KR20230140174A - Cosmetic composition for improving whitening, anti oxidant and treating allergy - Google Patents

Abstract

The present invention relates to a cosmetic composition for improving whitening effect, improving antioxidant effect, and preventing and improving allergies. More specifically, the whitening effect by cysteine and acetylcysteine is improved and thiazolidine-4-carboxylic acid, or 2-methyl -The antioxidant effect is improved by including thiazolidine-4-carboxylic acid, and the content of formaldehyde and acetaldehyde is reduced, so skin troubles, including skin problems and allergies, caused by formaldehyde and acetaldehyde are prevented and improved in the cosmetic composition. It's about.

Description

Cosmetic composition for improving whitening effect, improving antioxidant effect, and preventing and improving allergies {COSMETIC COMPOSITION FOR IMPROVING WHITENING, ANTI OXIDANT AND TREATING ALLERGY}

The present invention relates to a cosmetic composition for improving whitening effect, improving antioxidant effect, and preventing and improving allergies. More specifically, the whitening effect by cysteine and acetylcysteine is improved and thiazolidine-4-carboxylic acid, or 2-methyl -The antioxidant effect is improved by including thiazolidine-4-carboxylic acid, and the content of formaldehyde and acetaldehyde is reduced, so skin troubles, including skin problems and allergies, caused by formaldehyde and acetaldehyde are prevented and improved in the cosmetic composition. It's about.

Formaldehyde is a naturally occurring organic compound with the chemical formula CH2O and has the simplest structure among aldehydes (R-CHO). Pure formaldehyde compound is a colorless gas with a pungent odor and is stored as an aqueous solution (formalin) because it spontaneously polymerizes into paraformaldehyde. Formaldehyde is an important precursor for many other substances and compounds and is mainly used in the production of industrial resins such as particleboard and coatings (Reuss et al. 2000, "Formaldehyde". Ullmann's Encyclopedia of Industrial Chemistry, Weinheim, Wiley-VCH).

Acetaldehyde is an organic compound with the chemical formula CH3CHO and is one of the most important aldehydes. It occurs widely in nature but is also produced on a large scale in industry. Acetaldehyde occurs naturally during the manufacturing process of alcoholic beverages, coffee, bread, various fermented foods, cosmetics, and household chemical products [Uebelacker et al. 2011, J Autom Methods Manag Chem, 907317].

Formaldehyde is produced by the amino acid serine producing formaldehyde and glycine through Reaction (1) below, and this reaction is catalyzed by serine hydroxymethyltransferase (National Research Council, 2014, Review of the Formaldehyde Assessment in the National Toxicology Program 12th Report on Carcinogens. Washington DC, The National Academies Press. p 91)

HOCH ₂ CH(NH ₂ )CO ₂ H → CH ₂ O +H ₂ C(NH ₂ )CO ₂ H ------- Reaction (1)

Traditionally, acetaldehyde is produced naturally by partial dehydrogenation of ethanol (Eckert et al. 2007, "Acetaldehyde" in Ullmann's Encyclopedia of Industrial Chemistry, Weinheim, Wiley-VCH).

CH ₃ CH ₂ OH → CH ₃ CHO + H ₂ ------- Reaction (2)

Formaldehyde and acetaldehyde are also intermediates produced in the biological metabolism of mammals and humans (Reuss et al. 2000, "Formaldehyde". Ullmann's Encyclopedia of Industrial Chemistry, Weinheim, Wiley-VCH). Therefore, formaldehyde and acetaldehyde are found in all living organisms, from plants to animals and humans, but are rapidly metabolized and decomposed in the living body and do not accumulate in the body.

However, in vitro, formaldehyde and acetaldehyde are widely used, toxic and volatile, posing serious risks to human health. Formaldehyde and acetaldehyde are carcinogens to humans. In 1988, the International Agency for Research on Cancer (IARC) stated, “There is sufficient evidence for the carcinogenicity of acetaldehyde (the main metabolite of ethanol) in laboratory animals.” Acetaldehyde, which is naturally produced, was classified as a Group 1 human carcinogen (IARC, 2006, Monographs on the Evaluation of Carcinogenic Risks to Humans, Volume 88, Formaldehyde, 2-Butoxyethanol and 1-tert-Butoxypropan-2-ol; IARC , 2009, World Health Organization. 1988. Alcohol drinking. Lyon: World Health Organization).

Formaldehyde is a well-known mucosal irritant and is known to be a major skin sensitizer associated with contact dermatitis (type IV allergy) and immediate anaphylactic reactions (type I allergy) (Lyapina1 et al. 2012, Allergic contact dermatitis fromformaldehyde exposure, Journal of IMAB, 18, 255). Additionally, exposure to formaldehyde or acetaldehyde can cause sick building syndrome or bronchial asthma. In particular, low concentrations of acetaldehyde synergistically worsen allergic airway inflammation (Kawano et al. 2012, Acetaldehyde at a Low Concentration Synergistically Exacerbates Allergic Airway Inflammation as an Endocrine-Disrupting Chemical and as a Volatile Organic Compound, Respiration, 84, 135?141). Therefore, reducing formaldehyde or acetaldehyde in cosmetics or household chemical products is very important for consumer health.

Conventional methods for reducing or removing formaldehyde and acetaldehyde include using a mixture of urea (Korean Patent No. 10-0741365-0000), ethylene urea or its derivatives, and ammonium phosphate (Japanese Patent No. JP). -0069615). In addition, a formaldehyde remover composition containing hydrazine or a derivative thereof and a polyoxyethylene alkyl ether phosphate ester type anionic surfactant (Japanese Patent No. JP-0189824), an aqueous solution or alcohol solution of sulfanilic acid or its derivative (Japanese registered patent JP-0094606) or an aqueous solution of chitosan and its derivatives (US Patent US-0201812) or several types of carbodiimide (Japanese Patent JP-0084563) are disclosed. However, the above methods not only damage the original product quality when used in cosmetics, but are also harmful to the human body, so they cannot be used, and only reduce formaldehyde to some extent, but the removal efficiency is not high.

Meanwhile, a method that can effectively reduce acetaldehyde in alcoholic beverages is the use of an oxidation catalyst (US Patent US-6569479, International Patent WO-0130900, European Patent EP-1242524). However, this method has never been used in cosmetics, and it is believed that the original product quality will be damaged.

The purpose of the present invention is to provide a new cosmetic composition that is safe while removing formaldehyde or acetaldehyde in order to solve the problems of the prior art as described above.

In order to solve the above problems, the present invention provides a cosmetic composition containing thiazolidine-4-carboxylic acid or 2-methyl-thiazolidine-4-carboxylic acid.

The technical feature of the present invention is that formaldehyde and acetaldehyde, which are carcinogens and volatile components harmful to the respiratory tract, are removed from the cosmetic composition, and at the same time, thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4, which have antioxidant and anticancer effects, are removed from the cosmetic composition. -Carboxylic acid is produced.

The technical feature of the present invention is that cysteine and acetylcysteine, which are added to the cosmetic composition to remove formaldehyde and acetaldehyde, which are volatile components harmful to the respiratory tract, act as a whitening effect when they remain in the cosmetic composition.

In the cosmetic composition according to the present invention, cysteine or acetylcysteine used as a remover are compounds well known as antioxidants and skin conditioning agents, and are ingredients that have been used as additives in cosmetics for this purpose (Korean Cosmetic Association, https:// kcia.or.kr/cid/search/ingd_view.phpno=1703). Therefore, cysteine or acetylcysteine acts as an antioxidant and skin conditioning agent even when it reacts with formaldehyde and acetaldehyde and remains. Therefore, when added in a range that does not cause problems with the function of cosmetics, the remaining cysteine or acetylcysteine will additionally exhibit antioxidant and whitening functions.

The cosmetic composition according to the present invention removes formaldehyde and acetaldehyde, which are carcinogens and volatile respiratory components, and at the same time contains thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4-carboxylic acid, which have antioxidant and anticancer effects. It is characterized by being created.

Thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4-carboxylic acid, which are produced when formaldehyde and acetaldehyde, which are the causes of skin allergies and respiratory allergies, combine with cysteine, etc., have antioxidant effects [De la Fuente et al. 1998, Enhancement of leukocyte functions in aged mice supplemented with the antioxidant thioproline, Mech. Aging Dev. 104, 213-225], hepatoprotective properties [Roberts et al. 1987, Prodrugs of l-cysteine as protective agents against acetaminophen-induced hepatotoxicity. 2-(Polyhydroxyalkyl)- and 2-(polyacetoxyalkyl)thiazolidine-4(R)-carboxylic acids, J. Med. Chem. 30, 1891-1896], immune function [Navarro et al. 2007, Dietary thioproline decreases spontaneous food intake and increases survival and neurological function in mice, Antioxid. Redox Signal. 9, 131-141], antitumor properties and detoxification properties [Kumagai et al. 2004, Thioproline inhibits development of esophageal adenocarcinoma induced by gastroduodenal reflux in rats, Carcinogenesis, 25, 723-727; Suo et al. 2006, Thioproline prevents carcinogenesis in the remnant stomach induced by duodenal reflux, Cancer Lett. 237, 256?262] is known to be excellent.

In particular, it eliminates potential side effects caused by nitroso compounds and nitrites [Shozo et al. 2007, Ingestion of thioproline suppresses rat esophageal adenocarcinogenesis caused by duodenogastroesophageal reflux, Oncol. Rep. 18, 1443-1449], elevated glutathione function [Gullner et al. 2003, l-2-oxo-4-thiazolidine-carboxylic acid treatment leads to both elevated glutathione levels and accumulation of mRNA encoding the pathogenesis-related PR-1a protein in tobacco, Free Radic. Res. 37, 48-49], function as an influenza NA inhibitor [Liu et al. 2011, Design, synthesis and biological activity of thiazolidine-4-carboxylic acid derivatives as novel influenza neuraminidase inhibitors, Bioorg. Med. Chem. 19, 2342-2348] is well known.

The cosmetic composition according to the present invention is characterized in that it contains the thiazolidine-4-carboxylic acid at a concentration of 1 to 4000 mg/kg.

The cosmetic composition according to the present invention is characterized in that it contains the 2-methyl-thiazolidine-4-carboxylic acid at a concentration of 1 to 500 mg/kg.

The cosmetic composition according to the present invention is characterized by containing cysteine or acetylcysteine at a concentration of 0.5 to 1000 mg/kg.

The cosmetic composition according to the present invention contains R-cysteine or S-cysteine at a concentration of 10 to 1000 mg/kg, and acetyl-R-cysteine, acetyl-S-cysteine, and 2-Amino-propane- as second ingredients. 1-thiol, 2-Amino-butane-1-thiol, 2-Amino-pentane-1-thiol, 2-Amino-hexane-1-thiol, 2-Amino-heptane-1-thiol, penicillamine, and asparagine It is characterized in that it contains one or more selected from the group consisting of at a concentration of 1 to 100 mg/kg.

The cosmetic composition according to the present invention is characterized in that it contains formaldehyde at a concentration of 50 mg/kg or less.

The cosmetic composition according to the present invention is characterized by containing acetaldehyde at a concentration of 20 mg/kg or less.

As discussed earlier, acetaldehyde is a primary decomposition product of alcohol and is a carcinogen. If acetaldehyde is not quickly decomposed into acetic acid in the body, it stays in the blood vessels or cells of the body and causes various side effects. It acts as a toxin, and in particular, it is a very harmful substance that directly causes symptoms such as dizziness and vomiting when drinking. The cosmetic composition according to the present invention can minimize side effects that may occur when using cosmetics by controlling formaldehyde and acetaldehyde, which have these side effects, below a certain concentration.

The cosmetic composition according to the present invention is characterized in that it is manufactured in one or more formulations selected from lotions, emulsions, serums, shampoos, and soaps. Specifically, basic cosmetic formulations consisting of shampoo, lotion, gel, water-soluble liquid, cream, essence, oil-in-water (O/W) type and water-in-oil (W/O) type; It can be manufactured with a cosmetic composition selected from oil-in-water or water-in-oil type makeup base, foundation, skin cover, lipstick, lip gloss, face powder, two-way cake, eye shadow, cheek color, and eyebrow pencil.

The cosmetic composition according to the present invention removes formaldehyde and acetaldehyde, which are carcinogens and volatile respiratory components, and contains thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4-carboxylic acid, which have antioxidant and anticancer effects. This is produced and safe, but cysteine and acetylcysteine, which have special whitening effects, remain, so not only are most allergenic substances removed, but the antioxidant and whitening effects are greatly improved.

Figures 1 and 2 show calibration curves for changes in concentration of formaldehyde and acetaldehyde, respectively.
Figure 3 shows the thiazolidine-4-carboxylic acid standard solution prepared to 0, 10, 50, 100, 250, 500, 1000, 2000 mg/L and then immediately measured by high performance liquid chromatography (HPLC) to obtain the area and concentration of each peak. This is the result of finding the truth equation for .
Figure 4 shows the 2-methyl-thiazolidine-4-carboxylic acid standard solution prepared to 0, 10, 50, 100, 250, 500, 1000, 2000 mg/L and then immediately measured by high performance liquid chromatography (HPLC). This is the result of calculating the true equation for peak area and concentration.

Hereinafter, various embodiments are presented to aid understanding of the invention. The following examples are provided to make the invention easier to understand, and the scope of protection of the invention is not limited to the following examples.

<Analysis method> Analysis method of formaldehyde and acetaldehyde

The calibration curve for the change in concentration of formaldehyde and acetaldehyde is shown in Figures 1 and 2. Figure 1 shows formaldehyde standard solutions prepared to be 0, 1.0, 5.0, 10, 20, 50, and 100 mg/L, then adding 300 μg of 2,6-dinitrophenylhydrazine to each sample solution and derivatizing it at 40°C for 30 minutes to obtain high performance This is the result of measuring using liquid chromatography (HPLC) and obtaining the true equation for each peak area and concentration.

Figure 2 shows that acetaldehyde standard solutions were prepared to 0, 2.0, 5.0, 10, 20, 30, and 50 mg/L, and then 300 μg of 2,6-dinitrophenylhydrazine was added to each sample solution and derivatized at 40°C for 30 minutes to obtain high performance This is the result of measuring using liquid chromatography (HPLC) and obtaining the true equation for each peak area and concentration.

In Examples and Comparative Examples, when the concentrations of formaldehyde and acetaldehyde in the samples were outside the concentration range of the calibration curve, the samples were diluted and reanalyzed.

<Comparative Example 1> Measurement of formaldehyde and acetaldehyde production in cosmetic raw materials and finished products according to conventional manufacturing methods

When cosmetics were manufactured according to conventional manufacturing methods, an experiment was performed according to the following method to determine the amount of formaldehyde and acetaldehyde produced in the cosmetics.

2.0 g of the manufactured cosmetics and household chemical products were placed in a 15 mL glass test tube and 3 mL of purified water was added to dissolve the sample. 300 μg of 2,6-dinitrophenylhydrazine was added to the sample solution, derivatized at 40°C for 30 minutes, and measured using high performance liquid chromatography (HPLC).

The amounts of formaldehyde and acetaldehyde produced in the raw materials and finished products of cosmetics manufactured according to the comparative example are shown in Table 1 below. As shown in Table 1 below, the amount of formaldehyde and acetaldehyde produced in the raw materials and finished products of cosmetics manufactured according to the conventional manufacturing method was measured to be 37-785 mg/kg on average in the case of formaldehyde in cosmetic raw materials or finished products. Acetaldehyde was measured at an average of 10-48 mg/kg.

<Example 2> Measurement of formaldehyde and acetaldehyde production in cosmetic raw materials and finished products according to the present invention

In order to measure the amount of formaldehyde and acetaldehyde produced in the raw materials and finished products of cosmetics according to the present invention, the analysis of formaldehyde and acetaldehyde was performed in the same manner as in Example 1.

Cysteine was added to the raw materials or finished products at a concentration of 1000 mg/kg, mixed by vortexing for 5 minutes, and then allowed to stand at room temperature for 1 hour. The formaldehyde and acetaldehyde contents in the raw materials and finished products of each cosmetic were then measured.

The amounts of formaldehyde and acetaldehyde produced in the raw materials and finished products of cosmetics according to the present invention are shown in Table 1 above. From the results in Table 1, it was shown that more than 98% of formaldehyde was removed from the raw materials and finished products of cosmetics according to the present invention, and more than 97% of acetaldehyde was removed. In other words, according to the present invention, the amount of formaldehyde produced in the raw materials and finished products of cosmetics was completely removed or remained at a maximum of 14 mg/kg. Acetaldehyde was completely removed or remained up to 0.6 mg/kg.

<Example 3> Measurement of thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4-carboxylic acid production amount

A prior research method was used to determine the amount of thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4-carboxylic acid produced after adding cysteine to a cosmetic composition to 1000 mg/L and preparing the cosmetic composition ( Shin et al. J Mass Spectrom, 2007, 42, 1225) was slightly modified to conduct the experiment.

The calibration curve for the change in concentration of thiazolidine-4-carboxylic acid (TZCA) and 2-methyl-thiazolidine-4-carboxylic acid (MTZCA) is shown in Figure 3. Figure 3 shows the thiazolidine-4-carboxylic acid standard solution prepared to 0, 10, 50, 100, 250, 500, 1000, 2000 mg/L and then immediately measured by high performance liquid chromatography (HPLC) to obtain the area and concentration of each peak. This is the result of finding the truth equation for . When the concentrations of thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4-carboxylic acid in the sample were outside the concentration range of the calibration curve, the sample was diluted and reanalyzed.

2.0 g of the prepared cosmetic composition was placed in a 15 mL glass test tube and 3 mL of purified water was added to dissolve the sample. Approximately 50 mg of carbonate buffer (Na2CO3:KHCO3, 1:2, w/w) was added to the sample solution. Approximately 150 μL of ethyl chloroformate, 1.5 mL of methanol/pyridine solution (4/1, v/v) and 100 μL of Me-TZCA-d4 solution (2.0 mg/L in water) as internal standard were added to the sample and was extracted with 3 mL of toluene by mechanical shaking for 20 minutes. The organic phase was dried with nitrogen, the dried residue was dissolved in 100 μL of ethyl acetate, and 2.0 μL of the solution was injected into the GC system for analysis.

The amount of thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4-carboxylic acid produced by removing formaldehyde and acetaldehyde from the cosmetic composition was confirmed, and the results are shown in Table 2.

As can be seen from Table 2, when cysteine was added to the cosmetic composition, formaldehyde and acetaldehyde were removed, and the amount of thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4-carboxylic acid produced was confirmed. Thiazolidine-4-carboxylic acid and 2-methyl-thiazolidine-4-carboxylic acid are important antioxidants and substances with anticancer effects. As shown in Table 2, they are contained in cosmetic compositions at an average amount of about 143 mg/kg and standard weight, respectively. The deviation was produced in an amount of 54 mg/kg.

So far, the present invention has been examined focusing on its preferred embodiments. A person skilled in the art to which the present invention pertains will understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the equivalent scope should be construed as being included in the present invention.

Claims (8)

Cosmetic composition containing thiazolidine-4-carboxylic acid, or 2-methyl-thiazolidine-4-carboxylic acid
According to paragraph 1,
The cosmetic composition includes the thiazolidine-4-carboxylic acid at a concentration of 1 to 4000 mg/kg.
According to paragraph 1,
The cosmetic composition includes the 2-methyl-thiazolidine-4-carboxylic acid at a concentration of 1 to 500 mg/kg.
According to paragraph 1,
The cosmetic composition contains cysteine or acetylcysteine at a concentration of 0.5 to 1000 mg/kg.
According to paragraph 1,
The cosmetic composition contains either R-cysteine or S-cysteine at a concentration of 10 to 1000 mg/kg,
Acetyl-R-cysteine, Acetyl-S-cysteine, 2-Amino-propane-1-thiol, 2-Amino-butane-1-thiol, 2-Amino-pentane-1-thiol, 2-Amino-hexane-1- A cosmetic composition comprising at least one selected from the group consisting of thiol, 2-Amino-heptane-1-thiol, penicillamine, and asparagine at a concentration of 1 to 100 mg/kg.
According to paragraph 1,
The cosmetic composition includes formaldehyde at a concentration of 50 mg/kg or less.
According to paragraph 1,
The cosmetic composition includes acetaldehyde at a concentration of 20 mg/kg or less.
According to paragraph 1,
The cosmetic composition is characterized in that it is manufactured in one or more formulations selected from lotion, emulsion, serum, shampoo, and soap.