KR100715241B1 - Process for preparing carboxylated alginic acid and its containing cosmetic compositions for removal of heavy metal - Google Patents

Abstract

The present invention relates to a method for producing carboxylated alginic acid by carboxylating alginic acid using hydrogen peroxide as a way to improve the adsorption of heavy metals of alginic acid. Still another object of the present invention is to provide a cosmetic composition for cleaning heavy metals containing carboxylated alginic acid.

Seaweed, Carboxylic Alginate, Heavy Metal Removal, Cosmetics

Description

Process for preparing carboxylated alginic acid and its containing cosmetic compositions for removal of heavy metal}

Figure 1 shows the heavy metal adsorption capacity of the carboxylated alginic acid according to the hydrogen peroxide treatment concentration.

Figure 2 shows the adsorption of heavy metals of carboxylated alginic acid according to the carboxylation reaction temperature.

Figure 3 shows the adsorption of heavy metals of carboxylated alginic acid according to the carboxylation reaction time.

Figure 4 compares the adsorption of heavy metals of alginic acid and carboxylated alginic acid.

The present invention relates to a method for producing carboxylated alginic acid by carboxylating alginic acid using hydrogen peroxide as a way to improve the adsorption of heavy metals of alginic acid. Still another object of the present invention is to provide a cosmetic composition for cleaning heavy metals containing carboxylated alginic acid.

In recent years, heavy metals, which are closely related to our daily life with the development of the industry, not only directly cause occupational diseases, but also indirectly contaminate food, water, air, and soil, causing acute and chronic damage to the human body. Coating. In particular, heavy metals contained in air, factory emissions, automobile emissions, yellow dust, etc., are contaminating the skin of people living in urban areas and industrial complexes. Cosmetics, precious metals, watches, eyeglass frames, etc. Heavy metals can also be contaminated with skin by metal items such as clips and zippers. Such heavy metal skin contamination has emerged as a serious risk factor for the safety of the skin, such as dermatitis and allergies. As a way to solve the above problems, the use of cosmetics for skin cleansing that can absorb and remove heavy metals present on the skin has been requested. Heavy metals removal techniques in general industrial sites are used for precipitation, flocculation, flotation, ion exchange, solvent extraction, complexation, filtration, evaporation, membrane separation, etc., but they cannot be used to remove heavy metals from humans. There are cases of using alginic acid, chitosan, and dietary fiber to remove heavy metals in the body, but there are no studies on human skin.

In the present invention, alginic acid, which is a natural product derived from algae, has no chemical risk for the manufacture of cosmetics for skin cleansing. Alginic acid is a polyuronic acid found in seaweed and contains 15 to 40% of dry weight in brown seaweed, seaweed, kelp, maban, and shellfish. Alginic acid has 1,4-glycosidic bonds in a proportion of D-mannuronic acid and L-guluronic acid as in (Formula 1), and each has one carboxyl group. Phosphorus exists in nature in the form of sodium (Na), potassium (K), calcium (Ca ^{2 +} ), magnesium (Mg ^{2 +} ) and salts.

As described above, alginic acid has a property of binding to divalent metal ions, and the binding force is known to increase as the number of carboxyl groups increases. In this paper, the adsorption capacity of heavy metals was improved by increasing the number of carboxyl groups of alginic acid using potassium permanganate (KMnO ₄ ) as a method for removing heavy metals from industrial wastewater (Water Research vol. 36, p 1814-1824). , 2002). However, potassium permanganate itself contains manganese (heavy metal), so if processed in large quantities for industrial production, some of it may remain in alginic acid. do. The present invention was intended to devise a method for preparing carboxylated alginic acid (Formula 2) by increasing the carboxyl group of alginic acid by using a material that does not contain heavy metals and is less likely to remain in the production process and relatively safe to the human body.

The configuration of the present invention is largely related to a technique for increasing the carboxyl group of alginic acid using hydrogen peroxide and a cosmetic composition having a heavy metal cleaning ability containing carboxylated alginic acid.

One. Of carboxylated alginic acid  Produce

(1) Preparation of carboxylated alginic acid using alginic acid

Heavy metal adsorption reaction of alginic acid is known to be caused by one carboxyl group present in each of its components, mannuronic acid and gluronic acid. Therefore, by converting the hydroxyl group of the alginic acid into a carboxyl group using an oxidizing agent, it is possible to improve the heavy metal adsorption power of the alginic acid. The present invention devised a method of increasing the carboxyl group of alginic acid using hydrogen peroxide (H ₂ O ₂ ), which does not contain heavy metals, and is less likely to remain in the production process, and is relatively safe for the human body.

In more detail, 100 g of alginic acid is added to 1 liter of 1-9 mM hydrogen peroxide solution, and the carboxylation reaction of alginic acid is proceeded at 10-60 ° C. for 10-60 minutes. When the reaction is completed, the carboxylated alginic acid precipitates, which is washed several times with deionized water until the alginate residue and hydrogen peroxide generated in the carboxylation process are removed, and then dried in a dryer at 40-80 ° C. and then pulverized to 50-100 mesh. Used in the manufacture of cosmetics. At this time, it is preferable to use a centrifuge as a method for facilitating washing.

(2) Preparation of carboxylated alginic acid using sodium alginate

Generally, alginic acid products for industrial use are distributed in the form of sodium alginate. Therefore, in order to industrially mass-produce carboxylated alginic acid, sodium alginate should be used as a raw material. To this end, sodium alginate must be converted to alginic acid to prepare carboxylated alginic acid. In detail, 100 g of sodium alginate is dissolved in 1 liter of deionized water, and 20 g of calcium chloride (CaCl ₂ ) is added, and the mixture is left at 15 to 30 ° C. for 3 to 6 hours to form and precipitate calcium alginate. When 1M inorganic acid or organic acid is added thereto and the pH is adjusted to 3.0, alginic acid is generated and precipitated. Using this to prepare a carboxylated alginic acid as described above.

2. Carboxylation  Heavy Metal Adsorption Capacity of Alginic Acid According to Conditions

In the present invention, 1g of carboxylated alginic acid is added to 100ml of lead solution having a concentration of 100ppm in order to measure the heavy metal adsorption power of the carboxylated alginic acid and reacted in a constant temperature shaking bath at 30 ° C. for 24 hours. Measured by (Inductively Coupled Plasma spectroscopy) was calculated by the following equation.

In order to determine the carboxylation conditions of alginic acid, the adsorption power of carboxylated alginic acid according to the amount of hydrogen peroxide was measured. As shown in FIG. 1, the concentration of hydrogen peroxide increased from 1mM to 5mM in proportion to the concentration, but it did not change much above 5mM. It became.

The adsorption of heavy metals of carboxylated alginic acid according to the carboxylation reaction temperature was measured (FIG. 2). The carboxylation reaction of alginic acid was relatively low at 560 mg lead / g dry mass at 10 ° C., but 650 mg lead / g at 20 ° C. The dry mass was high and the increase was low at higher temperatures. Therefore, it is judged that the suitable carboxylation reaction temperature of alginic acid is 20-30 degreeC.

The heavy metal adsorption capacity of carboxylated alginic acid according to the carboxylation reaction time was measured. (FIG. 3) The carboxylation reaction time of alginic acid was relatively low at 520 mg lead / g dry mass at 10 minutes but at 651 mg lead / g at 30 minutes. The dry mass was high and the increase was low at more times. Therefore, the proper carboxylation reaction time of alginic acid is considered to be suitable for 30 to 40 minutes.

3. Alginic acid Of carboxylated alginic acid  Heavy Metal Adsorption

Carboxylated alginic acid and reagents prepared by conventional methods (Water Research vol. 36, p 1814-1824, 2002) using carboxylated alginic acid and potassium permanganate (KMnO ₄ ) prepared by the present invention (Sigma A7003) The heavy metal adsorption capacity of alginic acid in circulation was compared. As shown in FIG. 4, the heavy metal adsorption of alginic acid is 481 mg lead / g dry mass, and the alginic acid carboxylated with potassium permanganate is 640 mg lead / g dry mass, and the alginic acid carboxylated with hydrogen peroxide is 651 mg lead / g dry mass. The superiority of the present invention has been demonstrated.

4. Carboxylated alginic acid  Preparation of cosmetic composition containing

In order to investigate the manufacturing conditions of the cosmetic composition containing carboxylated alginic acid, four kinds of cosmetic compositions to which carboxylated alginic acid was added were prepared, and cosmetic preparation, skin toxicity and heavy metal removal rate were measured. In other words, the cosmetic formulation was evaluated by five evaluators using a five-step scoring method. After 24 hours after the closed patch (Finn Chamber) in the forearm, the patch was removed and waited for the loss of the transient erythema and observed the erythema. The heavy metal removal rate was 100 ml of lead solution applied to the skin of pigs that had been immediately removed, and then washed with a heavy metal removal cosmetic. The amount of heavy metal remaining on the skin was measured and the heavy metal removal rate was calculated according to the following equation. .

(1) Alginic acid peeling gel

Peeling gel is a cosmetic that removes dead skin, waste products, sebum, etc. by adding the carboxylated alginic acid of the present invention having a heavy metal removal function to the basic blended amount by content, and reviewed the formulation and heavy metal removal rate, 5% The content of carboxylated alginic acid was 70%, and in all cases, it was found to be non-dermal toxic.

  Preparation and Heavy Metal Removal Rate of Alginate Filling Gel According to Carboxylated Alginate Content 5% carboxylated alginic acid content (% by weight) Formation (5 scale) Skin toxicity Heavy metal removal rate (%) Constellation Compoundability Compoundability 50 5.0 5.0 5.0 - 93.2 60 5.0 5.0 5.0 - 95.3 70 5.0 5.0 5.0 - 98.5 80 4.1 4.0 3.8 - 99.0 90 2.8 2.5 2.0 - 99.2

  Level 5 rating: 1, very bad; 2, poor; 3, normal; 4, good; 5, excellent

  -Skin toxicity: +++, severe erythema; ++, obvious erythema; +, Mild erythema; -, No erythema

(2) Algin acid massage cream

Massage cream is a cosmetic that provides nutrition to the skin, prevents dryness and roughness, and makes the skin more flexible and maintains healthy skin. By adding the carboxylated alginic acid of the present invention having a heavy metal removal function to the basic compounding specification by content As a result of reviewing the formulation and removal rate of heavy metals, it was found that the content of 5% carboxylated alginic acid was 20% and in all cases, it was not skin toxic.

  Deforming and Heavy Metal Removal Rate of Alginate Massage Cream by Carboxylation Alginate Content 5% carboxylated alginic acid content (% by weight) Formation (5 scale) Skin toxicity Heavy metal removal rate (%) Constellation Compoundability Feeling 10 5.0 5.0 4.6 - 80.3 15 5.0 5.0 4.9 - 85.3 20 5.0 5.0 5.0 - 89.2 25 3.9 4.1 4.0 - 90.1 30 2.8 3.0 3.1 - 90.5

  Level 5 rating: 1, very bad; 2, poor; 3, normal; 4, good; 5, excellent

  -Skin toxicity: +++, severe erythema; ++, obvious erythema; +, Mild erythema; -, No erythema

(3) alginic acid foam Cleansing

Foam cleansing is a carboxylated alginate of the present invention that has heavy metal removal function in the basic compounding specification as a cosmetic that has a cleansing power such as soap but enhances skin protection functions such as moisturizing so that the skin is less pulled after use and maintains a moist texture. As a result, the formulation and the heavy metal removal rate were added, and the content of 5% carboxylated alginic acid was 40%.

  Formation and Heavy Metal Removal Rate of Alginate Foam Cleansing by Carboxylation Alginate Content 5% carboxylated alginic acid content (% by weight) Formation (5 scale) Skin toxicity Heavy metal removal rate (%) Constellation Compoundability Feeling 20 5.0 5.0 4.5 - 90.0 30 5.0 5.0 4.8 - 91.3 40 5.0 5.0 5.0 - 94.3 50 3.8 3.5 4.1 - 95.5 60 3.2 2.0 3.0 - 95.8

  Level 5 rating: 1, very bad; 2, poor; 3, normal; 4, good; 5, excellent

  -Skin toxicity: +++, severe erythema; ++, obvious erythema; +, Mild erythema; -, No erythema

(4) alginic acid Cleansing cream

Cleansing cream is an effective cosmetics for removing dark makeup that is not easily erased by soap or foam cleansing. The result of examining the formulation and removal rate of heavy metals by adding the carboxylated alginic acid of the present invention having heavy metal removal function to the basic compounding specification by content, The content of 5% carboxylated alginic acid was 20%, and in all cases, it was proved to be non-dermal toxicity.

  Deforming and Heavy Metal Removal Rate of Alginate Cleansing Cream by Carboxylation Alginate Content 5% carboxylated alginic acid content (% by weight) Formation (5 scale) Skin toxicity Heavy metal removal rate (%) Constellation Compoundability Feeling 10 5.0 5.0 4.3 - 81.3 15 5.0 5.0 4.8 - 86.4 20 5.0 5.0 5.0 - 90.8 25 3.5 3.9 4.2 - 91.0 30 2.5 2.8 3.3 - 91.5

  Level 5 rating: 1, very bad; 2, poor; 3, normal; 4, good; 5, excellent

  -Skin toxicity: +++, severe erythema; ++, obvious erythema; +, Mild erythema; -, No erythema

The following describes the content of the present invention in more detail using examples, but the present invention does not limit the claims of the present invention.

Example  1: alginic acid ( Alginic  acid) Carboxylation  Preparation of Alginic Acid

① Add 100 g of alginic acid to 1 liter of 5mM hydrogen peroxide solution and react at 150rpm for 30 minutes in 30 ℃ shaking water bath.

② After completion of the reaction, centrifuge for 30 minutes with a centrifugal force of 5,000 × g to remove the supernatant, and then repeat the process of centrifugation under the same conditions by adding deionized water again.

③ The above precipitate is used directly in cosmetics manufacturing, or dried in a dryer at 60 ℃ and then pulverized to 80mesh used for cosmetics.

Example  2 : Sodium alginate  Used Carboxylation  Preparation of Alginic Acid

① Dissolve 100g of sodium alginate in 1 liter of deionized water, and add 20g of calcium chloride (CaCl ₂ ) and leave at 30 ℃ for 5 hours.

② Centrifuge ① for 30 minutes at 5,000 × g centrifugal force to remove supernatant, add 1 liter of deionized water to it, and then crush it with homogenizer, add 1 / 10N citric acid until pH 3.0, and apply for 24 hours. Leave it.

③ Centrifuge ② for 30 minutes at 5,000 × g centrifugal force to remove the supernatant, add deionized water to the precipitate again, and centrifuge it under the same conditions three times. To prepare alginic acid.

Using alginic acid produced in ④ ③, carboxylated alginic acid is prepared in the same manner as in ① to ③ of Example 1.

Example  3: Carboxylated alginic acid  Preparation of heavy metal cleaning cosmetic composition comprising

① 5 parts by weight of dried carboxylated alginic acid is added to 95 parts by weight of deionized water and swelled at 30 ° C. for 24 hours to give 5% by weight of carboxylated alginic acid.

(2) The swelled carboxylated alginic acid is blended with a composition as shown in the following table to prepare a cosmetic composition for heavy metal washing in a conventional manner.

Composition of Alginate Filling Gel (Unit Weight%) division Composition content(%) A-1 Carboxylated Alginic Acid (5%) 70.000 Purified water 10.495   A-2 Fiji-400 4.000 Betaine 3.000 Gardenia Florida Extract 0.040 Cellulose 8.000 Carbomer 0.250  B Fiji-60 Hydrogenated Gas Oil 0.200 Astaxanthin 0.100 ethanol 3.000 Combination spices 0.060   C Imidazolidinylurea 0.200 Ubiquinone 0.005 Hyaluronic Acid Extract 0.100 Astaxanthin 0.100 Hydrolyzed keratin / hydrolyzed collagen / elastin 0.100 Rosa Centifolia Extract 0.100 D Triethanolamine 0.250 Sum 100.000  Formulation Order (1) The material of A-1 is sufficiently dissolved by stirring at room temperature (dispersion check). ② The material of A-2 is sufficiently dissolved by stirring at room temperature (dispersion check). ③ Slowly add B to A and mix (mixing confirmation) ④ Slowly add C and D.

  Composition of Alginate Massage Cream (Unit Weight%) division Composition content(%)    A-1 Carboxylated Alginic Acid (5%)  20.000 Purified water  14.960 Allantoin   0.100 Methylparaben   0.200 Betaine   5.000 Butylene glycol   3.000 Propylene glycol   2.000 A-2 Xanthan Gum   0.100 Carbomer   0.040       B Stearic acid   0.700 Glyceryl Stearate   1.800 Cetearyl Alcohol   0.800 Fiji-40 Stearate   2.500 Sorbitan sesquioleate   0.300 Griseryl Stearate / Fiji-100 Stearate   1.000 Cetyl esters   0.300 beeswax   1.100 Mineral Oil  41.000 Triethanolamine   1.500 Dimethicone   0.300 Tocopherol Acetate   0.100 Propylparaben   0.100 C Cyclomethicone   2.000    D Phenoxyethanol   0.200 Combination spices   0.080 Ubiquinone   0.100 Hyaluronic Acid Extract   0.100 Astaxanthin   0.100 Hydrolyzed keratin / hydrolyzed collagen / elastin   0.010 Gardenia Florida Extract   0.400 Rosa centifolia flower extract   0.010 E Microcrystalline Wax   0.100 Sum 100.000 Formulation Order ① The material of A-2 is sufficiently dissolved by stirring at room temperature. ② The material of A-1 is melted by heating at 75 ~ 80 ℃ (dissolution confirmation). ③ The material of B is heated and dissolved at 75 to 80 ° C (dissolution confirmation). ④ Slowly add B to A, emulsify at 75 ~ 80 ℃ and add C just before completion. ⑤ Check the contents after emulsification and cool. ⑥ Put D at 50 ℃. ⑦ Put E at 40 ℃ and check dispersion. ⑧ Cool until it reaches 30 ℃ while defoaming.

  Composition of Alginate Foam Cleansing (Unit Weight%) division Composition content(%) A-1 Carboxylated Alginic Acid (5%)  40.000 Purified water   2.300 A-2 Sodium Laureth Sulfate  37.850 Sodium Lauryl Sulfate  12.000  A-3 Betaine   0.500 Citric acid   0.170 Glyceline   2.000    B Combination spices   0.100 Methylchloroisothiazolinone and methylisothiazolinone mixture   0.050 Ubiquinone   0.100 Hyaluronic Acid Extract   0.100 Astaxanthin   0.100 Hydrolyzed keratin / hydrolyzed collagen / elastin   0.010 Gardenia Florida Extract   0.400 Rosa centifolia flower extract   0.010  C Coca Middopropyl Betaine   5.000 Disodium coco ampodiacetate  10.000 Styrene / acrylamide copolymer   0.100 Sum 100.000 Formulation Order (1) The material of A-1 is sufficiently dissolved by stirring at room temperature (dispersion check). ② The material of A-2 is sufficiently dissolved by stirring at room temperature (dispersion check). (3) Dissolve the material of A-3 at room temperature with sufficient stirring (dispersion check). ④ Slowly add B to A and mix (mix). ⑤ Slowly insert C (bubble caution).

  Composition of Alginate Cleansing Cream (Unit Weight%) division Composition content(%)   A-1 Carboxylated Alginic Acid (5%)  20.000 Purified water  10.710 Allantoin   0.050 Methylparaben   0.200 Betaine   1.000 Propylene glycol   5.000 A-2 Carbomer   0.210     B Stearic acid   1.450 Glyceryl Stearate   0.450 Stearyl alcohol   1.000 Glyceryl Stearate / Pig-100stearate   0.600 Sorbitan sesquioleate   0.400 Fiji-40 Stearate   2.100 Mineral Oil  53.330 Dimethicone   0.300 Propylparaben   0.100 Triethanolamine   2.000    C Phenoxyethanol   0.200 Combination spices   0.080 Ubiquinone   0.100 Hyaluronic Acid Extract   0.100 Astaxanthin   0.100 Hydrolyzed keratin / hydrolyzed collagen / elastin   0.010 Gardenia Florida Extract   0.400 Rosa centifolia flower extract   0.010 D Microcrystalline Wax   0.100 Total 100.000 Formulation Order ① The material of A-2 is sufficiently dissolved by stirring at room temperature. ② The material of A-1 is dissolved by heating at 75 to 80 ° C (dissolution confirmation). (3) The material of B is dissolved in warming at 75 to 80 ° C (dissolution confirmation). ④ Slowly add B to A and emulsify at 75 ~ 80 ℃. ⑤ Check the contents after emulsification and cool. ⑥ Put C material at 50 ℃. ⑦ Insert D material at 40 ℃ and check dispersion. ⑧ Cool until temperature reaches 30 ℃ while degassing.

According to the present invention, it is possible to produce cosmetics that can effectively remove heavy metals contaminated on the skin, and to prevent heavy metal contamination of the human skin, which is expected to have a significant effect on human health. And it is expected to have a remarkable effect on the creation of high value-added industries.

Claims (8)

A method for producing carboxylated alginic acid by treating alginic acid with hydrogen peroxide at 30-40 ° C. for 30-50 minutes. The method of claim 1, wherein the alginic acid is obtained by treating sodium alginate with calcium chloride. The method for producing carboxylated alginic acid according to claim 1, wherein the alginic acid is alginic acid derived from seaweed. A cosmetic composition for cleaning heavy metals containing a carboxylated alginic acid prepared according to any one of claims 1 to 3 as an active ingredient. The cosmetic composition for cleaning heavy metals according to claim 4, wherein the cosmetic composition is a peeling gel containing carboxylated alginic acid as an active ingredient with respect to the total weight of the composition. The cosmetic composition for cleaning heavy metals according to claim 4, wherein the cosmetic composition is a massage cream containing carboxylated alginic acid as an active ingredient with respect to the total weight of the composition. According to claim 4, The cosmetic composition is a heavy metal cleaning cosmetic composition for foam cleaning containing 1.0 to 2.0% by weight relative to the total weight of the composition of the carboxylated alginic acid as an active ingredient. The cosmetic composition for cleaning heavy metals according to claim 4, wherein the cosmetic composition is a cleansing cream containing carboxylated alginic acid as an active ingredient, based on the total weight of the composition.

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