Composition containing PQQ or salt thereof, cosmetic raw material, application and cosmetic

Abstract

The invention relates to the technical field of skin care products, in particular to a composition containing PQQ or salt thereof, a cosmetic raw material, application and a cosmetic. The composition provided by the invention is prepared from the following components in parts by weight: 0.01 to 0.05 part of PQQ or salt thereof, 0.1 to 10 parts of trimethyl pentanediol / adipic acid / glycerol cross-linked polymer, 0.1 to 5 parts of polyquaternium-51 and 0.01 to 0.1 part of sodium citrate. The PQQ or the salt thereof in the composition can be kept in a stable state under various conditions, and has good moisturizing and / or redness removing effects. In addition, the composition can also be combined with other active substances to prepare cosmetic raw materials, and good physiological activity is still kept after the cosmetic raw materials are prepared into cosmetics.

Description

Technical Field

[0001] The present invention relates to the technical field of skin care products, and particularly to a composition containing PQQ or its salt, a cosmetic raw material, an application, and a cosmetic. Background Art

[0002] Pyrroloquinoline Quinone (abbreviated as PQQ) is a class of compounds with unique biological activities. Common salts of PQQ include sodium salt, magnesium salt, or calcium salt of PQQ.

[0003] In recent years, PQQ has attracted much attention in the fields of medicine, food, and cosmetics. As a new type of redox coenzyme, PQQ has various physiological functions such as antioxidant, promoting mitochondrial function, anti-inflammatory and soothing effects. In the field of cosmetics, the application prospects of PQQ and its salts are particularly broad. Its strong antioxidant ability and skin repair effect make it a very potential skin care ingredient.

[0004] However, in the development of cosmetics, in order to further enrich the efficacy of products, PQQ usually needs to be used in combination with other functional components. However, it has been found in research that many common cosmetic ingredients, such as humectants, antioxidants, preservatives, etc., may have a significant negative impact on the stability of PQQ. For example, some cosmetics containing PQQ will change color after being stored for a period of time, and the activity will also decrease. The main reasons for the degradation of PQQ include: ① Light and oxidation will accelerate its degradation, resulting in color change; ② Alkaline environment will promote the degradation of PQQ; ③ PQQ reacts with amino acids to form yellow oxazole derivatives; ④ Metal ions may complex with PQQ, affecting its stability and changing the color. It can be seen that when designing a cosmetic formula, ensuring that the activity of PQQ is fully utilized and it still exists stably after being compounded with other components has become a key problem to be solved urgently.

[0005] It is precisely due to the unstable characteristics of PQQ that its application in the field of cosmetics is still restricted. Therefore, developing a cosmetic formula that can not only maintain the high biological activity of PQQ but also coexist stably with humectants, skin feel regulators, and other active substances is still a problem to be solved urgently in this field. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a composition containing PQQ or its salt, a cosmetic raw material, an application, and a cosmetic.

[0007] The composition provided by the present invention is composed of the following components in parts by mass:

[0008] 0.01 to 0.05 parts of PQQ or its salt, 0.1 to 10 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.1 to 5 parts of polyquaternium-51, and 0.01 to 0.1 parts of sodium citrate.

[0009] In order to improve the stability of PQQ or its salt and at the same time exert better physiological activity, in the composition provided by the present invention, humectants, skin feel regulators and pH regulators are screened. The obtained composition can not only maintain the color change or degradation of PQQ or its salt during storage, but also support each other to produce better skin care effects. Moreover, the composition can be prepared by mixing and stirring each component according to a conventional method, which is simple and convenient, and the components are safe and non-irritating.

[0010] In the present invention, the salt of PQQ is mainly the sodium salt of PQQ. For example, pyrroloquinoline quinone disodium salt (abbreviated as PQQ-2Na).

[0011] In the examples of the present invention, the composition is composed of the following components in parts by mass: 0.02 to 0.03 parts of PQQ-2Na, 1 to 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.5 to 3 parts of polyquaternium-51, and 0.00828 to 0.0449 parts of sodium citrate.

[0012] In some embodiments, the composition is composed of the following components in parts by mass: 0.02 to 0.03 parts of PQQ-2Na, 1.5 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.5 parts of polyquaternium-51, and 0.00828 to 0.0449 parts of sodium citrate.

[0013] In other embodiments, the composition is composed of the following components in parts by mass: 0.02 to 0.03 parts of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.00828 to 0.0449 parts of sodium citrate.

[0014] In other embodiments, the composition is composed of the following components in parts by mass: 0.02 to 0.03 parts of PQQ-2Na, 1 part of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 3 parts of polyquaternium-51, and 0.00828 to 0.0449 parts of sodium citrate.

[0015] In other embodiments, the composition is composed of the following components in parts by mass: 0.02 to 0.03 parts of PQQ-2Na, 2 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 2 parts of polyquaternium-51, and 0.00828 to 0.0449 parts of sodium citrate.

[0016] In some other embodiments, the composition is composed of the following components in parts by mass: 0.02 - 0.03 parts of PQQ-2Na, 2.66 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1.33 parts of polyquaternium-51, and 0.00828 - 0.0449 parts of sodium citrate.

[0017] In some specific embodiments, the composition is composed of the following components in parts by mass: 0.03 parts of PQQ-2Na, 1.5 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.5 parts of polyquaternium-51, and 0.00828 - 0.0449 parts of sodium citrate.

[0018] In some other specific embodiments, the composition is composed of the following components in parts by mass: 0.03 parts of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.00828 - 0.0449 parts of sodium citrate.

[0019] In some other specific embodiments, the composition is composed of the following components in parts by mass: 0.03 parts of PQQ-2Na, 1 part of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 3 parts of polyquaternium-51, and 0.00828 - 0.0449 parts of sodium citrate.

[0020] In some other specific embodiments, the composition is composed of the following components in parts by mass: 0.03 parts of PQQ-2Na, 2 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 2 parts of polyquaternium-51, and 0.00828 - 0.0449 parts of sodium citrate.

[0021] In some other specific embodiments, the composition is composed of the following components in parts by mass: 0.03 parts of PQQ-2Na, 2.66 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1.33 parts of polyquaternium-51, and 0.00828 - 0.0449 parts of sodium citrate.

[0022] More specifically, the composition is composed of the following components in parts by mass: 0.03 parts of PQQ-2Na, 1.5 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.5 parts of polyquaternium-51, and 0.0149 parts of sodium citrate.

[0023] Or the composition is composed of the following components in parts by mass: 0.03 parts of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.0149 parts of sodium citrate.

[0024] Alternatively, the composition consists of the following components by mass: 0.03 parts of PQQ-2Na, 1 part of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 3 parts of polyquaternium-51, and 0.0149 parts of sodium citrate.

[0025] Alternatively, the composition consists of the following components by mass: 0.03 parts of PQQ-2Na, 2 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 2 parts of polyquaternium-51, and 0.0149 parts of sodium citrate.

[0026] Alternatively, the composition consists of the following components by mass: 0.03 parts of PQQ-2Na, 2.66 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1.33 parts of polyquaternium-51, and 0.0149 parts of sodium citrate.

[0027] Alternatively, the composition consists of the following components by mass: 0.03 parts of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.00828 parts of sodium citrate.

[0028] Alternatively, the composition consists of the following components by mass: 0.03 parts of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.0214 parts of sodium citrate.

[0029] Alternatively, the composition consists of the following components by mass: 0.03 parts of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.0449 parts of sodium citrate.

[0030] Alternatively, the composition consists of the following components by mass: 0.03 parts of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.00328 parts of sodium citrate.

[0031] Alternatively, the composition consists of the following components by mass: 0.03 parts of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.01061 parts of sodium citrate.

[0032] Alternatively, the composition consists of the following components by mass: 0.03 parts of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.034 parts of sodium citrate.

[0033] Alternatively, the composition consists of the following components in parts by mass: 0.03 part of PQQ-2Na, 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 1 part of polyquaternium-51, and 0.019 part of sodium citrate.

[0034] The present invention also provides a cosmetic raw material, comprising the aforementioned composition and a functional component; the functional component is selected from at least one of Spectrastat™ PHL, sodium hyaluronate hydrolyzate, hydroxyethyl urea, PEG / PPG-14 / 7 dimethyl ether, and D-panthenol.

[0035] In the present invention, the mass ratio of the functional component to PQQ in the composition is (0.1 - 2):(0.02 - 0.03).

[0036] In some embodiments, the cosmetic raw material comprises the following components in parts by mass: 0.1 - 2 parts of the functional component, 0.01 - 0.03 part of PQQ-2Na, 1 - 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.5 - 3 parts of polyquaternium-51, and 0.00828 - 0.0449 part of sodium citrate.

[0037] In some specific embodiments, when the functional component is D-panthenol, the cosmetic raw material comprises the following components in parts by mass: 0.5 part or 2 parts of D-panthenol, 0.02 - 0.03 part of PQQ-2Na, 1 - 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.5 - 3 parts of polyquaternium-51, and 0.00828 - 0.0449 part of sodium citrate.

[0038] In some specific embodiments, when the functional component is Spectrastat™ PHL, the cosmetic raw material comprises the following components in parts by mass: 0.3 part of Spectrastat™ PHL, 0.02 - 0.03 part of PQQ-2Na, 1 - 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.5 - 3 parts of polyquaternium-51, and 0.00828 - 0.0449 part of sodium citrate.

[0039] In some specific embodiments, when the functional component is sodium hyaluronate hydrolyzate, the cosmetic raw material comprises the following components in parts by mass: 0.1 part of sodium hyaluronate hydrolyzate, 0.02 - 0.03 part of PQQ-2Na, 1 - 3 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.5 - 3 parts of polyquaternium-51, and 0.00828 - 0.0449 part of sodium citrate.

[0040] In some specific embodiments, the functional component is PEG / PPG-14 / 7 dimethyl ether, and the cosmetic raw materials include the following components in parts by weight: 2 parts of PEG / PPG-14 / 7 dimethyl ether, 0.02-0.03 parts of PQQ-2Na, 1-3 parts of trimethylpentanediol / adipic acid / glycerol crosslinked polymer, 0.5-3 parts of polyquaternium-51 and 0.00828-0.0449 parts of sodium citrate.

[0041] Furthermore, the present invention also provides the use of the above-mentioned composition, or the above-mentioned cosmetic raw material, in the preparation of cosmetics.

[0042] In the present invention, the cosmetics are moisturizing and / or redness-removing cosmetics.

[0043] In the present invention, the moisturizing includes reducing transepidermal water loss, and the redness removal includes reducing skin hemoglobin. In view of this, the cosmetic may also have the effects of moisturizing and locking water, soothing and anti-inflammatory, repairing the barrier, anti-oxidation or brightening the skin color.

[0044] The present invention does not particularly limit the dosage form of the composition, and can adopt a form known as a cosmetic or quasi-drug. As a feasible case, the cosmetics are carried out in the form of water-based agents (such as perfume, lotion, floral water), oil-based agents (such as sunscreen oil, massage oil, hair oil), emulsions (including cleansing cream, moisturizing cream, moisturizing lotion), powder products (such as scented powder, talcum powder, prickly heat powder), block products (such as pressed powder, rouge), suspended products (such as liquid foundation), surfactant solvent products (such as shampoo, hand soap, shower gel), gel products (such as cleansing gel, sleeping mask), aerosol products (including hair spray, mousse), paste products (including shampoo, paste mask, lipstick), tablet products (such as lipstick), pen products (such as lip liner, eyebrow pencil), etc.

[0045] Furthermore, the present invention also provides a cosmetic, which includes the composition as described above, or the cosmetic raw material as described above.

[0046] In the present invention, other excipient components are also included in the cosmetic. After verification, water or pentylene glycol has no effect on the stability of PQQ in the cosmetic. In addition, common excipients in cosmetics include solvents (such as water, including deionized water and purified water; alcohols such as ethanol, propylene glycol, butylene glycol, and glycerol; oils and fats (such as argan oil, evening primrose oil, olive oil, coconut oil, jojoba oil, rosehip oil, almond oil, shea butter, squalane, hydrogenated vegetable oil, triglyceride caprylate / caprate, cetyl ethylhexanoate, isononyl isononanoate, silicone oil, beeswax, palm wax, candelilla wax, lanolin, horse oil, etc.), thickeners (natural thickeners such as xanthan gum, carrageenan, and pectin; synthetic thickeners such as carbomer and sodium polyacrylate), humectants (such as sodium PCA, sodium hyaluronate, ceramide, oat extract, aloe extract, tea extract, peptides), emulsifiers (anionic emulsifiers such as fatty acid soap and sodium dodecyl sulfate; cationic emulsifiers are quaternary ammonium salts; nonionic emulsifiers such as polysorbates, i.e., Tween, glycerol monostearate, sorbitan esters, polyglycerol fatty acid esters, lecithin, cetearyl olivate, PEG-100 stearate, and poloxamer), preservatives (alcohol preservatives include benzyl alcohol and phenethyl alcohol; acid preservatives contain benzoic acid and its salts, sorbic acid and its salts; phenolic preservatives are parabens, i.e., nipagin esters), antioxidants (phenolic antioxidants such as butylated hydroxyanisole, i.e., BHA, and dibutylhydroxytoluene, i.e., BHT; quinone antioxidants include coenzyme Q10; natural antioxidants include vitamin C, vitamin E, and tea polyphenols), fragrances (natural fragrances such as rose essential oil, lavender essential oil, and peppermint oil; synthetic fragrances include coumarin, geraniol, and phenethyl alcohol), pigments (natural pigments such as carmine, chlorophyll, and carotene; synthetic pigments include ponceau 4R, tartrazine, and sunset yellow), and chelating agents (such as disodium ethylenediaminetetraacetate, i.e., EDTA-2Na, citric acid, and tartaric acid). As mentioned above, the excipients can also be added to the cosmetic after verification that they have no or little effect on stability and / or physiological activity.

[0047] In the present invention, the cosmetic comprises the following components in mass fractions: PQQ-2Na 0.02% - 0.03%, trimethylpentanediol / adipic acid / glycerol cross-polymer 1% - 3%, Lipidure-PMB(Ph10) polyquaternium-51 0.5% - 3%, pentylene glycol 4%, sodium citrate 0.00828% - 0.0449%, and the balance is water.

[0048] Furthermore, the present invention also provides a skin care method, which includes applying the cosmetic as described above on the skin surface.

[0049] In the present invention, the application methods on the skin surface include but are not limited to: smearing, that is, taking an appropriate amount of cosmetics and gently spreading them evenly on the skin surface; wiping, that is, dipping cosmetics with tools such as cotton pads and gently wiping them on the skin surface; spraying, if the cosmetics are in the form of a spray, they can be directly sprayed on the skin surface; massaging, that is, applying the cosmetics on the skin and then performing specific massage techniques to promote absorption.

[0050] In the present invention, the skin surface includes but is not limited to facial skin, periorbital skin, lip skin, periauricular skin, scalp, neck skin, shoulder skin, chest skin, abdominal skin, back skin, arm skin, hand skin, cubital fossa skin, leg skin, knee skin, foot skin, ankle skin, skin around the fingernails / toenails, areola skin, and skin of private parts.

[0051] The composition provided by the present invention is composed of 0.01 - 0.05 parts of PQQ or its salt, 0.1 - 10 parts of trimethylpentanediol / adipic acid / glycerol cross-linked polymer, 0.1 - 5 parts of polyquaternium-51, and 0.01 - 0.1 parts of sodium citrate. The PQQ or its salt in this composition can maintain a stable state under various conditions and has good moisturizing and / or anti-reddening effects. Moreover, this composition can also be combined with other active substances to form a cosmetic raw material, and still maintain good physiological activity after being prepared into a cosmetic. Detailed implementation manners

[0052] The present invention provides a composition, a cosmetic raw material, an application, and a cosmetic containing PQQ or its salt. Those skilled in the art can draw on the content of this article and appropriately modify the process parameters to achieve it. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention. The methods and applications of the present invention have been described through preferred embodiments, and relevant personnel can obviously make changes or appropriate alterations and combinations to the methods and applications in this article without departing from the content, spirit, and scope of the present invention to implement and apply the technology of the present invention.

[0053] The numerical ranges and parameters involved in the present invention have been presented as precisely as possible in the specific embodiments. However, any numerical value inevitably contains standard deviations caused by individual testing methods. Therefore, unless otherwise clearly stated, it should be understood that all numerical ranges or specific data used in this disclosure may have certain reasonable deviations within a certain range, such as within ±10%, ±5%, ±1%, or ±0.5%.

[0054] Some cases are described in the embodiments and comparative examples of the present invention. Among them, the embodiments show certain implementation manners of the present invention. However, this does not mean that the effects of the present invention can only be achieved in these cases. In fact, good effects can be achieved at any concentration of each component between the two endpoint values shown in the embodiments. Among the cases with relatively good effects, PQQ-2Na, trimethylpentanediol / adipic acid / glycerol cross-linked polymer, Lipidure-PMB(Ph10) polyquaternium-51, and sodium citrate can cooperate well to jointly maintain the stability of PQQ. Some cases with poor effects in the tests are also listed in the following embodiments, such as using different components and different ratios, etc. However, the effects of these attempts are not as good as those under the ratios described above, and will not be elaborated here.

[0055] The test materials used in the present invention are all ordinary commercially available products and can be purchased in the market. Among them:

[0056] BINESTER GL, from Shanghai Zibang Biopharmaceutical Co., Ltd.;

[0057] Lipidure-PMB(Ph10), from NOF CORPORATION;

[0058] Sodium citrate, from Shandong Yingxuan Industry Co., Ltd.

[0059] Spectrastat™ PHL from INOLEX, Inc.

[0060] The detection method for the loss rate of PQQ-2Na involved in the embodiments is as follows:

[0061] 1 Principle: PQQ-2Na is dissolved, separated by reversed-phase high-performance liquid chromatography, detected by an ultraviolet detector, and quantified by the standard curve method.

[0062] 2 Reagents and materials: Unless otherwise specified, all reagents used in this method are of analytical grade, and the water is the first-grade water specified in GB / T6682-2008 Specifications and Test Methods for Water for Analytical Laboratory Use.

[0063] 2.1 Dipotassium hydrogen phosphate trihydrate. 2.2 Tetrabutylammonium bromide. 2.3 Phosphoric acid. 2.4 Acetonitrile: chromatographic grade. 2.5 PQQ-2Na standard: purity ≥97.0%. 2.6 Aqueous microporous filter membrane: 0.22 μm.

[0064] 2.7 10 mmol / L Dipotassium Hydrogen Phosphate - 15 mmol / L Tetrabutylammonium Bromide Mixed Solution (pH 7.4): Weigh 2.28 g of dipotassium hydrogen phosphate trihydrate and 4.84 g of tetrabutylammonium bromide into a beaker, add 800 mL of water, dissolve by ultrasonic treatment, adjust the pH to 7.4 with phosphoric acid, transfer to a 1000 mL volumetric flask, make up the volume with water, and shake well. Filter through a 0.22 μm aqueous microporous membrane under vacuum, and then ultrasonic until there are no bubbles.

[0065] 2.8 Acetonitrile - Water Solution (Volume Ratio 1:3): Measure 250 mL of acetonitrile and 4750 mL of water respectively, add them into a reagent bottle, and mix well.

[0066] 3 Instruments and Equipment

[0067] 3.1 High - performance liquid chromatograph, equipped with an ultraviolet detector and an automatic sampler.

[0068] 3.2 Electronic balance: The sensitivity is 0.01 mg.

[0069] 4 Analytical Procedures

[0070] 4.1 Preparation of Standard Solution Weigh 40 mg of PQQ - 2Na standard (accurate to 0.01 mg), place it in a 100 mL volumetric flask, add acetonitrile - water solution to dissolve and make up the volume to the mark, shake well, and obtain a PQQ - 2Na standard stock solution with a concentration of 0.4 mg / mL. Dilute this solution to prepare a series of PQQ - 2Na standard solutions with concentrations of 0.04 mg / mL, 0.08 mg / mL, 0.12 mg / mL, 0.16 mg / mL, 0.20 mg / mL, and 0.24 mg / mL.

[0071] 4.2 Sample Treatment Weigh 20 mg each of the PQQ - 2Na samples in Examples 9 - 12 (accurate to 0.01 mg), place them in 50 mL volumetric flasks, add acetonitrile - water solution to dissolve and make up the volume to the mark, shake well; then accurately pipette 5.0 mL of the above solution into a 10 mL volumetric flask, dilute to the mark with acetonitrile - water solution, shake well, and filter the filtrate through a 0.22 μm aqueous microporous membrane under vacuum for determination.

[0072] 4.3 Liquid Chromatography Reference Conditions

[0073] 4.3.1 Chromatographic column: PFchromE PC18 88031205 - 4625 (4.6 mm × 250 mm, 5 μm, 120 Å) or a chromatographic column with equivalent performance.

[0074] 4.4 Determination

[0075] Under the specified chromatographic conditions, take 20 μL of each standard solution and sample solution, inject them into the liquid chromatograph respectively, conduct chromatographic analysis, and record the peak areas of PQQ-2Na in the chromatograms of the obtained standard solutions and sample solutions. Using the peak area of PQQ-2Na in the standard solution as the Y-axis and the corresponding standard solution concentration as the X-axis, plot the standard curve to obtain the PQQ-2Na standard curve. According to the peak area of PQQ-2Na in the chromatogram of the sample solution, calculate the concentration of PQQ-2Na in the sample solution from the standard curve.

[0076] 5 Results Calculation

[0077] 5.1 Calculation of PQQ-2Na Content Results

[0078] The content of PQQ-2Na in the sample is calculated as its mass fraction W1, and the value is expressed as a percentage (%), calculated according to formula (1):

[0079]

[0080] In formula (1): C—the concentration of pyrroloquinoline quinone in the sample solution obtained from the standard curve, unit: milligram per milliliter (mg / mL); V—the dilution volume of the sample, unit: milliliter (mL); f—the purity of the PQQ-2Na standard product; m—the mass of the sample, unit: milligram (mg); W2—the mass fraction of water in the sample, and the value is expressed as a percentage (%). Take the arithmetic mean of the parallel determination results as the determination result, and express the result to two decimal places.

[0081] 5.2 Calculation of PQQ-2Na Residual Rate Results

[0082] PQQ-2Na residual rate = 1 - [((PQQ-2Na content in the initial sample - PQQ-2Na content in the stability sample) / PQQ-2Na content in the initial sample) × 100%]

[0083] It should be understood that in various embodiments of the present invention, the magnitude of the serial numbers does not mean the order of execution. Some or all of the steps can be executed in parallel or successively, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation to the implementation process of the embodiments of this application. The present invention will be further elaborated below with reference to the embodiments:

[0084] Experimental Example 1 Verification of the Combination for Improving the Residual Rate of PQQ-2Na

[0085] The components shown in Table 1 below (in mass percentage) were sequentially added to cold deionized water and mixed evenly to prepare each test solution. These test solutions were filled into 30 ml plastic bottles and then placed under two test conditions of 48°C and cycling between -15°C and 45°C for one month. The samples under high temperature and cycling conditions were quantified by liquid chromatography, and the residual rate (%) of PQQ-2Na after the stability test was determined. The results are shown in Table 1:

[0086] Table 1

[0087]

[0088] From the data in the above table, it can be seen that in Examples 1-7, the trimethylpentanediol / adipic acid / glycerol crosslinked polymer and Lipidure-PMB(Ph10) polyquaternium-51 were compounded in different ratios or used alone, and compared with Comparative Example 1, they could all significantly improve the residual rate of PQQ-2Na. Among them, when the addition amounts of the trimethylpentanediol / adipic acid / glycerol crosslinked polymer and Lipidure-PMB(Ph10) polyquaternium-51 were compounded at a ratio of 3:1 (Examples 1 and 2), the system was more stable and the residual rate of PQQ-2Na was higher.

[0089] Experimental Example 2 Stability Test of PQQ-2Na with Different pH Regulators

[0090] The components shown in Table 2 below (in mass percentage) were sequentially added to cold deionized water and mixed evenly, and the pH was adjusted to a similar pH gradient with different pH regulators to prepare each test solution. These test solutions were filled into 30 ml plastic bottles and then placed under two test conditions of 48°C and cycling between -15°C and 45°C for one month. The physical and chemical indexes and appearance changes of the samples were tested respectively. The samples under high temperature and cycling conditions were quantified by liquid chromatography, and the residual rate (%) of PQQ-2Na after the stability test was determined.

[0091] Table 2

[0092]

[0093] As can be seen from the above table, when the pH was adjusted with sodium citrate (Examples 8-10), the pH fluctuation was very small at each gradient. On the contrary, the pH of 2-amino-2-methyl-1-propanol and sodium hydroxide fluctuated, especially when pH > 6 (Comparative Examples 7-8), the fluctuation was greater. Too large a pH fluctuation had a strong negative impact on the stability of the product.

[0094] Experimental Example 3 Stability Test of Different pH Regulators when Introducing Components Incompatible with PQQ-2Na (Taking Panthenol as an Example)

[0095] The components shown in Table 3 below (in mass percentage) were successively added to cold deionized water and mixed evenly. Different pH regulators were used to adjust to similar pH gradients to prepare each test solution. These test solutions were filled into 30 ml plastic bottles and then placed in two test conditions of 48 °C and -15~45 °C cycling for one month. The physical and chemical indexes and appearance changes of the samples were tested respectively. The samples under high temperature and cycling conditions were quantified by liquid chromatography, and the residual rate (%) of PQQ-2Na after stability test was calculated.

[0096] Table 3

[0097]

[0098] As can be seen from the above table, in Examples 12-14, PQQ-2Na can maintain a high residual rate under various pH conditions, and its residual rate is higher than that in Comparative Examples 10-15. Especially when the pH is about 5.6, Example 13 (adjusting pH with sodium citrate) is significantly higher than Comparative Example 12 (adjusting pH with aminomethylpropanol) and Comparative Example 13 (adjusting pH with sodium hydroxide). In summary, it shows that when introducing substances incompatible with PQQ-2Na and under extreme conditions (high temperature of 48 °C), sodium citrate can better stabilize PQQ-2Na, and compared with Comparative Example 1 (without adding any pH regulator), when the pH is between 4-6, sodium citrate can also increase the residual rate of PQQ-2Na.

[0099] Experimental Example 4 Stability Test of PQQ-2Na

[0100] The components shown in Table 4 below (in mass percentage) were successively added to cold deionized water and mixed evenly. Different pH regulators were used to adjust to similar pH to prepare each test solution. These test solutions were filled into 30 ml plastic bottles and then placed in the 48 °C test condition for one month. The samples under high temperature conditions before and after the test were quantified by liquid chromatography, and the residual rate (%) of PQQ-2Na after stability test was calculated.

[0101] Table 4

[0102]

[0103] As can be seen from the above table, when trimethylpentanediol / adipic acid / glycerol cross-linked polymer and Lipidure-PMB(Ph10) polyquaternium-51 are compounded at 1.5:0.5 and adjusted to a higher pH with sodium citrate (Example 15), a relatively high residual rate can still be maintained. It shows that the combination of adjusting pH with sodium citrate (Example 15) has a significantly higher residual rate of PQQ-2Na than the combinations of aminomethylpropanol and sodium hydroxide (Comparative Examples 16-17).

[0104] Experimental Example 5 Stability Test of PQQ-2Na in a Formulation Containing D-Panthenol

[0105] The components shown in Table 5 below (in mass percentages) were sequentially added to cold deionized water and mixed evenly to prepare each test solution. These test solutions were filled into 30-ml plastic bottles and then placed under two test conditions: 48°C and cycling between -15°C and 45°C for one month. The PQQ-2Na content before and after the investigation was quantified by liquid chromatography, and the residual rate (%) of the component after storage was calculated.

[0106] Table 5

[0107]

[0108] As can be seen from Table 5, in the solution of PQQ-2Na alone (Comparative Example 18), due to the co-use with D-panthenol, the residual rate of PQQ-2Na decreased by at least 25.74%. However, by incorporating trimethylolpentanediol / adipic acid / glycerol cross-linked polymer and Lipidure-PMB (Ph10) polyquaternium-51, the content of PQQ2Na was restored by at least about 8.46%.

[0109] Experimental Example 6 Stability Test of PQQ-2Na in a Formulation Containing Spectrastat™ PHL

[0110] The components shown in Table 6 below were sequentially added to cold deionized water and mixed evenly to prepare each test solution. These test solutions were filled into 30-ml plastic bottles and then placed under two test conditions: 48°C and cycling between -15°C and 45°C for one month. The PQQ-2Na content before and after the investigation was quantified by liquid chromatography, and the residual rate (%) of the component after storage was calculated.

[0111] Table 6

[0112]

[0113] As can be seen from Table 6, in the solution of PQQ-2Na alone (Comparative Example 19), due to the co-use with the preservative PHL, the content of PQQ-2Na decreased significantly by at least 9.88%. Additionally, by incorporating trimethylolpentanediol / adipic acid / glycerol cross-linked polymer and Lipidure-PMB (Ph10) polyquaternium-51, the content of PQQ-2Na was restored by at least about 4%.

[0114] Experimental Example 7 Stability Test of PQQ-2Na in a Formulation Containing Sodium Hyaluronate Hydrolysate

[0115] The components shown in Table 7 below (in mass percentages) were sequentially added to cold deionized water and mixed evenly to prepare each test solution. These test solutions were filled into 30-ml plastic bottles and then placed under two test conditions of cycling between 48°C and -15 to 45°C for one month. The PQQ-2Na content before and after the investigation was quantified by liquid chromatography, and the residual rate (%) of the components after storage was calculated.

[0116] Table 7

[0117]

[0118] As can be seen from Table 7, in the solution of PQQ-2Na alone (Comparative Example 20), due to being used in combination with sodium hyaluronate hydrolyzate, the content of PQQ-2Na decreased significantly by at least 8.04%. In addition, by incorporating trimethylolpentanediol / adipic acid / glycerol crosslinked polymer and Lipidure-PMB (Ph10) polyquaternium-51, the content of PQQ-2Na was restored by at least about 5.83%.

[0119] Experimental Example 8 Stability Test of PQQ-2Na in a Formulation Containing Hydroxyethyl Urea

[0120] The components shown in Table 8 below were sequentially added to cold deionized water and mixed evenly to prepare each test solution. These test solutions were filled into 30-ml plastic bottles and then placed under two test conditions of cycling between 48°C and -15 to 45°C for one month. The PQQ-2Na content before and after the investigation was quantified by liquid chromatography, and the residual rate (%) of the components after storage was calculated.

[0121] Table 8

[0122]

[0123] As can be seen from Table 8, in the solution of PQQ-2Na alone (Comparative Example 21), due to being used in combination with hydroxyethyl urea, the content of PQQ-2Na decreased significantly by at least 27.16%. In addition, by incorporating trimethylolpentanediol / adipic acid / glycerol crosslinked polymer and Lipidure-PMB (Ph10) polyquaternium-51, the content of PQQ-2Na was restored by at least about 10.25%.

[0124] Experimental Example 9 Stability Test of PQQ-2Na in a Formulation Containing PEG / PPG-14 / 7 Dimethyl Ether

[0125] The components shown in Table 9 below (in mass percentage) were successively added to cold deionized water and mixed evenly to prepare each test solution. These test solutions were filled into 30-ml plastic bottles and then placed under two test conditions of cycling between 48°C and -15 to 45°C for one month. The PQQ-2Na content before and after the investigation was quantified by liquid chromatography, and the residue rate (%) of the components after storage was calculated.

[0126] Table 9

[0127]

[0128] As can be seen from Table 9, in the solution of PQQ-2Na alone (Comparative Example 22), due to the co-use with PEG / PPG-14 / 7 dimethyl ether, the content of PQQ-2Na decreased significantly by at least 12.62%. In addition, by incorporating trimethylolpropane / adipic acid / glycerol cross-linked polymer and Lipidure-PMB (Ph10) polyquaternium-51, the content of PQQ-2Na was restored by at least about 5.47%.

[0129] Experimental Example 10 Instant Repair and Soothing Efficacy Test

[0130] Table 10

[0131]

[0132] Test Purpose: A single-center open trial, with more than 30 participants. The skin barrier was damaged by tape stripping, and the participants used the sample once. By means of instrument testing, the repair and soothing effects before and after using the sample were verified.

[0133] Test Instruments: Skin Melanin and Hemoglobin Meter Mexameter MX18 (Courage&Khazaka, Germany), Transdermal Water Loss Meter Teaxmeter (Courage&Khazaka, Germany)

[0134] Test Environment: Environmental Requirements: Temperature 21.0°C ± 1.0°C; Humidity 50% ± 10%

[0135] Trial Design: Before use, immediately after stripping damage, 4 hours after use, 6 hours after use

[0136] Test procedure: After signing in at the laboratory, wipe the inner sides of both hands and forearms with dry paper towels uniformly, mark a test area of 2 cm * 2 cm, with at least 1 cm interval between each area, and rest in the test environment for 15 - 20 minutes. Set up blank controls and sample application areas, with the areas randomly distributed. The test area is peeled 20 times with tape, and data is collected immediately after peeling using a Teaxmete instrument. After the test, apply the sample to the sample application area of the subject according to the sample usage method, and collect data on the arm using instruments such as CM825 and Teaxmeter 4 hours and 6 hours after use.

[0137] Data statistical analysis method: Use software to perform descriptive statistics on each measured value, including quantity, mean, standard deviation, minimum value, maximum value, etc. Use the Shapiro-Wilk Test for the significance test of data normal distribution. If Sig. (two-tailed) > 0.05, it is normally distributed; if the test data is normally distributed, the t-test method is used for statistical analysis; if the test data is non-normally distributed, the rank sum test method is used for statistical analysis.

[0138] Table 11 Comparison of skin transdermal water loss improvement rate between groups - sample application and blank control

[0139]

[0140] Table 12 Comparison of skin heme improvement rate between groups - sample application and blank control

[0141]

[0142] Note: The P-values and significance analysis in Table 11 and Table 12 are all obtained from the analysis between the examples and the blank control.

[0143] For 30 volunteers, the skin barrier was damaged by tape stripping. After single use of the sample of Example 26 (composition compounding), the transdermal water loss in the test area at 4 hours and 6 hours after use was improved compared with the immediate value after tape stripping damage, and there were significant differences in the values (P < 0.05). The results are shown in Tables 11 - 12. 6 hours after sample use, when the sample application area was compared with the blank control area and Comparative Examples 23 - 24, the change rate of transdermal water loss in the sample application area was greater than that in the blank control area, and there were significant differences in the values (P < 0.05). It shows that this stable composition can cooperate with PQQ to enhance the repair and soothing effects.

[0144] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A composition containing PQQ or its salt, characterized in that, It consists of the following components in parts by mass: PQQ or its salt: 0.01 - 0.05 parts, trimethylolpentanediol / adipic acid / glycerin cross-linked polymer: 0.1 - 10 parts, polyquaternium-51: 0.1 - 5 parts, and sodium citrate: 0.01 - 0.1 part.

2. The composition according to claim 1, wherein It consists of the following components in parts by mass: PQQ-2Na: 0.02 - 0.03 parts, trimethylolpentanediol / adipic acid / glycerin cross-linked polymer: 1 - 3 parts, polyquaternium-51: 0.5 - 3 parts, and sodium citrate: 0.00828 - 0.0449 part.

3. A cosmetic raw material, characterized in that, It includes the composition according to claim 1 or 2 and a functional component; The functional component is selected from at least one of Spectrastat™ PHL, sodium hyaluronate hydrolyzate, hydroxyethyl urea, PEG / PPG-14 / 7 dimethyl ether, and D-panthenol.

4. The cosmetic raw material according to claim 3, wherein The mass ratio of the functional component to PQQ in the composition is (0.1 - 2):(0.02 - 0.03).

5. The cosmetic raw material according to claim 3, characterized in that, It includes the following components in parts by mass: functional component: 0.1 - 2 parts, PQQ-2Na: 0.01 - 0.03 parts, trimethylolpentanediol / adipic acid / glycerin cross-linked polymer: 1 - 3 parts, polyquaternium-51: 0.5 - 3 parts, and sodium citrate: 0.00828 - 0.0449 part.

6. Use of the composition according to claim 1 or 2, or the cosmetic raw material according to any one of claims 3 - 5, in the preparation of cosmetics.

7. The application according to claim 6, characterized in that The cosmetic is a moisturizing and / or anti - redness cosmetic.

8. A cosmetic, characterized in that, It includes the composition according to claim 1 or 2, or the cosmetic raw material according to any one of claims 3 - 5.

9. The cosmetic according to claim 8, characterized in that, Among them, it includes the following components in mass fractions: PQQ-2Na: 0.02% - 0.03%, trimethylolpentanediol / adipic acid / glycerin cross-linked polymer: 1% - 3%, polyquaternium-51(Ph10) polyquaternium-51: 0.5% - 3%, pentanediol: 4%, sodium citrate: 0.00828% - 0.0449%, and the balance is water.

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