Citrus reticulata composition and preparation method thereof

Abstract

The invention discloses a citrus reticulata composition and a preparation method thereof. The citrus reticulata composition comprises citrus reticulata and hydrophilic modified flavonoid glycoside in a mass ratio of 1: (4-10), the preparation method of the pomelo peel composition comprises the following steps: adding a solvent into pomelo peel, hydrophilic modified flavonoid glycoside or pomelo peel, hydrophilic modified flavonoid glycoside and an auxiliary agent for dissolving, so that the solid content of the pomelo peel composition is 3-10%, carrying out heat preservation and stirring for 20-40 minutes, cooling to 25 DEG C or below, and filtering to obtain a clear and transparent solution 1; and removing the solvent in the solution 1 to obtain the citrus reticulata composition. The citrus reticulata composition has the characteristics of good water solubility, low-temperature stability and light and heat stability, and can be applied to a clear and transparent system.

Description

Technical Field

[0001] The invention relates to a pomelo composition, in particular to a pomelo composition and a preparation method thereof. Background Art

[0002] Citrus grandis is a flavonoid compound derived from the immature or nearly mature dried outer peel or pulp of the Rutaceae plant Citrus grandis (L.) Osbeck and grapefruit (C. paradisi Macfad.). It has antibacterial, anti-inflammatory and blood pressure lowering effects, and has synergistic effects with vitamin C. When applied to the skin, it can promote wound healing, improve local microcirculation and enhance the skin barrier. However, Citrus grandis has poor solubility and is easily discolored by light, which limits its application.

[0003] At present, in order to improve the solubility of citrus, the commonly used methods include: chemical modification methods such as methylation, acylation and glycosylation of citrus; preparation technology of citrus into nanoemulsion and liposome. However, the water / alcohol solution of the citrus composition prepared by the above methods has low transparency and has certain precipitates or suspended matter, and cannot be applied to transparent systems.

[0004] The existing Chinese public invention patent CN201710079501.7, a method for preparing a water-soluble inclusion compound of citrus flavonoids, discloses the use of hydroxypropyl-β-cyclodextrin to molecularly include citrus flavonoids to obtain a clear and transparent inclusion solution, that is, to obtain a water-soluble inclusion compound of citrus flavonoids.

[0005] Although the supramolecular system of citrus flavonoids prepared by cyclodextrin encapsulation disclosed in the above-mentioned Chinese open invention patent can meet the requirements of transparency and stability to a certain extent, the molecular weight of citrus tangerine is 580.53, and the internal cavity of cyclodextrin is limited, and the loading capacity of citrus tangerine is insufficient. When the addition amount is high or other substances with poor solubility are contained in the system, precipitation will still occur; and the water-soluble inclusion compound obtained by cyclodextrin encapsulation of citrus tangerine has poor low-temperature performance and low stability, and is easy to precipitate at a low temperature of 5°C. Therefore, the supramolecular system prepared by cyclodextrin encapsulation of citrus tangerine has poor low-temperature stability when used in cosmetics, and is not suitable for cosmetic formulas of transparent systems. Summary of the invention

[0006] The object of the present invention is to provide a pomelo composition and a preparation method thereof. The pomelo composition of the present invention has the characteristics of being water-soluble, having good low temperature stability and light and heat stability, and being able to be applied to a clear and transparent system.

[0007] The technical solution of the present invention is a citrus fruit composition, comprising citrus fruit and hydrophilic modified flavonoid glycoside in a mass ratio of 1:(4-10).

[0008] In the aforementioned citrus fruit composition, the hydrophilic modified flavonoid glycoside includes any one of glucosyl hesperidin, hesperidin methyl chalcone and troxerutin.

[0009] The aforementioned citrus fruit composition further comprises an auxiliary agent, which comprises any one or at least two of tocosolan, cyclodextrin, polyglycerol-10 fatty acid esters, polyoxyethylene hydrogenated castor oil, polyvinyl pyrrolidone, and polyethylene glycol.

[0010] In the aforementioned citrus fruit composition, the mass ratio of the auxiliary agent, citrus fruit and hydrophilic modified flavonoid glycoside is (0.1-1):1:(2-8.9).

[0011] In the aforementioned citrus fruit composition, the HLB value of the polyglycerol-10 fatty acid esters is in the range of 13-18; the HLB value of the polyoxyethylene hydrogenated castor oil is in the range of 12-15; the K value of the polyvinyl pyrrolidone is 50 or less; and the molecular weight of the polyethylene glycol is not less than 3000.

[0012] The above-mentioned citrus fruit composition is used in the preparation of transparent cosmetics. In the transparent system, the solid content of citrus fruit is 0.1-0.5%.

[0013] In the aforementioned application, the transparent system is an aqueous solution, a polyol solution or a transparent system containing water and a polyol.

[0014] The preparation method of the above-mentioned pomelo composition comprises the following steps:

[0015] S1, adding a solvent to the citrus fruit, the hydrophilic modified flavonoid glycoside or the citrus fruit, the hydrophilic modified flavonoid glycoside and the auxiliary agent to dissolve the citrus fruit composition to make the solid content of the citrus fruit composition 3-10%, stirring at a temperature of 20-40 minutes, cooling to below 25° C., filtering through a filter membrane, and obtaining a clear and transparent solution 1;

[0016] S2, removing the solvent in solution 1 to obtain a citrus aurantium composition.

[0017] In the above-mentioned preparation method, in step S1, the solvent is water or 5-10% by mass ethanol water, and the insulation temperature is 60-70°C.

[0018] In the aforementioned preparation method, in step S2, the method of removing the solvent includes spray drying or freeze drying.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The pomelo composition of the present invention adopts a certain proportion of pomelo and hydrophilic modified flavonoid glycoside, thereby improving the water solubility and dissolution rate of the pomelo, and further adding a specific proportion of an auxiliary agent can improve the dissolution rate of the pomelo in the composition; at the same time, the pomelo composition prepared by the present invention can be applied to a transparent system formula, is in a clear and transparent state in the transparent system, has no precipitation or precipitation phenomenon under low temperature and light and heat conditions, has good low temperature stability and light and heat stability, and is suitable for a transparent system cosmetic formula. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 These are the appearance pictures of the transparent essence, sample A, and sample B after being stored at 5°C for 28 days. DETAILED DESCRIPTION

[0022] The present invention will be further described below in conjunction with the embodiments, but they are not intended to limit the present invention.

[0023] Example:

[0024] A citrus fruit composition comprises citrus fruit and hydrophilic modified flavonoid glycoside in a mass ratio of 1:(4-10).

[0025] The hydrophilic modified flavonoid glycoside includes any one of glucosyl hesperidin, hesperidin methyl chalcone and troxerutin.

[0026] The hydrophilically modified flavonoid glycosides also include glycosyl compounds, hydroxyethyl compounds or methyl compounds of hydrophilically modified flavonoid glycosides.

[0027] The citrus fruit composition further comprises an auxiliary agent, which comprises any one or at least two of tocosolan, cyclodextrin, polyglycerol-10 fatty acid esters, polyoxyethylene hydrogenated castor oil, polyvinyl pyrrolidone, and polyethylene glycol.

[0028] In the citrus aurantium composition, the mass ratio of the auxiliary agent, citrus aurantium and the hydrophilic modified flavonoid glycoside is (0.1-1):1:(2-8.9).

[0029] The pomelo peel tangerine is extracted from the peel or pulp of pomelo, tangerine and orange, with a CAS number of 10236-47-2 and a purity of not less than 98%.

[0030] The tocosolan is a mixture of vitamin E succinate and polyethylene glycol esterification, mainly composed of monoesterified polyethylene glycol and a small amount of diesterified polyethylene glycol products. It has the fat solubility of vitamin E succinic acid and the water solubility of polyethylene glycol, and is safe, efficient, antioxidant and promotes the absorption of active ingredients. The CAS number is 9002-96-4.

[0031] The polyglycerol-10 fatty acid esters are fatty acid ester derivatives of decaglycerol, have water-oil amphiphilicity, and have an HLB value range of 13-18.

[0032] The polyoxyethylene hydrogenated castor oil is a mixture obtained by reacting natural castor oil with ethylene oxide after hydrogenation and saturation, has surface activity, and an HLB value range of 12-15.

[0033] The polyvinyl pyrrolidone is a non-ionic polymer compound with good water solubility and the functions of film-forming, bonding, solubilizing, and coagulating. It is widely used in the field of medicine and cosmetics due to its good biocompatibility and safety. The K value of polyvinyl pyrrolidone is 50 or less.

[0034] The polyethylene glycol is a high molecular polymer, non-irritating, has good water solubility, and has good compatibility with many organic components. It has excellent lubricity, moisture retention, dispersibility, and adhesion, and can be used as an antistatic agent and softener, etc. The molecular weight of the polyethylene glycol is not less than 3,000.

[0035] The preparation method of the above-mentioned pomelo composition comprises the following steps:

[0036] S1, weighing citrus aurantium, hydrophilic modified flavonoid glycoside or citrus aurantium, hydrophilic modified flavonoid glycoside and auxiliary agent according to mass percentage, adding 60-70° C. deionized water or 5-10% by mass ethanol deionized water solution as solvent, so that the solid content of the citrus aurantium composition is 3-10%, keeping warm and stirring for 20-40 minutes, cooling to below 25° C., filtering through a 0.4 um filter membrane, and obtaining a clear and transparent solution 1;

[0037] S2. Removing the solvent from the solution 1 by spray drying or freeze drying to obtain a solid powder, which is the citrus aurantium composition.

[0038] The prepared citrus fruit composition of the present invention can be directly dissolved in water, polyol or a transparent formula system containing water and polyol, and the clarity of the transparent formula system is maintained, and there is no precipitation and suspension of particles visible to the naked eye, and it is light-transmissive, has good compatibility with a variety of active ingredients and preservative ingredients, and can be used in the preparation of cosmetics of a transparent system. The solid content of citrus fruit is 0.1-0.5%.

[0039] Unless otherwise specified, the percentages described in the present invention are all by mass percentages.

[0040] Embodiment 1:

[0041] A citrus aurantium composition is prepared by using the following components in percentage by mass: 20% citrus aurantium, 70% glucosyl hesperidin, 9% polyvinyl pyrrolidone and 1% tocosolan.

[0042] The preparation method of the above composition is:

[0043] S1, weighing citrus aurantium, glucosyl hesperidin, polyvinyl pyrrolidone and tocopherol according to mass percentage, adding 65° C. deionized water as a solvent to make the solid content of the citrus aurantium composition 8%, keeping warm, stirring for 30 minutes, cooling to below 25° C., filtering through a 0.4 um filter membrane, and obtaining a clear and transparent solution 1;

[0044] S2. Removing the solvent from the solution 1 by spray drying to obtain a light yellow solid powder, i.e., the citrus aurantium composition.

[0045] Embodiment 2:

[0046] Example 2 is substantially the same as Example 1, except that the citrus aurantium composition uses 20% citrus aurantium and 80% glucosyl hesperidin in a mass percentage.

[0047] Embodiment 3:

[0048] Example 3 is substantially the same as Example 1, except that the citrus aurantium composition uses 20% citrus aurantium, 70% glucosyl hesperidin and 10% polyvinyl pyrrolidone in weight percentage.

[0049] Embodiment 4:

[0050] Example 4 is basically the same as Example 1, except that the citrus aurantium composition uses 10% citrus aurantium, 89% troxerutin and 10% polyvinyl pyrrolidone by mass percentage, and the solvent used in the preparation process is 10% ethanol aqueous solution.

[0051] Embodiment 5:

[0052] Example 5 is basically the same as Example 1, except that the citrus aurantium composition uses 10% citrus aurantium, 85% hesperidin methyl chalcone and 5% polyvinyl pyrrolidone by mass percentage. The solvent used in the preparation process is 5% ethanol aqueous solution, and the obtained citrus aurantium composition is a yellow solid powder.

[0053] Embodiment 6:

[0054] Example 6 is substantially the same as Example 1, except that the citrus aurantium composition uses 9.09% citrus aurantium and 90.91% glucosyl hesperidin in a mass percentage.

[0055] Embodiment 7:

[0056] Example 7 is basically the same as Example 1, except that the citrus aurantium composition uses 20% citrus aurantium, 70% glucosyl hesperidin, 9% polyvinyl pyrrolidone and 1% polyglycerol-10 stearate in mass percentage, and the citrus aurantium composition is an off-white solid powder.

[0057] Embodiment 8:

[0058] Example 8 is substantially the same as Example 7, except that the citrus aurantium composition uses 20% citrus aurantium, 70% glucosyl hesperidin, 9% polyvinyl pyrrolidone and 1% cyclodextrin in mass percentage.

[0059] Embodiment 9:

[0060] Example 9 is substantially the same as Example 1, except that the citrus aurantium composition uses 20% citrus aurantium, 70% glucosyl hesperidin, 9% polyvinyl pyrrolidone and 1% PEG-40 hydrogenated castor oil in mass percentage.

[0061] Embodiment 10:

[0062] Example 10 is substantially the same as Example 1, except that the citrus aurantium composition uses 25% citrus aurantium, 50% glucosyl hesperidin and 25% PEG-3350 by mass; and freeze drying is used to remove the solvent during the preparation process.

[0063] Comparative Example 1:

[0064] Comparative Example 1 is substantially the same as Example 1, except that the citrus aurantium composition uses 30% citrus aurantium and 70% glucosyl hesperidin in a mass percentage.

[0065] Comparative Example 2:

[0066] Comparative Example 2 is substantially the same as Example 1, except that the citrus aurantium composition uses 20% citrus aurantium and 80% polyvinyl pyrrolidone in a mass percentage.

[0067] Comparative Example 3:

[0068] Comparative Example 3 is substantially the same as Example 1, except that the citrus aurantium composition uses 20% citrus aurantium and 80% cyclodextrin in a mass percentage.

[0069] Comparative Example 4:

[0070] Comparative Example 4 is substantially the same as Example 1, except that the citrus aurantium composition uses 20% citrus aurantium and 80% polyglycerol-10 stearate in mass percentage.

[0071] Comparative Example 5:

[0072] Comparative Example 5 is substantially the same as Example 1, except that the citrus aurantium composition uses 20% by mass of citrus aurantium and 80% by mass of PEG-40 hydrogenated castor oil.

[0073] Comparative Example 6:

[0074] Comparative Example 6 is substantially the same as Example 1, except that the citrus aurantium composition uses 20% citrus aurantium and 80% tocosolan by mass.

[0075] Comparative Example 7:

[0076] Comparative Example 7 is substantially the same as Example 10, except that the citrus aurantium composition uses 20% citrus aurantium and 80% PEG-3350 in a mass percentage.

[0077] Comparative Example 8:

[0078] Comparative Example 8 is substantially the same as Example 1, except that the citrus aurantium composition is prepared by using 100% citrus aurantium by mass without any processing.

[0079] Comparative Example 9:

[0080] Comparative Example 9 is substantially the same as Example 1, except that the citrus aurantium composition is prepared by using 100% by mass of glucosyl hesperidin without any process treatment.

[0081] The ingredients of different embodiments are shown in Table 1, and the ingredients of different comparative examples are shown in Table 2.

[0082] Table 1. Specific ingredients of different examples

[0083]

[0084]

[0085] Table 2. Specific ingredients of different examples

[0086] sample Citrus Hydrophilic modified flavonoid glycosides Additives Comparative Example 1 30％ 70% Glucosyl Hesperidin Comparative Example 2 20％ 80% Polyvinylpyrrolidone Comparative Example 3 20％ 80% Cyclodextrin Comparative Example 4 20％ 80% Polyglyceryl-10 Stearate Comparative Example 5 20％ 80% PEG-40 hydrogenated castor oil Comparative Example 6 20％ 80% Tocosolan Comparative Example 7 20％ 80% PEG-3350 Comparative Example 8 100％ Comparative Example 9 100% Glucosyl Hesperidin

[0087] Examples 1-9 were used as samples, and the content of citrus aurantium was determined by HPLC. The results are shown in Table 3.

[0088] Table 3. Appearance of each group of samples and determination results of citrus content

[0089]

[0090]

[0091] As shown in Table 3, the mass content of citrus aurantium detected in Examples 1-10 is close to the mass content of citrus aurantium in the theoretical composition, indicating that citrus aurantium has not chemically reacted with the hydrophilic modified flavonoid glycoside or the auxiliary agent to generate other substances.

[0092] The solubility test of Examples 1-10 and Comparative Example 8 was conducted, and the specific method was as follows: 1g of the samples of Examples 1-10 and 0.2g of the sample of Comparative Example 8 were weighed, added to a certain volume of water, placed in an environment of 25±2°C, shaken at a speed of 3200rpm for 30 seconds every 5 minutes, and observed the dissolution within 30 minutes. If there were no visible solute particles or droplets, it was considered to be completely dissolved, and the amount of water required for the complete dissolution of 1g of the sample was recorded or calculated, and the mass fraction of the pomelo in the corresponding solution was calculated. At the same time, the dissolution rate was evaluated. If the complete dissolution time was less than 15 minutes, the dissolution rate was determined to be fast, if it was greater than 15 minutes and less than 20 minutes, it was determined to be medium, and if it was greater than 20 minutes, it was determined to be slow. The results are shown in Table 4.

[0093] Table 4. Solubility test results of different samples

[0094]

[0095] As can be seen from Table 4, according to the solubility judgment standard, the solubility and dissolution rate of the pomelo composition prepared by the present invention are significantly improved compared with the single pomelo, and the solubility of pomelo is increased from less than 0.01% to 2% and above, which is increased by more than 200 times, and the further addition of different auxiliary agents is beneficial to improving the dissolution rate of the pomelo composition, which may be due to the fact that the auxiliary agent is a hydrophilic or amphiphilic substance, which can further improve the surface wettability of the solid powder.

[0096] The samples of Examples 1-10 and Comparative Examples 1-7 were prepared into aqueous solutions with the mass percentages of 0.1%, 0.3% and 0.5% of citrus aurantium respectively (0.5%wt hexylene glycol and 0.5%wt p-hydroxyacetophenone were added to the aqueous solution for preservation), and the aqueous solution of Comparative Example 9 was prepared into aqueous solutions with the mass percentages of 1%, 3% and 5% of glucosyl hesperidin respectively (0.5%wt hexylene glycol and 0.5%wt p-hydroxyacetophenone were added to the aqueous solution for preservation), and were placed at 5°C, 25°C and light (45°C) conditions, respectively. The appearance of the samples was observed after 14 days. If the solutions of each group were opaque or precipitated upon preparation, no subsequent test was performed. The results are shown in Table 5.

[0097] Table 5. Solubility test results of different samples

[0098]

[0099]

[0100]

[0101] As shown in Table 5, the examples 1-9 with a mass percentage of 0.1%, 0.3%, and 0.5% of citrus aurantium are all clear, transparent, stable, and without precipitation at 5°C, 25°C, and light (45°C), and the color has no obvious change, while the comparative examples 1-7 have different degrees of precipitation at 5°C and 25°C. Therefore, the citrus aurantium composition of the present invention can be directly dissolved in an aqueous solution, and the overall system is kept clear and transparent at 5°C, 25°C, and light (45°C), and has good low temperature stability and light and heat stability.

[0102] In addition, in the light stability test, it was found that comparative example 9 changed color under light, while the composition samples containing both citrus aurantium and glucosyl hesperidin of the present invention did not change color under light conditions. Therefore, the light stability of the citrus aurantium composition of the present invention is better than that of single glucosyl hesperidin.

[0103] Comparative Example 8 and Example 1 were added to the transparent essence at a mass percentage of 0.1% of pomelo, respectively as sample A and sample B. The formula compositions of the transparent essence, sample A and sample B are shown in Table 6.

[0104] Table 6. Formula composition of different samples

[0105] Components Transparent Essence Sample A Sample B water 88.85 88.75 88.35 glycerin 5 5 5 Butanediol 2 2 2 Carbomer 0.1 0.1 0.1 Xanthan gum 0.05 0.05 0.05 Adenosine 0.1 0.1 0.1 Allantoin 0.1 0.1 0.1 Panthenol 0.2 0.2 0.2 Niacinamide 2 2 2 Tetrahydroxypyrimidine carboxylic acid 0.5 0.5 0.5 Tromethamine 0.1 0.1 0.1 1,2-Hexanediol 0.5 0.5 0.5 p-Hydroxyacetophenone 0.5 0.5 0.5 Example 1 0.5 Comparative Example 8 0.1

[0106] Place the transparent essence, sample A and sample B at 5℃ and observe the samples after 28 days. Figure 1 shown. Figure 1 From left to right in the figure are blank transparent essence, sample A, and sample B.

[0107] Since different proportions of active ingredients with different solubility are added to the essence formula, such as adenosine and allantoin with average solubility, these may affect the low-temperature stability of the citrus fruit composition, and then precipitate and affect the transparency of the system. Figure 1 The results show that the fine particles precipitated from sample A (pure citrus aurantium) are suspended in the system and are opaque, while sample B (citrus aurantium composition) is clear and transparent, with no particles precipitated and suspended, and has good low-temperature stability. Therefore, the citrus aurantium composition of the present invention is clear and transparent in a transparent system containing alcohol and active substances, and has good low-temperature stability.

[0108] In summary, the combination of citrus aurant and hydrophilic modified flavonoid glycoside in a specific proportion can improve the solubility of citrus aurant, and the further addition of an auxiliary agent in a specific proportion can improve the dissolution rate of citrus aurant in the composition. At the same time, the citrus aurant composition prepared by the present invention is clear and transparent in water, polyol or a transparent formula system containing water and polyol, has no precipitation or precipitation phenomenon under low temperature and light and heat conditions, has good low temperature stability and light and heat stability, and can be applied to transparent system cosmetic formulas.

[0109] It should be understood that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. For those skilled in the art, the technical solutions described in the above embodiments can be modified, or some of the technical features therein can be replaced by equivalents; and all these modifications and replacements should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A pomelo composition, characterized in that: The invention comprises citrus aurantium and hydrophilic modified flavonoid glycoside in a mass ratio of 1:(4-10).

2. The pomelo composition according to claim 1, characterized in that: The hydrophilic modified flavonoid glycoside includes any one of glucosyl hesperidin, hesperidin methyl chalcone and troxerutin.

3. The pomelo composition according to claim 1, characterized in that: The invention also includes auxiliary agents, which include any one or at least two of tocosolan, cyclodextrin, polyglycerol-10 fatty acid esters, polyoxyethylene hydrogenated castor oil, polyvinyl pyrrolidone and polyethylene glycol.

4. The pomelo composition according to claim 3, characterized in that: The mass ratio of the auxiliary agent, citrus aurantium and hydrophilic modified flavonoid glycoside is (0.1-1):1:(2-8.9).

5. The pomelo composition according to claim 3, characterized in that: The HLB value of the polyglycerol-10 fatty acid esters is in the range of 13-18; the HLB value of polyoxyethylene hydrogenated castor oil is in the range of 12-15; the K value of the polyvinyl pyrrolidone is 50 or less; and the molecular weight of the polyethylene glycol is not less than 3000.

6. Use of the pomelo composition according to any one of claims 1 to 5 in the preparation of transparent cosmetics, characterized in that: The citrus aurantium composition is used in transparent cosmetics, and the solid content of citrus aurantium is 0.1-0.5%.

7. The use according to claim 6, characterized in that: The transparent system is an aqueous solution, a polyol solution or a transparent system containing water and polyol.

8. The method for preparing the pomelo composition according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, adding a solvent to the citrus fruit, the hydrophilic modified flavonoid glycoside or the citrus fruit, the hydrophilic modified flavonoid glycoside and the auxiliary agent to dissolve the citrus fruit composition to make the solid content of the citrus fruit composition 3-10%, stirring at a temperature of 20-40 minutes, cooling to below 25° C., filtering through a filter membrane, and obtaining a clear and transparent solution 1; S2, removing the solvent in solution 1 to obtain a citrus aurantium composition.

9. The preparation method according to claim 8, characterized in that: In step S1, the solvent is water or 5-10% ethanol water by mass, and the insulation temperature is 60-70°C.

10. The preparation method according to claim 8, characterized in that: In step S2, the method of removing the solvent includes spray drying or freeze drying.

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