Base oil with transdermal absorption characteristic as well as preparation method and application thereof

Abstract

The invention belongs to the field of light industry grease, and particularly relates to a preparation method and application of base oil with a transdermal absorption characteristic. The method comprises the following steps: taking diglyceride as skin care product emulsion base oil for the first time, taking oleic acid, capric acid and glycerol as raw materials, carrying out catalytic esterification through a specific enzyme method to obtain diglyceride, carrying out molecular distillation purification, and further separating and purifying through a solvent method to control the proportion of 1-oleic acid-3-capric acid diglyceride in the diglyceride, so as to obtain the skin care product emulsion. The base oil which has improved transdermal absorption performance and can be applied to skin care product emulsion is prepared. The composition of diglyceride acyl and the content of isomers (especially 1-oleic acid-3-decanoic acid diglyceride in diglyceride) are controlled, compared with traditional grease, when tocotrienol is delivered, the permeability and the permeation amount per unit area in 24 hours are remarkably improved, and the retention amount of tocotrienol delivered to a corium layer is remarkably increased.

Description

Technical Field

[0001] The invention belongs to the field of light industrial oils and fats, and specifically relates to a base oil that can be used for daily chemical skin care products and cosmeceutical products for transdermal delivery and absorption, and a preparation method and application thereof. Background Art

[0002] Oils and fats are crucial in the formulation of skin care products. They not only have multiple functions such as moisturizing, wetting and softening the skin, but also directly affect the quality of skin care products, such as appearance, paste viscosity, stability and skin feel. According to the chemical structure, lipid raw materials can be divided into the following categories: synthetic esters, silicones, triglycerides (mainly from animal and plant oils) and hydrocarbons (such as mineral oils and waxes). Synthetic esters generally have good stability and ductility, but some synthetic esters may cause skin sensitivity or allergic reactions. Siloxane compounds can provide a silky touch, but studies have shown that siloxane compounds may enter the human body through breathing, digestion and skin routes, thus posing a potential threat to health. Mineral oils and waxes have excellent sealing and moisturizing properties, and a wide range of viscosity options. However, these substances lack bioactive ingredients, and mineral oil aromatic hydrocarbons (MOAH) and polycyclic hydrocarbons (PAH) may exist in the raw materials or during processing, which are considered to be potentially carcinogenic. As consumers become more aware of health and environmental protection, they are increasingly inclined to choose green and natural skin care products. In this regard, animal and plant oils have become the most commonly used base oils due to their natural origin, high safety and good skin affinity.

[0003] Triglyceride-type vegetable oils not only have good moisturizing and nutritional value, but also contain a variety of bioactive ingredients, such as vitamins and antioxidants, and are widely used in various cosmetic formulas for skin and hair care. Its limitations are also obvious. The larger structure and non-polar properties of triglyceride molecules limit their penetration ability, which limits the effective penetration and absorption of some active ingredients. Furthermore, the lower penetration ability easily forms a thick oil film on the skin surface, bringing a greasy feeling. In order to overcome the limitations of triglyceride-type oils, oil modification technology has been introduced to improve the functionality and usage experience of oils. By partially hydrolyzing the fatty acids in the triglyceride molecular structure, diglycerides with a smaller molecular weight and a certain polarity can be obtained. This modification can significantly improve the penetration ability of oils and enhance their skin affinity and usage experience.

[0004] Compared with triglycerides, diglycerides can better interact with polar components in the stratum corneum (such as fatty acids and neutral lipids) through hydrogen bonds and van der Waals forces, thereby showing better skin permeability. This superior permeability makes diglycerides an important oil phase component in skin care products, especially in skin care product formulations that need to enhance the penetration of active ingredients. Summary of the invention

[0005] Aiming at the problem that plant oil-based base oil has low permeability and weak active ingredient delivery effect in skin care product system, the purpose of the present invention is to provide a method for preparing a skin care product base oil with high transdermal absorption characteristics and efficient delivery of tocotrienol. In order to obtain a skin care product base oil that deeply delivers tocotrienols, while increasing skin permeability and skin accumulation, the present invention uses oleic acid and capric acid as raw materials, adopts specific enzymatic esterification, prepares oleic acid-capric acid diglyceride, obtains 1-oleic acid-3-capric acid diglyceride with a glycerol skeleton by purification, and improves the skin permeability and skin accumulation of diglyceride as a skin care product emulsion base oil during transdermal absorption.

[0006] The present invention also provides a skin care product base oil with transdermal absorption characteristics obtained by the method.

[0007] The present invention also provides application of the above-mentioned skin care product base oil with transdermal absorption characteristics.

[0008] The purpose of the present invention is achieved through the following technical solutions: A method for preparing a skin care product base oil with transdermal absorption properties comprises the following steps: (1) mixing oleic acid and capric acid and subjecting them to enzymatic specific esterification with glycerol, and obtaining a diglyceride composition after molecular distillation; (2) The content of 1-oleo-3-capryloylglycerol in diglyceride is increased by a solvent purification method to obtain oil rich in 1-oleo-3-capryloylglycerol, that is, to obtain the skin care base oil with transdermal absorption characteristics.

[0009] The oleic acid and capric acid in step (1) are commercially available, and the purity is both greater than 99%.

[0010] In the enzymatic specific catalytic esterification described in step (1), the enzyme is a lipase, preferably one of the lipases LipozymeCALB, LipozymeRMIM, Lipozyme TL IM or Lipozyme 435; the mass ratio of oleic acid to capric acid is 1:1-1:1.5, and the ratio of the total mass of oleic acid and capric acid to the mass of glycerol is 3.5:1-2:1; the amount of enzyme added is 1-3% of the total mass of oleic acid and capric acid, the temperature of the esterification reaction is 60-80°C, the reaction time is 60-120 min, and the vacuum degree is ≤2000pa.

[0011] After the esterification reaction in step (1) is completed, centrifugal filtration is performed, and the upper oil phase is taken for molecular distillation; The molecular distillation in step (1) obtains crude diglyceride in the light phase, and the diglyceride content is greater than 99%.

[0012] The molecular distillation of step (1) is operated according to the following parameters: distillation temperature is 180-190°C, vacuum degree is 0.5-1.0 Pa, scraper speed is 150-200 rpm, condenser temperature is 30-50°C, and feed flow rate is ≤0.5 mL / min.

[0013] The purification described in step (2) is a solvent purification, and the specific steps are: add 8-20 times (preferably 15 times) the weight of the crude product as an organic reagent (n-hexane: ethyl acetate = 90:10 (V / V)) to the crude diglyceride, and place the system at 0-4°C for crystallization for more than 5 hours. Use vacuum filtration to obtain the solid phase component, and after removing the organic reagent, obtain a diglyceride composition rich in 1-oleo-3-decanoic acid diglyceride (>20%), that is, a skin care base oil with transdermal absorption properties.

[0014] A skin care product base oil with transdermal absorption characteristics prepared by the method.

[0015] The use of the above-mentioned skin care base oil with transdermal absorption characteristics in transdermal absorption skin care products is preferably used in transdermal absorption emulsions.

[0016] A skin care emulsion with transdermal absorption properties, which is prepared from the above-mentioned base oil with transdermal absorption properties, wherein the base oil with transdermal absorption properties accounts for 4-8wt%, preferably 6%; the emulsion also includes tocotrienol, and the mass of tocotrienol is 5-80wt% of the mass of the base oil with transdermal absorption properties. The prepared skin care emulsion has a transdermal permeation rate of tocotrienol delivered transdermally>10.66μg / cm 2 ·h, 24-hour cumulative permeation per unit area>172.41μg / cm 2 , the skin retention of tocotrienols in the dermis was >40.84 μg.

[0017] Compared with the prior art, the present invention has the following advantages and beneficial effects: The present invention is the first to use diglyceride as a base oil for skin care emulsions. Compared with other oils and processes, the present invention controls the acyl composition and isomer content of diglyceride (especially 1-oleoyl-3-decanoyl diglyceride in diglyceride). As a base oil for skin care emulsions that deliver tocotrienols transdermally, the transdermal penetration effect of the emulsion, including the permeability and the 24-hour permeation per unit area, is significantly improved, and the retention of tocotrienols delivered to the dermis is significantly increased. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The fluorescent graphs are the transdermal penetration effects of some embodiments and comparative examples. DETAILED DESCRIPTION

[0019] The present invention is further described in detail below in conjunction with the examples and drawings, but the embodiments of the present invention are not limited thereto. The raw materials, reagents, etc. involved in the present invention can be purchased directly from the market. For process parameters not particularly noted, conventional techniques can be used. The lipases used in the examples were purchased from Novozymes.

[0020] The present invention aims to obtain diglyceride by specific enzymatic catalytic esterification, and to control the ratio of 1-oleoyl-3-decanoyl diglyceride in diglyceride by solvent purification to prepare a base oil with improved transdermal absorption performance that can be used in skin care emulsions. Compared with traditional oils, the oil has significantly improved permeability and 24-hour permeation per unit area when delivering tocotrienols, and significantly improved the retention of tocotrienols delivered to the dermis. The experimental data and comparative test data of the physical and chemical properties of the base oil are studied in the following examples, and the method is as follows: (1) Analysis of diacylglycerol content: HPLC (Shimadzu 20A Corp, Kyoto, Japan) equipped with an ELSD-LTII low-temperature evaporative light scattering detector and a C18 column (5 μm, 250 mm × 4.6 mm) (Dikma Technology, Beijing, China) was used for component analysis. Mobile phase setting: Solvent A was isopropanol, solvent B was acetonitrile, and the column temperature was set at 30°C. 5 mg of the sample and 10 mL of acetone were taken and mixed thoroughly before injection. The mobile phase was in 0.8 mL / min gradient mode, and the mobile phase elution conditions were shown in the table, where the drift tube temperature was 55°C; the gain was set to 1.

[0021] Table 1 HPLC mobile phase elution conditions (2) Determination of isomer content in diacylglycerol use 1 The isomer ratio of 1,3 diacylglycerol to 1,2 diacylglycerol in the sample was determined by H–NMR technology: 20 mg of sample was weighed respectively, and the samples before and after purification were dissolved in 0.5 mL of CDCl3, and then the dissolved samples were transferred to the NMR tube for testing. The test conditions were: acquisition time 3.17 s, scan number 80, pulse width 12.76 μs, spectral width 10330.6 Hz, temperature 25 °C.

[0022] Table 2 NMR shift distribution corresponding to functional groups (3) Preparation of tocotrienol (TRF) loaded skin care emulsion The microemulsion was prepared using a skin care base oil with transdermal absorption characteristics as the oil phase (the oil phase contained 5% tocotrienols by weight of the base oil), 1,3-propylene glycol as a co-emulsifier, and RH40 as an emulsifier. The specific experimental steps are as follows: the microemulsion was prepared by titrating the oil phase (the oil phase accounted for 6%) and the mixed surfactant. The emulsifier (Cremopher®RH40 (22%, w / w)) and the co-emulsifier (1,3-propylene glycol (36%, w / w)) were mixed to form a mixed emulsifier, and then a magnetic stirrer was used to stir at a rate of 400r / min for 30 min. The mixed surfactant and the oil phase (6%, w / w) were stirred at 400 r / min for 30 min. Deionized water (36%, w / w) was added to the mixed system, and magnetic stirring was performed during the addition process to make the system change from clear to turbid. Deionized water was continued to be added until the system changed from turbid to clear and remained stable.

[0023] (4) In vitro permeation test In vitro skin permeation experiments were performed using Franz diffusion cells with slight modifications. Fresh pig skin was placed between the receiving cell and the donor cell, with the stratum corneum side facing the donor cell and the dermis side facing the receiving cell. 200 μL of microemulsion was added to the donor cell and evenly applied to the skin. The donor cell was sealed with a parafilm to prevent water evaporation. The receiving solution was a 50% v / v ethanol aqueous solution containing 0.5% w / v (g / mL) Tween80®. The volume of the receiving cell was 14.5 mL, and the effective diffusion area was 0.6 cm 2 , placed in a diffusion cell at (32±0.5°C) with a stirring speed of 300r / min. 1mL of sample was taken at 1, 2, 4, 6, 8, 12, and 24h, and an equal volume of fresh receiving solution was added. The experiment was carried out in the dark to prevent TRF degradation. The TRF concentration was determined by HPLC, and the cumulative permeation per unit area Q (μg / cm 2 ).

[0024] (1) In the formula, C n represents the mass concentration of TRF measured in the receiving solution corresponding to the nth sampling point (μg / mL); C i is the TRF mass concentration (μg / mL) measured in the receiving solution corresponding to the i-th (i=1,2,3…n-1) sampling point; V n is the total volume of the receiving pool (mL); V i is the volume of the i-th liquid taken out (mL); A is the effective pig skin area on the diffusion cell (cm 2 ).

[0025] The in vitro permeation kinetic curve was drawn by plotting the cumulative amount of permeation versus time t. The linear part of this curve was subjected to linear regression, and the slope of the obtained line was the permeation rate constant J. ss (μg / cm 2 ·h).

[0026] (5) Skin accumulation of microemulsions After the transdermal experiment, the skin was removed, the residual preparation on the skin surface was removed, and it was mounted on a cork board to evaluate the skin deposition of the microemulsion. The stratum corneum was peeled off with tape (Scotch 600, 3M, USA) (about 22 strips, until the skin became translucent). The collected tape was soaked in 100% MeOH for 24 hours to extract TRF. The epidermis was separated from the dermis by thermal separation. The epidermis and dermis were also homogenized with 100% MeOH for 24 hours to extract TRF. Then centrifuged at 12000 rpm for 15 minutes, the supernatant was filtered with a 0.22μm microporous membrane, and the TRF content was determined by HPLC after rotary evaporation.

[0027] (6) Visualization of skin active ingredient distribution using laser confocal electron microscopy Coumarin was used as a fluorescent probe and coumarin was used to replace tocotrienol to prepare a microemulsion, where the amount of coumarin was 0.01% w / v (mg / mL) of the amount of skin care base oil with transdermal absorption characteristics. The distribution and retention of the microemulsion in the pig skin layer were observed by CLSM. The microemulsion was diffused on the pig skin in the Franz diffusion cell for 1, 4, and 8 h. After the diffusion, the unspread emulsion on the surface was removed, and the skin was placed in a -20 °C refrigerator for frozen sections and observed using a laser confocal microscope.

[0028] Example 1 (1) Weigh 50g of oleic acid, 50g of capric acid, and 40g of glycerol in a beaker and melt them. Then add 2g of Lipozyme435 lipase, react at 70℃ and vacuum degree 2000Pa for 100 min, centrifuge and filter. The upper oil phase is crude diglycerol. The crude diglycerol is purified by molecular distillation at a distillation temperature of 180℃, a vacuum degree of 0.5 Pa, a scraper speed of 200 rpm, a condenser temperature of 30℃, and a feed flow rate of 0.5 mL / min to obtain pure diglycerol with a diglycerol content of 99.1%.

[0029] (2) Weigh 10 g of pure diglyceride, add 150 ml of organic reagent (n-hexane: ethyl acetate = 90:10 (V / V)), and place the system at 4°C for crystallization for 5 h. Use vacuum filtration to obtain the solid phase component, and after removing the organic reagent, obtain a diglyceride composition rich in 1-oleyl-3-decanoyl diglyceride, that is, a skin care base oil with transdermal absorption properties.

[0030] According to calculation, the content of 1-oleoyl-3-decanoyl diglyceride in the composition is 33%. The composition is used to prepare a skin care emulsion loaded with tocotrienol, and the transdermal permeation rate of tocotrienol delivered through the skin is 13.00 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 222.41μg / cm 2 , the skin retention of tocotrienols in the dermis was 50.13 μg.

[0031] Example 2 This embodiment is the same as Embodiment 1 except for the following technical features: In step (1), the reaction temperature is set to 60° C. and the reaction time is 60 min.

[0032] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 21%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 10.66 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 172.41μg / cm 2 , the skin retention of tocotrienols in the dermis was 40.84 μg.

[0033] Example 3 This embodiment is the same as Embodiment 1 except for the following technical features: In step (1), the reaction temperature is set to 80° C. and the reaction time is 120 min.

[0034] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 38%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 12.12 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 180.03μg / cm 2 , the skin retention of tocotrienols in the dermis was 41.35 μg.

[0035] Example 4 This embodiment is the same as Embodiment 1 except for the following technical features: In step (1), the reaction temperature is set to 70° C. and the reaction time is 120 min.

[0036] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 36%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 12.55 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 200.02μg / cm 2 , the skin retention of tocotrienols in the dermis was 47.27 μg.

[0037] Example 5 This embodiment is the same as Embodiment 1 except for the following technical features: In step (1), the lipase is Lipozyme RM IM.

[0038] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 22%. When used to prepare a skin care emulsion loaded with tocotrienol, the transdermal permeation rate of tocotrienol delivered through the skin is 10.70 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 175.11μg / cm 2 , the skin retention of tocotrienols in the dermis was 40.30 μg.

[0039] Example 6 This embodiment is the same as Embodiment 1 except for the following technical features: In step (1), the lipase is Lipozyme TL IM.

[0040] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 22%. When used to prepare a skin care emulsion loaded with tocotrienol, the transdermal permeation rate of tocotrienol delivered through the skin is 11.32 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 181.10μg / cm 2 , the skin retention of tocotrienols in the dermis was 40.58 μg.

[0041] Example 7 This embodiment is the same as Embodiment 1 except for the following technical features: In step (1), the amount of capric acid added is 75 g.

[0042] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diester in the composition obtained in step (2) is 20.5%, which is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 10.68 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 177.77μg / cm 2 , the skin retention of tocotrienols in the dermis was 41.92 μg.

[0043] Example 8 This embodiment is the same as Embodiment 1 except for the following technical features: Step (1) The amount of capric acid added is 60 g.

[0044] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 28%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 13.01 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 205.63μg / cm 2 , the skin retention of tocotrienols in the dermis was 48.18 μg.

[0045] Example 9 This embodiment is the same as Embodiment 1 except for the following technical features: In step (1), the amount of glycerol added is 50 g.

[0046] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 31%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 12.71 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 210.13μg / cm 2 , the skin retention of tocotrienols in the dermis was 47.49 μg.

[0047] Example 10 This embodiment is the same as Embodiment 1 except for the following technical features: In step (1), the amount of lipase added is 3 g.

[0048] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 34%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 11.98 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 203.23μg / cm 2 , the skin retention of tocotrienols in the dermis was 42.11 μg.

[0049] Comparative Example 1 This comparative example is the same as Example 1 except for the following technical features: commercially available peanut oil diglyceride (with a diglyceride content of 88.6%, purchased from Guangdong Shanbainian Special Medical Food Co., Ltd.) is used as the final product diglyceride composition.

[0050] According to the calculation, the content of 1-oleoyl-3-decanoyl diglyceride in the obtained composition is 0%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 7.98 μg / cm 2·h, the cumulative permeation per unit area in 24 hours is 110.60μg / cm 2 , the skin retention of tocotrienols in the dermis was 28.08 μg.

[0051] Comparative Example 2 This comparative example is the same as Example 1 except for the following technical features: olive oil (oleic acid content of 87%, purchased from Kerry Special Oils Co., Ltd.) is used as the final product diglyceride composition.

[0052] According to calculation, the content of 1-oleoyl-3-decanoylglycerol in the obtained composition is 0%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol, and the transdermal permeation rate of tocotrienol delivered through the skin is 5.00 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 63.88μg / cm 2 , the skin retention of tocotrienols in the dermis was 21.31 μg.

[0053] Comparative Example 3 This comparative example is the same as Example 1 except for the following technical features: caprylic acid triglyceride (capric acid content of 45%, purchased from Kerry Special Oils Co., Ltd.) is used as the final product diglyceride composition.

[0054] According to the calculation, the content of 1-oleoyl-3-decanoylglycerol in the obtained composition is 0%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol, and the transdermal permeation rate of tocotrienol delivered through the skin is 9.50 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 140.87μg / cm 2 , the skin retention of tocotrienols in the dermis was 38.90 μg.

[0055] Comparative Example 4 This comparative example is the same as Example 1 except for the following technical features: step (2) does not involve solvent purification, i.e., the pure diglyceride obtained in step (1) is the diglyceride composition prepared in this comparative example.

[0056] According to the calculation, the content of 1-oleoyl-3-decanoyl diglyceride in the obtained composition is 11%, which is used to prepare a skin care emulsion loaded with tocotrienol, and the transdermal permeation rate of tocotrienol delivered through the skin is 9.34 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 150.37μg / cm 2 , the skin retention of tocotrienols in the dermis was 38.25 μg.

[0057] Comparative Example 5 This comparative example is the same as Example 1 except for the following technical features: Step (1) the reaction temperature is set to 50°C.

[0058] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 18%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 7.77 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 128.73μg / cm 2 , the skin retention of tocotrienols in the dermis was 25.88 μg.

[0059] Comparative Example 6 This comparative example is the same as Example 1 except for the following technical features: Step (1) the reaction temperature is set to 90°C.

[0060] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 20%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 10.19 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 160.34μg / cm 2 , the skin retention of tocotrienols in the dermis was 40.11 μg.

[0061] Comparative Example 7 This comparative example is the same as Example 1 except for the following technical features: the diglyceride content after molecular distillation is 58% (distillation temperature is 160°C, vacuum degree is 0.5 Pa, scraper speed is 200 rpm, condenser temperature is 40°C, feed flow rate is 0.5 mL / min), and then step (2) is performed.

[0062] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 19%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 6.08 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 89.66μg / cm 2 , the skin retention of tocotrienols in the dermis was 22.10 μg.

[0063] Comparative Example 8 This comparative example is the same as Example 1 except for the following technical features: the diglyceride content after molecular distillation is 89% (distillation temperature is 170°C, vacuum degree is 0.5 Pa, scraper speed is 200 rpm, condenser temperature is 35°C, feed flow rate is 0.5 mL / min), and then step (2) is performed.

[0064] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 29%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 7.13 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 112.08μg / cm 2 The skin retention of tocotrienol in the dermis is 23.91 μg Comparative Example 9 This comparative example is the same as Example 1 except for the following technical features: In step (1), only 100 g of oleic acid is used, and no capric acid is added.

[0065] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diester in the composition obtained in step (2) is 0%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 4.93 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 52.88μg / cm 2 , the skin retention of tocotrienols in the dermis was 18.01 μg.

[0066] Comparative Example 10 This comparative example is the same as Example 1 except for the following technical features: In step (1), only 100 g of capric acid is used without adding oleic acid.

[0067] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diester in the composition obtained in step (2) is 0%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 10.50 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 188.33μg / cm 2 , the skin retention of tocotrienols in the dermis was 22.43 μg.

[0068] Comparative Example 11 This comparative example is the same as Example 1 except for the following technical features: in step (1), caprylic acid is used instead of capric acid.

[0069] According to the calculation, the content of 1-oleoyl-3-octanoylglycerol diglyceride in the obtained composition is 33%, which is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 11.11 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 177.77μg / cm 2 , the skin retention of tocotrienols in the dermis was 21.12 μg.

[0070] Comparative Example 12 This comparative example is the same as Example 1 except for the following technical features: In step (1), linoleic acid is used instead of oleic acid.

[0071] According to the calculation, the content of 1-linoleyl-3-decanoyl diglyceride in the obtained composition is 33%, which is used to prepare a skin care emulsion loaded with tocotrienol, and the transdermal permeation rate of tocotrienol delivered through the skin is 7.51 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 150.91μg / cm 2 , the skin retention of tocotrienols in the dermis was 41.33 μg.

[0072] Comparative Example 13 This comparative example is the same as Example 1 except for the following technical features: the enzyme addition amount in step (1) is 5%.

[0073] According to calculation, the content of 1-oleoyl-3-decanoylglycerol diglyceride in the composition obtained in step (2) is 18%, and the composition is used to prepare a skin care emulsion loaded with tocotrienol. The transdermal permeation rate of tocotrienol delivered through the skin is 9.62 μg / cm 2 ·h, the cumulative permeation per unit area in 24 hours is 166.77μg / cm 2 , the skin retention of tocotrienols in the dermis was 31.03 μg.

[0074] Table 3 Comparative data of transdermal permeation performance of microemulsions made from products of the embodiments and comparative examples used in the present invention Table 4 Comparison of the retention effect of tocotrienol in the dermis of the microemulsions prepared from the products of the examples and the comparative examples Figure 1 The fluorescence diagrams of the transdermal penetration effects of some embodiments and comparative examples are shown, wherein the stronger the fluorescence intensity and the higher the depth, the higher the permeability and the better the skin absorption; conversely, the lower the permeability and the worse the skin absorption.

[0075] Conclusion: The present invention uses oleic acid and capric acid as raw materials, obtains diglyceride by specific enzymatic catalytic esterification, purifies by molecular distillation, and further separates and purifies by solvent method to control the ratio of 1-oleic acid-3-capric acid diglyceride in diglyceride, and prepares a base oil with improved transdermal absorption performance that can be used in skin care emulsions. Compared with traditional oils, the permeability and 24-hour permeation per unit area of ​​this oil are significantly improved when delivering tocotrienols, and the retention of tocotrienols delivered to the dermis is significantly increased.

[0076] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a skin care product base oil with transdermal absorption properties, characterized in that: The following steps are involved: (1) mixing oleic acid and capric acid and subjecting them to enzymatic specific esterification with glycerol, and obtaining a diglyceride composition after molecular distillation; (2) Obtaining oil rich in 1-oleyl-3-decanoylglycerol through a solvent purification method, that is, obtaining the skin care base oil with transdermal absorption properties.

2. The method for preparing a skin care base oil having transdermal absorption properties according to claim 1, characterized in that: In the enzymatic specific catalytic esterification described in step (1), the enzyme is one of lipase Lipozyme CALB, Lipozyme RMIM, Lipozyme TL IM or Lipozyme 435; the mass ratio of oleic acid to capric acid is 1:1-1:1.5, and the ratio of the total mass of oleic acid and capric acid to the mass of glycerol is 3.5:1-2:1; the amount of enzyme added is 1-3% of the total mass of oleic acid and capric acid, the temperature of the esterification reaction is 60-80°C, and the reaction time is 60-120 min.

3. The method for preparing a skin care base oil having transdermal absorption properties according to claim 1, characterized in that: The molecular distillation in step (1) obtains crude diglyceride in the light phase, and the diglyceride content is greater than 99%; The molecular distillation of step (1) is operated according to the following parameters: distillation temperature is 180-190°C, vacuum degree is 0.5-1.0 Pa, scraper speed is 150-200 rpm, condenser temperature is 30-50°C, and feed flow rate is ≤0.5 mL / min.

4. The method for preparing a skin care product base oil having transdermal absorption properties according to claim 1, characterized in that: The purification described in step (2) is a solvent purification, and the specific steps are: adding 8-20 times the weight of the crude product to the crude diglyceride with an organic reagent, wherein the organic solvent is n-hexane and ethyl acetate in a volume ratio of 90:10, and placing the system at 0-4°C for crystallization for more than 5 hours; using vacuum filtration to obtain a solid phase component, and after removing the organic reagent, obtaining a diglyceride composition rich in 1-oleo-3-decanoic acid diglyceride, that is, a skin care base oil with transdermal absorption properties.

5. The method for preparing a skin care product base oil having transdermal absorption properties according to claim 1, characterized in that: In the skin care base oil with transdermal absorption characteristics, the mass content of 1-oleyl-3-decanoyl diglyceride is greater than 20%.

6. A skin care base oil having transdermal absorption properties prepared according to the method according to any one of claims 1 to 5.

7. Use of the skin care base oil with transdermal absorption characteristics according to claim 6 in the preparation of transdermal absorption skin care products.

8. A skin care lotion with transdermal absorption properties, characterized in that The skin care product base oil with transdermal absorption characteristics is prepared according to claim 6, and also includes tocotrienol.

9. The skin care emulsion with transdermal absorption properties according to claim 8, characterized in that: In the emulsion, the base oil with transdermal absorption properties accounts for 4-8wt%; The mass of tocotrienol is 5-80wt% of the mass of the base oil having transdermal absorption characteristics.

10. The skin care emulsion with transdermal absorption properties according to claim 8 or 9, characterized in that: The prepared skin care emulsion has a transdermal permeation rate of tocotrienol>10.66 μg / cm 2 ·h, 24-hour cumulative permeation per unit area>172.41μg / cm 2 , the skin retention of tocotrienols in the dermis was >40.84 μg.

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