KR101181622B1 - Cosmetic composition for adsorbing volatile organic compound containing mesoporous materials - Google Patents

Abstract

The present invention relates to a cosmetic composition for adsorption of volatile organic compounds containing a porous material (Mesoporous), more specifically porous polymer composite spheres, activated carbon (including activated carbon, char and palm activated carbon), diatomite and zeolite ( It relates to a cosmetic composition for adsorbing a volatile organic compound containing at least one selected from the group consisting of zeolite) as an active ingredient. In addition, the cosmetic composition according to the present invention protects the skin from cytotoxicity caused by volatile organic compounds.

Porous polymer composite sphere, activated carbon, diatomaceous earth, zeolite, charcoal, palm activated carbon, volatile organic compound, VOC, cosmetic composition

Description

Cosmetic composition for adsorbing volatile organic compound containing mesoporous materials

The present invention relates to a cosmetic composition for adsorption of volatile organic compounds containing a porous material (Mesoporous), more specifically porous polymer composite spheres, activated carbon (including activated carbon, char and palm activated carbon), diatomite and zeolite ( Zeolite) relates to a cosmetic composition for adsorption of a volatile organic compound containing at least one selected from the group consisting of.

According to the World Health Organization and the US EPA, "Volatile Organic Compounds (VOCs) refer to substances containing carbon atoms and having a vapor pressure of at least 0.13 kPa at standard temperature and standard pressure. ₂ is excluded ". In most atmospheric environments, VOC is a generic term for hydrocarbon compounds. General hydrocarbons such as aromatic foot hydrocarbons (benze and toluene) and aliphatic hydrocarbons (paraffinic and olefinic), and heterogeneous hydrocarbons containing nitrogen, hydrogen and halogen elements. Hydrocarbons: aldehydes, ketones, etc.). In particular, the VOC can be directly harmful to the environment and health as the compound itself, such as aromatic hydrocarbons and halogen hydrocarbons, or mainly participate in photochemical reactions in the atmosphere, such as aliphatic hydrocarbons, to generate secondary pollutants such as photochemical carbides. Olefin hydrocarbon compounds are known to have high photochemical reactivity. The most exposed VOCs in our lives are mainly from VOC's main ingredient formaldehyde and tobacco smoke, wardrobe repellents, insecticides, herbicides, fragrances or white ant remedies used under floors. For example, formaldehyde is generated from plywood, vinyl cross, carpet adhesives, or adhesives used for walls or ceilings, and VOCs generated in buildings are plastics or adhesives for furniture or window coverings, adhesives, varnishes, waxes, plastic crosses or plywood. Occurs in molds and insect repellents contained in.

It is already known that VOC can cause allergies and sick house syndrome. In addition to increased cancer incidence and respiratory distress, VOCs from paints may also be a cause for children's atopy (Int J Hyg Environ Health. 2000 Mar; 203 (1): 23-8). In particular, formaldehyde, the main component of VOC, which causes sick house syndrome, may increase the expression of skin inflammation related factors. In addition, according to a study by Yon-Sook Lee's research team at Yonsei University, a survey of 170 housewives living in new apartments nationwide since 2001 showed that 94.1% had symptoms of sick house syndrome, and 54.1% of them had dry skin. It was found that sick house syndrome could be a cause of skin irritation and atopic dermatitis as well as dry skin.

Currently, the method performed to remove the VOC mainly uses VOC adsorption eco-friendly paint containing porous materials such as activated carbon, diatomaceous earth or zeolite, or removes VOC generated by displaying charcoal or palm activated carbon in the house. have. However, these methods are only a method of reducing the concentration of VOC in almost living environments, and there is no cosmetic product that has a function of directly adsorbing and removing VOC, which can directly protect the human body.

Accordingly, the present inventors have tried to prepare a cosmetic that can effectively protect the skin from VOCs such as formaldehyde, when a porous polymer composite sphere, activated carbon, diatomaceous earth, zeolite or a mixture thereof is added to the cosmetic composition as an active ingredient The present invention has been found to reduce the skin toxicity caused by VOC by adsorbing and removing VOC.

Accordingly, it is an object of the present invention to provide a cosmetic composition that is effective for adsorption of VOCs and reduces skin toxicity due to VOCs.

In order to achieve the above object, the present invention provides a cosmetic composition for adsorption of volatile organic compounds containing at least one selected from the group consisting of porous polymer composite spheres, activated carbon, diatomaceous earth and zeolite as an active ingredient.

VOC adsorption cosmetic composition according to the present invention by effectively adsorbing and removing VOCs such as formaldehyde accumulated on the skin to reduce the skin inflammation expression factors that can be caused by VOCs, reduce skin irritation, improve skin dry symptoms It was.

The present invention relates to a cosmetic composition for adsorption of VOC containing at least one selected from the group consisting of porous polymer composite spheres, activated carbon, diatomaceous earth and zeolite as an active ingredient.

Hereinafter, the present invention will be described in more detail.

Porous polymer composite spheres, activated carbon, diatomaceous earth, and zeolites used in the present invention occur in cigarette smoke, wardrobe repellents, insecticides, herbicides, fragrances, or various building materials or furniture, and effectively absorb and remove toxic VOCs.

Since the porous polymer composite sphere used in the present invention is a spherical body having an average particle size of 5 ~ 10 ㎛ in the form of fine powder, it is easy to be blended into various cosmetic formulations, and has excellent usability such as spreadability when applying skin. The porous polymer composite sphere may be prepared by the following process. 100 g was prepared by mixing methyl methacrylate / ethylene glycol dimethacrylate (crosslinking agent) / toluene in a ratio of 18:42:40 by weight in the reactor. 2,2-Azobis (2,4-dimethyl valeronitrile), which is an initiator, was introduced into the solution at 1 wt% based on the monomer, followed by stirring at room temperature to completely dissolve it. Subsequently, the prepared solution was placed in an aqueous solution in which 1% of polyvinyl alcohol (average degree of saponification of 89%) was dissolved and emulsified at 6,000 rpm for 5 minutes using a mechanical homogenizer. At this time, the methyl methacrylate / crosslinker / initiator / toluene solution has a concentration of 15% by weight in the water phase. Subsequently, after raising the temperature of the reactor to 70 ° C. and polymerizing for 10 hours, the porous polymer particles prepared through the filter paper were collected by filtration. The unreacted material and the dispersion stabilizer were repeatedly washed with methanol, and then dried in a vacuum oven for 24 hours to obtain a porous polymer composite sphere in powder form. The porous polymer composite sphere prepared by the above method may include methyl methacrylate-acrylonitrile copolymer, but is not limited thereto.

Activated carbon used in the present invention mainly manufactured oak trees such as larch oak, oyster oak, water oak, line oak, palm tree, etc. in Korea, the charcoal charcoal method, more preferably using charcoal (charcoal) or palm activated carbon Good to do.

Diatomite (Diatomite, diatom earth, diatomaceous earth or kieselgure) used in the present invention is a single cell algae deposited in the sea or river for a long time, after the decomposition of the protoplasts in the body, the main body of silicic acid (SiO ₂ ) It is made through a manufacturing process of firing a kind of fossil piled up at a high temperature of about 1250 ℃.

Zeolite used in the present invention refers to the anion generated by the combination of aluminum oxide and silicate oxide as a mineral to which alkali metal and alkaline earth metal are bonded, that is, crystalline aluminosilicate.

At least one member selected from the group consisting of the porous polymeric composite sphere, activated carbon, diatomaceous earth and zeolite is contained in an amount of 0.01 to 40.0% by weight, preferably 0.1 to 5.0% by weight, based on the total weight of the cosmetic composition. When the content of the active ingredient is less than 0.01% by weight, the VOC adsorption effect is not obtained, and when the content of the active ingredient exceeds 40.0% by weight, the usability is not good and it is difficult to commercialize.

The cosmetic composition of the present invention may further contain an oil component, natural oil or synthetic oil may be used, and hydrocarbon, triglyceride, ester or silicone oil may be used. The oil component is contained in an amount of 1.0 to 40.0% by weight, preferably 5.0 to 20.0% by weight, based on the total weight of the composition. If the content is less than 1.0% by weight, it is difficult to obtain a desired emulsion formulation, and if it exceeds 40.0% by weight, the stability of the emulsifier type is poor .

Cosmetic compositions according to the invention can be formulated in oil-in-water (O / W) or water-in-oil (W / O) emulsions, and can be formulated in the form of lotions, creams, emulsions, patches, sticks or sprays.

The cosmetic of the present invention may further include other ingredients usually blended into the cosmetic composition as needed in addition to the active ingredient. Specific examples include fats and oils, moisturizers, emollients, surfactants, organic and inorganic pigments, organic powders, ultraviolet absorbers, preservatives, fungicides, antioxidants, plant extracts, pH adjusters, alcohols, pigments, flavors, blood circulation accelerators. , Cooling agent, limiting agent and purified water.

Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples. However, these examples and test examples are only for helping understanding of the present invention, the scope of the present invention is not limited only to these examples.

Test Example 1 Formaldehyde Adsorption Effect

In order to confirm the adsorption effect of porous materials, namely porous polymer composites, charcoal, palm activated carbon, diatomaceous earth and zeolite, on formaldehyde, one of the main VOCs commonly encountered in everyday life, 100 ppm of formaldehyde is 5% by weight. After addition to purified water containing a porous material of each reaction for 30 minutes, the adsorption rate was measured by atomic absorption spectrometry (Atomic absorption spectrometry). The adsorption rate was calculated by dividing the concentration of the sample after the adsorption of the porous material by the concentration of the sample before adsorption (Equation 1). The higher the adsorption rate, the more effectively the formaldehyde was adsorbed and removed. The results are shown in Table 1 below. As a control, a group containing only purified water without a porous material was used.

Adsorption rate (%) = (concentration of sample after 1-porous material adsorption / concentration of sample before porous material adsorption) x 100

sample Formaldehyde Adsorption Rate (%) Control (purified water) - charcoal 57 Palm activated carbon 64 Diatomaceous earth 69 Zeolite 61 Porous Polymer Composite Sphere 75 Porous Polymer Composite Sphere + Charcoal 89 Porous Polymer Composite Sphere + Palm Activated Carbon 86 Porous Polymer Composite Sphere + Diatomaceous Earth 81 Porous Polymer Composite Sphere + Zeolite 93

In the results of Table 1, when the porous polymer composite spheres, activated charcoal, palm activated carbon, diatomaceous earth and zeolite containing porous materials, the adsorption rate of formaldehyde was high and the concentration of free formaldehyde was reduced. Therefore, it was confirmed that the porous polymer composite sphere, charcoal, palm activated carbon, diatomaceous earth, and zeolite, which are porous materials of the present invention, have an excellent adsorption effect of formaldehyde. In addition, it was confirmed that the formaldehyde adsorption effect was further improved due to the synergistic effect when two or more kinds of porous polymer composite spheres, charcoal, palm activated carbon, diatomaceous earth, and zeolite were mixed.

Test Example 2 Protective Effect of Skin Cells from Formaldehyde

Distribute human-derived fibroblasts at a concentration of 1 × 10 ⁵ per well in a 96-well plate incubator, incubate for 24 hours, and form 10 ppm of formaldehyde, porous polymer composites, charcoal, palm activated carbon, diatomaceous earth, zeolite or one or more The porous material 1: 1 mixture (1%) was treated simultaneously and the control group was further incubated for 24 hours with 10 ppm of formaldehyde alone. After incubation, MTT (Sigma) reagent was added and incubated for 4 hours, and then the culture solution was removed, stirred for 20 minutes by addition of 1N NaOH / isopropanol solution, and the absorbance was measured at 565 nm with an absorbance photometer. Calculation according to Equation 2 is shown in Table 2 below.

% Survival = A / B × 100

A: Laboratory Absorbance

B: formaldehyde untreated 24 hours culture absorbance

Test Fibroblast survival rate (%) Control group (formaldehyde alone) 20 charcoal 47 Palm activated carbon 52 Diatomaceous earth 46 Zeolite 56 Porous Polymer Composite Sphere 62 Porous Polymer Composite Sphere + Charcoal 88 Porous Polymer Composite Sphere + Palm Activated Carbon 71 Porous Polymer Composite Sphere + Diatomaceous Earth 85 Porous Polymer Composite Sphere + Zeolite 78

In the results of Table 2, the porous polymer composite spheres, charcoal, palm activated carbon, diatomaceous earth, and zeolite treatment groups, which are used in the present invention, have a viability of fibroblasts by inhibiting cell death induced by formaldehyde compared to the control group. It confirmed that it raises. Therefore, it was confirmed that the porous polymeric composite sphere, charcoal, palm activated carbon, diatomaceous earth, or zeolite according to the present invention can alleviate skin irritation by reducing skin irritation that may occur with formaldehyde.

Test Example 3 Reduction Effect of Skin Inflammation Expression Factor

Enzyme Linked ImmunoSorbent Assay (ELISA) was conducted to determine the effects of porous polymer composites, charcoal, palm activated carbon, diatomaceous earth, and zeolite on suppressing the expression of skin inflammatory factors MMP-1 and PGE-2 (SE Dunsmore, et. al., J Biol Chem, 271: 24576-24582, 1996).

Human-derived fibroblasts were cultured in cell culture (Lonza, Inc., Walkersville, Md.) According to Lonza instructions. That is, the FGM-2 bullet kit (Bullet kit, Clonetics CC-4126) was added to 500 ml of FBM (Clonetics CC-3131) medium. The medium was treated with 10 ppm of formaldehyde, incubated for 24 hours, exchanged with the medium, cultured for 24 hours, and the medium was recovered and coated in a 96-hole plate incubator. Primary antibodies (monoclonal antibodies; R & D ELIZA kits) corresponding to MMP-1 and PGE-2 were treated and reacted at 37 ° C. for 90 minutes. The secondary antibody, anti-mouse immunoglobulin (alkaline phosphatase conjugated anti-mouse IgG) was reacted for another 90 minutes, washed with a buffer solution, and then washed with an alkaline phosphatase substrate solution (p-nitrophenyl dissolved in diethanolamine buffer solution). Phosphate 1 mg / ml) was reacted at room temperature for 30 minutes and absorbance was measured at 405 nm using an absorbance spectrometer. The absorbance of the cell culture medium not treated with the porous material was used as a control. Expression inhibition effect of MMP-1 and PGE-2 was calculated by the following equation 3, the results are shown in Table 3 and FIG.

A: Absorbance of Wells Without Samples

B: Absorbance of Wells Added Samples

Test substance MMP-1 expression inhibition rate (%) PGE-2 expression inhibition rate (%) Control group - - charcoal 54 66 Palm activated carbon 57 56 Diatomaceous earth 67 58 Zeolite 70 61 Porous Polymer Composite Sphere 72 65 Porous Polymer Composite Sphere + Charcoal 78 68 Porous Polymer Composite Sphere + Palm Activated Carbon 80 71 Porous Polymer Composite Sphere + Diatomaceous Earth 81 79 Porous Polymer Composite Sphere + Zeolite 76 73

In the results of Table 3 and Figure 1, the porous polymer composite sphere, char, palm activated carbon, diatomaceous earth, zeolite or mixtures thereof (mixed in a 1: 1 weight ratio) used in the present invention are all skin inflammation factors MMP-1 and Expression of PGE-2 was inhibited. Therefore, it is understood that the porous polymer composite sphere, char, palm activated carbon, diatomaceous earth, or zeolite used in the present invention has an effect of preventing skin inflammation by inhibiting the expression of skin inflammatory factors that may be caused by VOC by adsorbing formaldehyde. Could.

[Examples 1-9 and Comparative Example 1]

The cosmetic compositions (oil-in-water emulsion formulations) of Examples 1 to 9 and Comparative Example 1 having the composition as shown in Table 4 were prepared. Comparative Example 1 is a cosmetic composition of a conventional oil-in-water emulsion formulation containing no porous polymeric composite sphere, activated carbon, diatomaceous earth and zeolite, and Examples 1 to 9 are selected from porous polymeric composite spheres, charcoal, palm activated carbon, diatomaceous earth and zeolite. It was manufactured from the cosmetic composition containing 1 or more types (unit: weight%).

No. Raw material name Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 One charcoal - 6 - - - - 3 - - - 2 Palm activated carbon - - 6 - - - - 3 - - 3 Diatomaceous earth - - - 6 - - - - 3 - 4 Zeolite - - - - 6 - - - - 3 5 Porous Polymer Composite Sphere - - - - - 6 3 3 3 3 6 Purified water Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance 7 Disodium ID 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 8 glycerin 5 5 5 5 5 5 5 5 5 5 9 Butylene glycol 5 5 5 5 5 5 5 5 5 5 10 Betaine 2 2 2 2 2 2 2 2 2 2 11 Sodium hyaluronate 4 4 4 4 4 4 4 4 4 4 12 Cetearyl alcohol 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 13 Stearic acid 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 14 Glyceryl Stearate /
Fiji-100 Tearate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 15 Polysorbate 60 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 16 Squalane 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 17 antiseptic Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount 18 Spices Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount Suitable amount

<Manufacturing Method>

1) The components 1-11 were uniformly mixed, and it melt | dissolved by heating at 70 degreeC.

2) The components 11-18 were uniformly mixed, and it melt | dissolved by heating at 75 degreeC.

3) While stirring (homomixing) at 70 ° C., 2) was slowly added to 1) to emulsify and cooled to 50 ° C. or lower to prepare a cosmetic composition of an oil-in-water emulsion formulation.

Test Example 4 Skin Irritation Test

In each group, 30 women in their 20s were tested for primary skin irritation according to CTFA guidelines (The Cosmetic, Toiletry and Fragrance Association. Inc. Washington, D.C., 20036, 1991). 20 μl of each of the test substances (10% in patch base) of Examples 1 to 9 and Comparative Example 1 prepared in the Finn Chamber was added dropwise, washed with 70% ethanol, dried, and the like. It was mounted on the site and fixed with a micropore tape. After 24 hours, the pin chamber was removed and the skin change was read visually and the results are shown in Table 5 below. In Table 5, the average reactivity was calculated according to Equation 4 below, and skin irritation was determined after 24 hours of patching (-) with no erythema or peculiar phenomenon, (±) being slightly redder than the surroundings, and (+) being significantly redder than the surroundings. , (++) was determined to be reddening and swelling more severely than the surroundings. Determination of skin irritation is Grade I (non-irritating range) if the average response is 0 to 0.1, Grade II (light stimulation range) if 0.11 to 0.3, Grade III (medium stimulation range) if 0.31 to 0.5, Grade IV or higher. (Strong stimulus range).

Average responsiveness = [(±) number * 1 + (+) number * 2 + (++) number * 3] / number of subjects

Judgment result Average reactivity Judgment grade
- ± + ++ Comparative Example 1 28 2 - - 0.06 I Example 1 30 - - - 0.00 I Example 2 29 One 0 - 0.03 I Example 3 29 - One - 0.06 I Example 4 29 One 0 - 0.03 I Example 5 30 - - - 0.00 I Example 6 29 One 0 - 0.03 I Example 7 29 - One - 0.06 I Example 8 29 One 0 - 0.03 I Example 9 29 - One - 0.06 I

In the results of Table 5, there was almost no skin irritation in the parts coated with Examples 1 to 9 containing one species selected from the group consisting of porous polymer composite spheres, charcoal, palm activated carbon, diatomaceous earth and zeolite according to the present invention. In addition, the stimulus judgment rating of I was confirmed that the skin is safe for the occurrence of no skin irritation.

[Test Example 5] Dry skin and inflammation improvement sensory evaluation test

Thirty housewives, aged 25 to 36, who visited the hospital for sick house syndrome, were treated with the emulsion of Examples 1-9 and Comparative Example 1 in the same manner as the usual emulsion for 4 weeks. According to the opinions of the users, the degree of dryness and skin inflammation caused by sick house syndrome was determined according to the following evaluation criteria. The test results are shown in Table 6 below.

<Evaluation Criteria>

+++: Very good improvement.

++: Significant improvement.

+: A slight improvement.

±: No improvement but no deterioration

-: No improvement, rather weakened.

Dryness improvement degree Test substance term 1 week 2 weeks 3 weeks 4 weeks Comparative Example 1 ± ± + + Example 1 ± + ++ ++ Example 2 ± + ++ ++ Example 3 ± + ++ ++ Example 4 ± + ++ ++ Example 5 + + + * +++ Example 6 ± + ++ +++ Example 7 + ++ +++ ++++ Example 8 ± + ++ +++ Example 9 ± ++ +++ +++

Improvement of skin inflammation Test substance term 1 week 2 weeks 3 weeks 4 weeks Comparative Example 1 ± ± ± ± Example 1 + ++ +++ +++ Example 2 ± + ++ ++ Example 3 + ++ ++ ++ Example 4 + ++ ++ ++ Example 5 ± + + +++ Example 6 ± + ++ ++ Example 7 ± + ++ +++ Example 8 ± ++ ++ ++ Example 9 ± + ++ +++

As can be seen from the results of Tables 6 and 7, the emulsion containing the porous polymer composite spheres, charcoal, palm activated carbon, diatomaceous earth and zeolite used in the present invention is the dryness and skin generated by VOC which is the main cause of sick house syndrome. It was confirmed that it has an excellent improvement effect on inflammation.

Through the above results, the cosmetic composition according to the present invention was confirmed that the adsorption of VOC, such as formaldehyde, has excellent skin cell protective effect to relieve skin dryness and inflammation resulting from VOC.

1 is a graph showing the effect of reducing the expression of inflammatory factors in the skin cells of porous materials according to the present invention.

Claims (4)

Methyl methacrylate-acrylonitrile copolymer; And At least one selected from the group consisting of activated carbon, diatomaceous earth and zeolite; Cosmetic composition for adsorbing volatile organic compounds for protecting skin cells, alleviating skin irritation or alleviating skin inflammation, comprising as an active ingredient. delete The cosmetic composition for adsorbing volatile organic compounds according to claim 1, wherein the activated carbon is charcoal or palm activated carbon. The method of claim 1, wherein the composition is characterized in that it contains 0.01 to 40.0% by weight relative to the total weight of the composition of one or more selected from the group consisting of methyl methacrylate-acrylonitrile copolymer, activated carbon, diatomaceous earth and zeolite Cosmetic composition for adsorption of volatile organic compounds.

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