KR101238379B1 - Titanium dioxide capsules containing ultraviolet absorber and the cosmetic composition containing the same - Google Patents

Abstract

The present invention is to encapsulate the ultraviolet absorber inside the titanium dioxide which is the ultraviolet scattering agent to encapsulate the ultraviolet absorber in order to maximize the advantages while improving the disadvantages of the conventional ultraviolet absorber and the ultraviolet scattering agent, thereby improving the stability of heat and light of the ultraviolet absorber and the ultraviolet absorber It relates to a titanium dioxide capsule and a cosmetic composition containing the UV absorber is improved UV protection effect and improve the feeling and color expression than when used to contain and containing titanium dioxide, respectively.

Description

Titanium dioxide capsules containing ultraviolet absorber and the cosmetic composition containing the same}

The present invention relates to a titanium dioxide capsule in which a UV absorber is collected, and more particularly, it is unstable to heat and light, so that it is difficult to sustain the UV blocking effect, and there is a skin irritation, so that the feeling is not good, so that a sufficient amount to use It relates to a titanium dioxide capsule produced by collecting a difficult ultraviolet absorber into the inside of the titanium dioxide pigment. The present invention also relates to a cosmetic composition containing a titanium dioxide capsule in which the ultraviolet absorber is collected as an active ingredient.

Ultraviolet radiation from the sun consists of a long wavelength (UV-ray A) (approximately 320-400 nm), short wavelength called UV B (UV-ray B) (approximately 290-320 nm), and shorter UV C. It is. About 6% of the ultraviolet rays A and B reach the surface of the sun, but the ultraviolet rays C are absorbed and scattered in the ozone layer and the atmosphere of the ground and do not reach the surface. These ultraviolet rays have harmful aspects that cause sunburn, skin cancer, skin aging, photosensitive dermatitis, mutations, and the like. Ultraviolet A penetrates the dermis, causing pigmentation and skin aging, and is involved in the development of photosensitive skin diseases.UV B penetrates the epidermis and upper dermis with higher energy rays of shorter wavelengths and is involved in sunburn, pigmentation and skin cancer. It is known. Types of sunscreens to prevent such side effects of sunlight are mainly UV absorbers that block UV rays through chemical absorption of sunlight and UV scatterers that prevent penetration into the skin through physical reflection and scattering of sunlight. have.

In general, sunscreen products are appropriately formulated by combining or absorbing UV absorbers and UV scatterers, and serves to block UV from direct contact with the skin, and its performance is generally Sun Protection Factor (Sun Protection Factor, SPF). Specifically, the UV blocking index is an index showing the blocking effect against UV B. The minimum Erythermal Dose (MED) obtained by irradiating UV B on a portion where the UV blocking product is not applied is applied to the UV blocking product. The relative value divided by the minimum amount of erythema. The minimum amount of erythema is the minimum amount of ultraviolet radiation that causes erythema to appear in most of the irradiated area after 16-24 hours after UV B is irradiated to human skin.

On the other hand, after 2-4 hours after irradiation with UV A, the minimum amount of ultraviolet radiation that is basically perceived as faint blackening of the entire area of the irradiation area is called the minimum persistent pigmentation darkening dose (MPPD). At this time, the MPPD ratio between the blocking product application site and the non-coating site is referred to as the Protection Factor of UV A (PFA). The outer A blocking grade (PA) is an index indicating the degree of blocking effect of UV A.

A typical UV absorber is a compound having a pi-conjugation molecular structure having an electron donating group such as an amine or methoxyl group in the ortho- or para- position of an aromatic ring structure. (para-aminobenzoic acid), PABA derivatives, cinnamate derivatives, salicylic acid derivatives, benzopheneone, anthranilates and the like.

When ultraviolet light stimulates a material of the structure, the material absorbs ultraviolet light and becomes photochemically excited, and when returning to the original energy state, the excess absorbed energy is released as modified secondary energy, and thus has ultraviolet light blocking ability. . However, UV absorbers do not withstand the energy accumulated in the photochemically excited state and are decomposed by heat or decomposed by heat to reduce the UV blocking effect. Also, most UV absorbers are skin irritants due to the toxicity of the compounds themselves. There is a disadvantage.

In order to overcome the disadvantages of the conventional ultraviolet absorbents as described above, Korean Patent Publication No. 10-2005-0022036 discloses a polymer capsule containing the ultraviolet absorbent, and the Republic of Korea Patent Publication No. 10-2009-0069370 A cosmetic composition containing a lipid capsule in which an absorbent or blocker is collected is disclosed.

However, the polymer capsules or lipid capsules proposed in the patent are only for overcoming heat and light stability and formulation problems. The problem remains. On the other hand, UV scattering agent is a component present in nature to protect the skin by reflecting and scattering ultraviolet rays penetrating the skin. Representative UV scattering agents include titanium dioxide, zinc oxide, talc, kaolin, magnesium oxide, and the most widely used titanium dioxide and UV to block UV B. Zinc oxide to block A. In particular, titanium dioxide does not have side effects such as contact dermatitis and is not easily erased by water, while it is difficult to maintain an effective content while realizing a desired formulation, it is easily combined to give a bad feeling, and whitening phenomenon when applied to the skin. There are disadvantages that appear.

In the present invention, in order to maximize the advantages while improving the disadvantages of the conventional ultraviolet absorber and ultraviolet scattering agent by encapsulating the ultraviolet absorber inside the titanium dioxide, which is an ultraviolet scattering agent, encapsulation, to improve the heat and light stability of the ultraviolet absorber and the ultraviolet absorber It is an object of the present invention to provide a titanium dioxide capsule and a cosmetic composition containing the UV absorber, which has a UV absorbing agent which improves the UV blocking effect and improves the feeling and color expression than when the titanium dioxide is contained and used respectively.

In order to achieve the above object, in the present invention, a titanium dioxide capsule in which a UV absorber is collected in a capsule made of titanium dioxide as an outer shell is manufactured.

The UV absorber capture titanium dioxide capsule according to the present invention is a surface of the UV absorber is trapped inside the hollow titanium dioxide pigment and the outside of the titanium dioxide pigment so that the UV absorber trapped inside does not escape to the outside of the pigment The structure is processed. For example, referring to FIG. 1, the ultraviolet absorber-collecting titanium dioxide capsule 100 according to the present invention includes a titanium dioxide structure 101 made of titanium dioxide fine particles and an inner wall for supporting the structure 101. 102 and the ultraviolet absorber 103 collected inside the inner wall 102, and the collected ultraviolet absorber 103 is composed of a surface treatment film 104 to make it difficult to escape to the outside of the titanium dioxide structure (101).

Here, the inner wall 102 may be any material capable of supporting the titanium dioxide structure 101, but pigment materials such as silica, mica, talc, and sericite, polyethylene, polypropylene, silicone resin, and polymethyl methacrylate (Polymethly). Select one or two or more kinds of resin materials such as methacrylate). However, it is most preferred to use natural mica or synthetic mica. In addition, as the surface treatment film 104, any material that makes it difficult for the collected ultraviolet absorber to escape to the outside of the capsule may be used, but any one of dimethyl polysiloxane and methyl polysiloxane (silicone); Bees waxes, carnauba waxes, silicone fatty esters (ideal waxes); Lauroyl lysine, glutamic acid metal salt (above amino acids); It is preferable to use polyethylene and polymethyl methacrylate.

Titanium dioxide capsule according to the present invention can be prepared in various sizes in micrometers unit is preferably characterized in that the average particle diameter is 1㎛ to 100㎛. It is difficult to effectively collect the ultraviolet absorbent when the particle size is less than 1㎛, and when the diameter exceeds 100㎛ is not suitable for application as a cosmetic because it is not smooth and uniform application due to too large particle size.

UV absorbers used in the present invention, such as ethyl hexyl methoxycinnamate, cinnamate derivatives such as octyl methoxycinnamate, butylmethoxy dibenzoylmethane, octylsalicylate ( Salicylic acid derivatives such as octyl salicylate, PABA (para aminobenzoic acid) derivatives, benzophenone, and anthracylates should be selected.

The ultraviolet absorber trapped in the titanium dioxide capsule according to the present invention is characterized in that it contains 1 to 60% by weight, preferably 10 to 40% by weight of the total capsule. It is difficult to expect the improvement of the sunscreen effect because the amount of the ultraviolet absorbent is less than 1% by weight, and when it exceeds 60% by weight, it is difficult for the titanium dioxide to sufficiently encapsulate the ultraviolet absorber, which makes particle preparation difficult and also stably stabilizes the formulation. Because it falls.

As a means for carrying out the present invention, generally, a hollow titanium dioxide pigment can be used. For example, the inside of the titanium dioxide pigment coated with nano-sized titanium dioxide fine particles on a plate-shaped mica substrate can be used. A hollow titanium dioxide pigment in the form in which the mica substrate has been substantially removed can be used.

Titanium dioxide capsule in which the ultraviolet absorber according to the present invention is collected, for example, is prepared by first preparing a titanium dioxide pigment having a hollow structure, and then collecting the ultraviolet absorber inside the pigment and surface-treating the exterior of the pigment. It can manufacture.

Hollow structure titanium dioxide pigments used in the present invention, for example, in the titanium dioxide pigment produced by coating the titanium dioxide on a plate-like substrate by dissolving only the substrate of the pigment with an acid or alkali to make the inside of the pigment into a hollow form (Japanese Patent Laid-Open No. 55-60565, Japanese Patent Laid-Open No. 91-94757) As the plate-based substrate, natural mica, synthetic mica, silica and the like can be used, but synthetic mica is preferably used. Examples of the acid used for dissolving the base material include mineral acids such as hydrofluoric acid, hydrochloric acid, sulfuric acid, acetic acid and phosphoric acid, and examples of the alkali include sodium hydroxide and potassium hydroxide.

Another method for producing a UV absorber trapping titanium dioxide capsule according to the present invention is to coat the titanium dioxide nanoparticles on the surface of the resin substrate, such as polyethylene, polymethyl methacrylate, and a resin such as polyethylene, polymethyl methacrylate It can be prepared by dissolving it using a solvent which can be dissolved.

A method of capturing a UV absorber inside a hollow titanium dioxide pigment is generally performed by impregnating the UV absorber with a titanium dioxide pigment and then coating the outside of the titanium dioxide pigment with a surface treatment material.

The present invention provides a cosmetic composition comprising a titanium dioxide capsule in which the ultraviolet absorber is collected. The cosmetic composition may be used for all kinds of cosmetics as well as cosmetics for the purpose of UV protection, but is not particularly limited in the formulation, for example, color cosmetics such as two-way cake, BB cream, loose powder, foundation, It may have a formulation such as nutrition cream, massage cream, sunblock cream, body lotion, body cream, shampoo, rinse and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, Formulation Examples, and Test Examples, but the scope of the present invention is not limited to these examples.

[ Example  One]

Ethylhexylmethoxycinnamate Captured  Titanium Dioxide Capsule Manufacturing

Titanium dioxide pigments were prepared in the following order.

① Slurry with 450 g of synthetic mica-based titanium dioxide pigment to a mixture of 620 g of concentrated sulfuric acid, 300 g of concentrated phosphoric acid, and 1500 g of water, and then stir for 6 hours at 90 ° C.

② After cooling to room temperature, when the slurry is dehydrated or dehydrated, wash it sufficiently until the pH of the filtrate becomes 2 or more.

③ The dehydrated cake is added to 5000 ml of 9% NaOH aqueous solution and slurried, followed by stirring at 90 ° C. for 2 hours.

④ After cooling to room temperature, when the slurry is dehydrated and dehydrated, wash it sufficiently until the pH of the filtrate reaches 10 or less.

⑤ 10-12 hours at 100 ℃.

=> The hollow titanium dioxide pigment obtained after drying was 145 g.

⑥ Impregnate 30 g of ethylhexylmethoxycinnamate UV absorber (DSM Parsol MCX) in 67 g of the hollow titanium dioxide pigment prepared in the above process.

⑦ 3g of dimethylpolysiloxane is additionally added and mixed in a laboratory mixer for pigment surface treatment and dried at 100 ° C. for 10-12 hours.

=> 100g of the titanium dioxide capsule which the ultraviolet absorber was collected was obtained.

As a result of analyzing the components of the titanium dioxide capsule prepared as described above, it was confirmed that the composition consists of 62% titanium dioxide, 30% ethylhexylmethoxycinnamate, 5% mica, 3% dimethylpolysiloxane.

[ Formulation Example  1 and comparison Formulation Example  One]

Formulation Example 1 and Comparative Formulation Example 1 were prepared in a formulation of BB cream with the composition shown in Table 1 below.

TABLE 1

No. Raw material Formulation Example 1 Comparative Formulation Example 1 One Wax 1.00 1.00 2 Cetyl Fiji / Fiji Fiji-10 / 1 Dimethicone 2.50 2.50 3 Sorbitan olivate 0.50 0.50 4 Caprylic / capric triglyceride 3.00 3.00 5 Phenyltrimethicone 12.00 12.00 6 Tocopheryl acetate 0.10 0.10 7 Disodium iodide 0.05 0.05 8 Butylene Glycol 5.00 5.00 9 glycerin 4.00 4.00 10 Sodium chloride 1.50 1.50 11 Titanium Dioxide Capsule (Example 1) 10.00 - 12 Ethyl hexylmethoxycinnamate - 3.00 13 Titanium dioxide - 6.20 14 Mica - 0.50 15 Dimethyl Polysiloxane - 0.30 16 Iron oxide Suitable amount Suitable amount 17 antiseptic a very small amount a very small amount 18 Combination fragrance a very small amount a very small amount 19 Purified water to 100 to 100

<Manufacturing Method>

Formulation Example 1 ;

Components 11 to 16 and 5 of Table 1 were prepared three times by using a three-stage roller dispersion mixing apparatus, and ingredients 1, 2, 3, 4, 6, and 17 were added to the manufacturing unit. After heating to 80-85 ° C., the components treated with the three-stage roller dispersion mixer are added and dispersed. 7, 8, 9, 10, and 19 were prepared by dissolving the components in a separate container, and the resultant was emulsified for 10 minutes while heating at 80-85 ° C. while stirring with a homo mixer. After emulsification, the mixture was cooled to 45 ° C. while stirring using a stirrer, and 18 ingredients were added, cooled to 25 ° C., and then floated to prepare.

Comparative Formulation Example 1 ;

It was prepared in the same manner as in Formulation Example 1, except that the powder of Example 1 was not contained.

[ Formulation Example  2 and compare Formulation Example  2]

Formulation Example 2 and Comparative Formulation Example 2 were prepared as two-way cake formulations using the compositions shown in Table 2 below.

<Table 2>

No. Phase separation Name Formulation Example 2 (wt%) Comparative Formulation Example 2 (wt%) One


A Nylon Powder 1.00 1.00 2 Mica 5.00 5.50 3 Silica 5.00 5.00 4 Magnesium stearate 2.00 2.00 5 Iron oxide Suitable amount Suitable amount 6 Titanium dioxide - 6.20 7 Titanium Dioxide Capsule (Example 1) 10.00 - 8 Talc to 100 to 100 9
B Dimethyl Polysiloxane 5.00 5.30 10 Ethyl hexylmethoxycinnamate - 3.00 11 antiseptic Quantity Quantity 12 Spices Quantity Quantity

<Manufacturing Method>

Formulation Example 2 ;

1) A is added to the Henschel mixer and mixed and stirred at a constant speed.

2) Mix and stir while spraying B on A phase.

3) Mixing A and B The mixed bulk is pulverized three times with an atomizer.

4) The semi-finished product is sifted and aged in airtight storage for 2 days, and then molded (tableted).

Comparative Formulation Example 2 ;

It was prepared in the same manner as in Formulation Example 2, except that the powder of Example 1 was not contained.

[ Formulation Example  3 and comparison Formulation Example  3]

Formulation Example 3 and Comparative Example 3 were prepared in the formulation of the face powder with the composition of Table 3 below.

<Table 3>

No. Upper division Name Formulation Example 2 (wt%) Comparative Formulation Example 2 (wt%) One

A Mica 5.00 5.50 2 Silica 5.00 5.00 3 Iron oxide Suitable amount Suitable amount 4 Titanium dioxide - 6.20 5 Titanium Dioxide Capsule (Example 1) 10.00 - 6 Talc to 100 to 100 7
B Dimethyl Polysiloxane 1.00 1.30 8 Ethyl hexylmethoxycinnamate - 3.00 9 antiseptic Quantity Quantity 10 Spices Quantity Quantity

<Manufacturing Method>

Formulation Example 3 ;

1) A is added to the Henschel mixer and mixed and stirred at a constant speed.

2) Mix and stir while spraying B on A phase.

3) Mixing A and B The mixed bulk is pulverized three times with an atomizer.

4) The semi-finished product is sifted and aged in airtight storage for 2 days, and then molded (tableted).

Comparative Formulation Example 3 ;

It was prepared in the same manner as in Formulation Example 3, except that the powder of Example 1 was not contained.

[ Test Example  One]

Ultraviolet absorber Capture  Analysis of UV Protection Effect of Titanium Dioxide Capsule

Lab scale for widespread quality of sunscreen cosmetics used in conventional cosmetics manufacturer (in By the test method of vitro ), the sunscreen effect of the titanium dioxide capsule of the present invention was analyzed. The instrument used in the experiment was Optometric's SPF analyzer SPF-290S, and the UV protection index (SPF) was set as the average of three experiments.

SPF value was measured using the sample of the BB cream of Formulation Example 1, the two-way cake of Formulation Example 2, the face powder of Formulation Example 3, BB cream of Comparative Formulation Example 1, two-way of Comparative Formulation Example 2 for relative comparison Cake, the face powder of Comparative Formulation Example 3 was also measured and the measurements are summarized in <Table 4>.

TABLE 4

Name of sample Test Items Test result BB cream formulation example 1 SPF / PA 61.99 / 19.19 BB cream comparative formulation example 1 SPF / PA 49.73 / 15.10 Two cake formulation example 2 SPF / PA 27.90 / 8.30 2AKE Comparative Formulation Example 2 SPF / PA 20.10 / 6.48 Face Powder Formulation Example 3 SPF / PA 16.91 / 5.61 Face Powder Comparative Formulation Example 3 SPF / PA 13.77 / 4.30

As can be seen from the results of <Table 4>, the cosmetic containing the ultraviolet absorbent-containing titanium dioxide capsule according to the present invention has a SPF value of 20 to 20 compared to the one containing the ultraviolet absorber and titanium dioxide separately (comparative formulation example). Higher than 30% was confirmed that excellent UV protection effect can be obtained.

[ Test Example  2]

In the formulation of UV absorbers Heat stability  compare

Ethylhexylmethoxycinnamate, one of the ultraviolet absorbents, which is unstable to heat and light and has a low UV protection effect when available for long-term storage in the formulation, is a titanium dioxide capsule in which ultraviolet absorbers are collected as in Example 1 and Comparative Formulation Example 1. BB cream of the general formulation prepared by separately containing each component of BB cream and titanium dioxide capsule containing each was prepared to check the thermal stability of each sample. The prepared samples were sampled at 1 week, 2 weeks, 1 month and 2 months after storage in 25 ℃ and 45 ℃ oven, respectively, and the thermal stability was confirmed by analyzing the concentration of UV absorbers using liquid chromatography. The results are shown in Table 5 below.

<Table 5>

division Storage temperature Initial concentration retention (%) After 1 week after 2 weeks After 1 month Two months later Formulation Example 1 25 ℃ 100 100 100 100 45 ° C 100 100 99 97 Comparative Formulation Example 1 25 ℃ 100 96 91 83 45 ° C 100 92 85 64

As can be seen from the results of Table 5, the BB cream of Formulation Example 1 containing the ultraviolet absorber trapped inside the structure made of titanium dioxide particles maintained an initial amount of 97% or more even after two months, showing excellent thermal stability. However, in the BB cream of Comparative Formulation Example 1 each containing a UV absorber and titanium dioxide separately, the thermal stability was significantly decreased after UV irradiation. As a result, the titanium dioxide capsule used in the present invention reduced the efficacy of the UV absorber due to heat. It can be seen that by preventing the thermal stability of the ultraviolet absorbent in the BB cream can be maintained.

[ Test Example  3]

Comparison of Light Stability in Formulations of UV Absorbers

In order to confirm the light stability of the BB cream prepared in Formulation Example 1 and Comparative Formulation Example 1, the absorbance difference before and after ultraviolet irradiation was confirmed using a UV spectrometer. The initial absorbance was measured using a UV spectrometer, and then the initial measured solution was irradiated with ultraviolet rays for 30 minutes using an ultraviolet lamp. After absorbing UV light, the absorbance of each solution was measured by UV spectroscopy, and the results were compared with those of the initial absorbance. The results of the light stability were calculated as a percentage of the absorbance after UV irradiation to the absorbance before UV irradiation. .

<Table 6>

division Before UV irradiation
Absorbance After ultraviolet irradiation
Absorbance Optical stability Formulation Example 1 One 0.96 96% Comparative Formulation Example 1 One 0.72 72%

As can be seen from the results of <Table 6>, the BB cream of Formulation Example 1 containing the ultraviolet absorber trapped inside the structure made of titanium dioxide particles maintained excellent initial stability of 96% even after UV irradiation, but showed excellent light stability. In the BB cream of Comparative Formulation Example 1 each containing a UV absorber and titanium dioxide separately, the light stability was significantly decreased after UV irradiation. Through this result, it was confirmed that the titanium dioxide capsule used in the present invention can effectively prevent the deterioration of the ultraviolet absorber can be stably protected from heat and light.

[ Test Example  4]

Of titanium dioxide capsule of the present invention Feeling  And color development evaluation

Formulation Example 1, Formulation Example 2 and Comparative Formulation Examples 1 and 2 each of 10 females in their 20s and 30s (total 40 persons) were used daily for two weeks, and the two sensory evaluation items as shown in Table 7 below. The evaluation was carried out in four stages: each excellent (4 points), excellent (3 points), moderate (2 points), and poor (1). As shown in Table 7, as a result of counting the average score of 10 evaluators for each item for each formulation, it can be seen that the formulation example of the present invention has an excellent effect on feeling and color expression.

<Table 7>

Sensory evaluation items Formulation Example 1 Comparative Formulation Example 1 Formulation Example 2 Comparative Formulation Example 2 It is good in terms of foreign matter, skin adhesion, and the like. 3.3 2.4 3.8 2.3 Skin tone is bright and natural color expression. 3.6 2.7 3.4 2.6 Average score 3.45 2.55 3.6 2.45

1 is a titanium dioxide capsule was collected UV absorber according to the present invention

100-Titanium Dioxide Capsule with UV Absorber

101-Titanium Dioxide Structures (101)

102-inner wall for supporting structure 101

103-UV absorbers

104-Surface Treatment Film

Claims (6)

Titanium dioxide structure 101 composed of titanium dioxide fine particles and the inner wall 102 for supporting the structure 101 is one of silica, mica, talc, sericite, polyethylene, polypropylene, silicone resin, and polymethyl methacrylate. It consists of two or more species, dimethylpolysiloxane for making the ultraviolet absorber 103 collected in the inner wall 102, and the collected ultraviolet absorber 103 difficult to escape to the outside of the titanium dioxide structure 101, Methylpolysiloxane; Bead wax, carnauba wax, silicone fatty esters; Laurolysine, glutamate metal salts; Titanium dioxide capsule with a UV absorber, characterized in that the surface treatment film 104 made of any one of polyethylene, polymethyl methacrylate (Polymethyl Methacrylate). delete The method of claim 1, The ultraviolet absorber is a titanium dioxide capsule, the ultraviolet absorber is characterized in that it contains 1 to 60% by weight relative to the total weight of the titanium dioxide capsule. The method of claim 1, UV absorbers include ethyl hexyl methoxycinnamate, octyl methoxycinnamate, butylmethoxy dibenzoylmethane, octyl salicylate, and PABA (para aminobenzoic acid) , Titanium dioxide capsules with ultraviolet absorbers, characterized in that the use of one or two or more selected from benzophenone, anthracylates. A cosmetic composition comprising a titanium dioxide capsule in which the ultraviolet absorber of any one of claims 1, 3 and 4 is collected. 6. The method of claim 5, The cosmetic composition is a UV cream, two-way cake, loose powder, foundation, nutrition cream, massage cream, sunblock cream, body lotion, body cream, shampoo, rinse UV absorber, characterized in that the formulation is prepared in any one of the collection Cosmetic composition prepared by containing a titanium dioxide capsule.

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