured under the same test conditions using the same equipment for the same subject in the same laboratory. The test method shall be tested in accordance with the KFDA Notification and Methods of Measuring UV Protection Effects.

After application, dry for at least 15 minutes in natural state, and soak in water.

Detailed methods for measuring the water resistance of the product are as follows.

① Get 20 minutes. ② Rest for 20 minutes outside the water. At this time, let it dry naturally and prohibit the use of towel on the application area of the product. ③ Get 20 minutes. ④ Let it dry naturally for more than 15 minutes until it comes out of water and dries out completely.

Thereafter, the minimum erythema amount measurement test shall be conducted in accordance with the KFDA's Notice of Methods and Standards for Measuring UV Protection Effect. The calculation is based on the calculation of the UV protection index of the KFDA Notification Methods and Standards of UV Protection Effect and the UV protection index and the water resistance UV protection index.

In SPF: Water resistant UV protection index of each subject, SPF: UV protection index of each subject, Average water resistance ratio: The average water resistance ratio is the average of the individual water resistance ratios of each subject.

Water resistance ratio confidence interval: The mean water resistance ratio confidence interval is expressed as a 95% confidence interval in one direction and the calculation is as follows.

(S: standard deviation, n: number of subjects, t value: degrees of freedom, t value of 1.833 when n is 10)

The determination can demonstrate water resistance when the water resistance ratio confidence interval is 50% or more.

(2) test result

The water resistance test results for 10 subjects are shown in Table 6 below.

Subject age Control Comparative Preparation Example 1 Comparative Production Example 2 Preparation Example 1 Production Example 2 B / W A / W B / W A / W B / W A / W B / W A / W B / W A / W KWK 39 30.3 10.1 35.0 13.5 39.5 22.2 43.7 29.9 48.5 35.5 PYS 25 35.3 13.5 37.2 13.7 38.2 19.8 48.9 30.2 53.3 35.3 KJH 20 27.2 12.7 32.1 15.4 36.8 20.5 38.4 17.4 38.3 25.9 LSJ 21 33.5 13.4 30.7 17.9 33.8 15.1 37.3 19.9 46.8 23.0 KBS 25 38.1 17.3 43.9 25.3 45.3 27.3 48.2 28.2 45.5 33.3 CKS 25 26.0 8.5 31.6 13.3 37.5 18.2 40.0 27.3 49.9 38.2 LTU 23 29.9 11.9 30.2 17.5 39.0 20.9 39.1 18.2 44.3 23.3 LJS 22 30.2 15.2 30.3 15.5 38.6 23.1 44.2 32.1 47.5 35.4 JYK 22 32.5 18.7 36.6 21.0 35.4 22.4 40.8 22.9 48.0 30.1 CES 25 25.1 7.4 32.9 12.4 43.8 20.0 41.3 27.4 39.1 25.3 Average 24.7 30 12 34 16 38 20 42 25 46 30 Subject's average water resistance ratio (%) 39 49 52 59 65 Water resistance ratio confidence interval (%) 33 42 45 50 55

In Table 6, B / W is the SPF value measured before entering the water, A / W is the SPF value measured after acquisition for 40 minutes (two times every 20 minutes).

6. UV protection Sunscreen  Adhesion and Brittle

(1) test method

Subjects who participated in the UV block index measurement method were subjective questionnaire about skin adhesion and spreadability based on the following scores.

* Score criteria for cohesive sensory evaluation (the same criterion)

Very good: 3 points, Excellent: 2 points, Normal: 1 point, Bad: -1 point,

Very bad: -2 points

(2) test result

The adhesion and spreadability test results of 10 subjects are shown in Table 7 below.

Subject age Control Comparative Preparation Example 1 Comparative Production Example 2 Preparation Example 1 Production Example 2 Adhesion Brittle stick
castle Brittle stick
castle Brittle stick
castle Brittle stick
castle Brittle KWK 39 -One One One One One 2 One 2 2 3 PYS 25 One 2 One One 2 One 2 2 2 3 KJH 20 -One One One 2 2 One 2 2 2 2 LSJ 21 -2 One One 2 One 2 One 2 3 One KBS 25 One 3 2 2 3 One 2 One 2 One CKS 25 2 2 2 2 2 One 2 2 One 2 LTU 23 One One 2 One 2 3 3 One 2 3 LJS 22 -One -One One One One 2 2 One 2 2 JYK 22 -2 -One One One One -One 2 2 2 3 CES 25 -2 One One 2 -One One One One 2 2 Average 24.7 -0.4 1.0 1.3 1.5 1.4 1.3 1.8 1.6 2.0 2.2

Claims (16)

A sunscreen booster consisting of an emulsion comprising an aqueous medium and an acrylic copolymer, The acrylic copolymer is a block copolymer composed of two or more monomers selected from the group consisting of alkyl esters of acrylic acid and alkyl esters of methacrylic acid, The alkyl group of the alkyl ester of acrylic acid and the alkyl ester of methacrylic acid is 1 to 8, characterized in that the sun protection booster. The method of claim 1, wherein the alkyl ester of acrylic acid is methyl acrylate (ethyl acrylate), ethyl acrylate (ethyl acrylate), butyl acrylate (butyl acrylate), and 2-ethylhexyl acrylate (2-ethylhexyl acrylate) And an alkyl ester of methacrylic acid is selected from methyl methacrylate or butyl methacrylate. The sunscreen booster according to claim 2, wherein the acrylic copolymer is a block copolymer composed of at least one monomer selected from alkyl esters of acrylic acid and at least one monomer selected from alkyl esters of methacrylic acid. A sunscreen booster consisting of an emulsion comprising an aqueous medium and an acrylic copolymer, The acrylic copolymer may include (a) at least one first monomer selected from the group consisting of alkyl esters of acrylic acid and alkyl esters of methacrylic acid; (b) a second monomer comprising at least one member selected from the group consisting of alkyl esters of acrylic acid and alkyl esters of methacrylic acid, the second monomer consisting of a material different from the first monomer; And (c) a crosslinking agent comprising at least two unsaturated bonds, The alkyl group of the alkyl ester of acrylic acid and the alkyl ester of methacrylic acid has 1 to 8 carbon atoms, The first monomer is 29 to 98.99% by weight, the second monomer is 1 to 70% by weight and the crosslinking agent is 0.01 to 1% by weight based on the total weight of the emulsion components excluding the aqueous medium. UV protection booster. The method of claim 4, wherein the alkyl ester of acrylic acid is methyl acrylate (ethyl acrylate), ethyl acrylate (ethyl acrylate), butyl acrylate (butyl acrylate), and 2-ethylhexyl acrylate (2-ethylhexyl acrylate) And an alkyl ester of methacrylic acid is selected from methyl methacrylate or butyl methacrylate. The method of claim 5, wherein the crosslinking agent is diallyl phthalate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, allyl methacrylate, 1,3-butanediol dimethacrylate (1). , 3-butanediol dimethacrylate), diethylene glycol dimethacrylate (diethylene glycol dimethacrylate), and a sunscreen booster, characterized in that at least one selected from the group consisting of divinylbenzene. 7. The sunscreen booster according to claim 6, wherein the first monomer is at least one selected from alkyl esters of acrylic acid, and the second monomer is at least one selected from alkyl esters of methacrylic acid. 8. The sunscreen booster of claim 7, wherein the first monomer is ethyl acrylate and the second monomer is methyl methacrylate. The sunscreen booster of claim 8, wherein the crosslinking agent is composed of diallyl phthalate and divinylbenzene. The method of claim 6, wherein the emulsion further comprises a phase stable emulsifier, The first monomer is 29 to 97.99% by weight, the second monomer is 1 to 55% by weight, the crosslinker is 0.01 to 1% by weight, and the phase is based on the total weight of the emulsion components, Stability emulsifier UV protection booster, characterized in that 1 to 15% by weight. The method of claim 10, wherein the phase stability emulsifier is polysorbate, sodium lauryl sulfate, sodium lauryl ether sulfate, sulfonated monoalkyl ester of succinic acid, succinic acid A sunscreen booster, characterized in that at least one selected from the group consisting of sulfonated dialkyl esters, spans (span, esters of sorbitan), and ethylene oxide-propylene oxide block copolymers. The sunscreen booster according to claim 11, wherein the first monomer is at least one selected from alkyl esters of acrylic acid, and the second monomer is at least one selected from alkyl esters of methacrylic acid. The method of claim 12, wherein the first monomer is ethyl acrylate, the second monomer is methyl methacrylate, and the crosslinking agent is diallyl phthalate and divinylbenzene. (divinylbenzene), wherein the phase stable emulsifier is polysorbate (Polysorbate), succinic acid sulfonated dialkyl ester and span (Span, ester of sorbitan), characterized in that the sun protection booster. The method of claim 9, wherein the second monomer is acryloxyacetic acid, acryloxypropionic acid, methacryloxyacetic acid, and methacryloxypropionic acid. methacryloxypropionic acid) sun protection booster, characterized in that it comprises one or more selected from the group consisting of. The method according to claim 9 or 13, wherein the first monomer forms a main chain of the acrylic copolymer, the second monomer forms a side chain of the acrylic copolymer, and the side chain and side chain are formed by the crosslinking agent. A sunscreen booster, characterized in that a crosslink is formed between the liver or the side chain and the main chain. 15. The method according to claim 14, wherein the first monomer forms the main chain of the acrylic copolymer, the second monomer forms the side chain of the acrylic copolymer, crosslinked between the side chain and the side chain or between the side chain and the main chain by the crosslinking agent. UV protection booster, characterized in that formed.