CN114886787B - Oil control essence and preparation method thereof - Google Patents
Oil control essence and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an oil control essence and a preparation method thereof, wherein the oil control essence comprises the following components in percentage by mass: 1 to 5 percent of rutin hydroxycinnamate, 1 to 13 percent of Leucasian willow herb and microzyme zinc fermentation compound, 1 to 17 percent of humectant, 1 to 9 percent of aromatic, 0.1 to 0.3 percent of chelating agent, 0.1 to 0.6 percent of preservative, 0.1 to 3.9 percent of skin conditioning agent, 0.1 to 0.3 percent of pH regulator and the balance of water, and adding the water into an emulsifying pot, heating, and adding the humectant and the chelating agent when preparing; cooling once, adding preservative and pH regulator, and stirring uniformly; and (3) cooling for the second time, adding a skin conditioner, rutin hydroxycinnamate, the Fulai willow herb and saccharomycete zinc fermentation complex and a flavoring agent, stirring, and filtering to obtain the oil control essence liquid. The invention has the advantages of inhibiting 5 alpha reductase, regulating sebaceous gland cell division and proliferation, realizing control of sebaceous gland secretion, reducing oil output, having good oil control effect and the like.
Description
Technical Field
The invention belongs to the technical field of essence, and particularly relates to an oil-control essence and a preparation method thereof.
Background
The total lipid content of human skin is generally 3.5-6.0% of the total weight of skin, and the skin is classified into oily skin, dry skin, neutral skin and mixed skin according to the amount of lipid on skin surface. The secretion function of sebaceous glands of oily skin is more vigorous, the face is greasy, the face is not easy to clean, the beautiful oily light is affected, and meanwhile, some corresponding skin diseases such as acne vulgaris, seborrheic dermatitis and the like are easy to occur. Thus, control of sebaceous gland secretion to reduce oil production is critical to maintaining healthy aesthetics of such skin.
After puberty begins, the sebaceous glands are again active under the control of androgens. The lipids of the skin surface consist mainly of three parts: sebum secreted by sebaceous glands, epidermal sebum formed by keratinocytes, and small amounts of lipids contaminated in vitro. The sebaceous gland of young people has vigorous secretion and high living and working pressure, so that the people with oily skin in the age group have high proportion, skin diseases caused by the dysfunction of grease secretion can be easily caused, and the beauty of the skin can be influenced. In order to achieve the purpose of controlling oil, people use some oil-controlling skin care products such as essence, wherein the essence contains active substances with oil-controlling effect, such as hydroxycinnamic acid, rutin, french willow herb, saccharomycete zinc and the like.
The salix volleyball is a perennial herb which grows in an open habitat. The stems are cylindrical, green, turn light red in autumn and are curved and soft. Is widely spread in tropical and temperate regions, but is abundant in the western north america; china is most abundant in the southwest. The Flemingiae leaf dish contains certain evening primrose element B. Oenotheran B is a macrocyclic dimeric ellagitannin and is commonly used in medical fields such as anti-tumor, anti-inflammatory, immunomodulating, antioxidant and antifungal. The evening primrose element B can permanently and permanently present the matte and oilless feel of the skin, restore the healthy appearance of the skin, shrink pores and make the skin cleaner and finer.
Rutin is also called rutin, and is a flavonoid compound widely existing in plants, and has molecular formula of C 27 H 30 O 16 Molecular weight: 610.51 it is crystallized in the form of pale yellow needles. It is soluble in pyridine, methanol and ethanol, is easily soluble in alkaline solution, is slightly soluble in ethyl acetate and acetone, and is hardly soluble in cold water. Rutin has two effects, one is the inhibition of microbial activity: has inhibiting effect on common pathogenic bacteria such as Staphylococcus aureus, escherichia coli, proteus, etc., and makes it possible to use it as natural plant extract for anti-infection treatment; secondly, has excellent antioxidation effect.
Hydroxy cinnamic acid is soluble in hot ether, hot ethanol, slightly soluble in benzene, insoluble in petroleum ether, and insoluble in water. It is a natural antioxidant existing in plants, can inhibit melanocyte activity, and can be used as whitening agent for skin care product.
The existing oil control essence is generally prepared by simply mixing four active substances of hydroxycinnamic acid, rutin, french willow leaf and saccharomycete zinc with other basic components in proportion, and the active substances have no reaction and only have intermolecular synergistic effect, so that the oil control effect is low. The hydroxy cinnamic acid, rutin and evening primrose extract B extracted from plants are generally extracted by water, and have the problem of low yield.
Disclosure of Invention
The invention aims to solve the problems in the background technology, and provides an oil control essence and a preparation method thereof, wherein the oil control essence can control the secretion of sebaceous glands to reduce oil production by adding a French willow leaf and saccharomycete zinc fermentation complex and hydroxy cinnamic acid rutin ester, inhibiting 5 alpha reductase and regulating sebaceous gland cell division and proliferation, and has good oil control effect.
In order to achieve the aim, the invention provides an oil control essence, which comprises the following components in percentage by mass: 1-5% of rutin hydroxycinnamate, 1-13% of a fermentation compound of the leaf of Flemingiae and saccharomycete zinc, 1-17% of a humectant, 1-9% of a flavoring agent, 0.1-0.3% of a chelating agent, 0.1-0.6% of a preservative, 0.1-3.9% of a skin conditioning agent, 0.1-0.3% of a pH regulator and the balance of water, wherein the rutin hydroxycinnamate is generated by the fermentation reaction of rutin and hydroxycinnamate through a first saccharomycete, and the fermentation compound of the leaf of Flemingiae and saccharomycete zinc is generated by the reaction of the evening primrose element B, a second saccharomycete and a zinc compound.
Preferably, the rutin hydroxycinnamate is prepared by the following preparation method:
drying plants containing rutin and hydroxycinnamic acid, and pulverizing;
placing plant powder into a subcritical fluid extraction device, adding water and polyalcohol, extracting at 40-60 ℃ and 0.3-1.0 MPa, and filtering to obtain an extract containing rutin and hydroxycinnamic acid;
adding first saccharomycete into the extracting solution, fermenting, and filtering to obtain rutin hydroxycinnamate.
Preferably, the plant is buddleia, the mass ratio of the water to the polyol is 1:1-2, the mass ratio of the plant powder to the water is 1:6-12, the polyol is at least one of 1, 2-butanediol, 1, 2-hexanediol, 1, 2-pentanediol, 1, 3-propanediol, 1, 5-pentanediol, butanediol, propanediol, hexanediol, 1, 6-hexanediol and 2, 3-butanediol, and the extraction time is 20-60 min.
Preferably, the first saccharomycete is at least one of beer yeast, grape juice yeast, schizosaccharomyces, roux yeast, combined yeast and hansenula yeast, the mass ratio of the first saccharomycete to the extracting solution is 1:90-100, the fermentation is carried out at the temperature of 10-40 ℃ and the fermentation time is 10-50 h.
Preferably, the preparation method of the Fullechesnea willow leaf and saccharomycete zinc fermentation complex specifically comprises the following steps:
oven drying herba Salicariae Chamomillae, and pulverizing;
placing the powder of the salix volvatus into a pressure extraction device, adding water and polyalcohol, extracting at 90-140 ℃ and under the pressure of 0.5-1.0 MPa, and filtering to obtain an extract containing the evening primrose element B;
adding a second saccharomycete and a zinc compound into the extracting solution, fermenting, and filtering to obtain a willow leaf and saccharomycete zinc fermentation compound;
wherein the zinc compound is at least one of zinc amino acid, zinc sulfate, zinc chloride, zinc nitrate, zinc citrate, zinc gluconate, zinc stearate, zinc laurate and zinc myristate, and the mass ratio of the zinc compound to the extracting solution is 1:80-99.
Preferably, the ratio of the powder of the salix fraxinus to the water is 1:100-200, the ratio of the water to the polyalcohol is 1-2:5, the extraction time is 0.5-4 h, and the polyalcohol is at least one of 1, 2-butanediol, 1, 2-hexanediol, 1, 2-pentanediol, 1, 3-propanediol, 1, 5-pentanediol, butanediol, propanediol, hexanediol, 1, 6-hexanediol and 2, 3-butanediol.
Preferably, the second yeast is at least one of beer yeast, grape juice yeast, schizosaccharomyces, roux yeast, combined yeast and hansenula yeast, the mass ratio of the second yeast to the extracting solution is 1:99-200, the fermentation is carried out at the temperature of 10-40 ℃ and the fermentation time is 10-50 h.
Preferably, the humectant comprises at least one of polyethylene glycol-32, glycereth-26, allantoin, octyl hydroxamic acid, phytosphingosine, panthenol ethyl ether, glycerin, butylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 2-hexanediol, 1, 2-pentanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, 2, 3-butanediol, propanediol, hexanediol, C20-22 alcohol, hyaluronic acid, acetylated sodium hyaluronate, hydrolyzed hyaluronic acid, tremella polysaccharide, and the chelating agent comprises at least one of disodium glutamate diacetate, disodium EDTA, trisodium EDTA, tetrasodium EDTA, disodium EDTA calcium, tripotassium EDTA, dipotassium EDTA, trisodium HEDTA, hydroxyethyl ethylenediamine triacetic acid, and hydroxyethyl diphosphate.
Preferably, the preservative comprises at least one of octanoyl hydroxamic acid, phenoxyethanol, sodium benzoate, potassium sorbate, sorbic acid, sodium sorbate, p-hydroxyacetophenone, ethylhexyl glycerol, and dehydroacetic acid, the pH adjuster comprises at least one of citric acid, arginine, sodium citrate, potassium citrate, succinic acid, tartaric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sebacic acid, the skin conditioner comprises at least one of glyceroglycosides, herba Portulacae extract, rhizoma Polygonati Odorati extract, rosewood seed extract, saw palmetto extract, neem leaf extract, neem flower extract, lactobacillus fermentation product, rhizoma Zingiberis recens extract, and herba Salvia officinalis leaf extract, and the aromatic comprises at least one of jasmine flower water, egypt blue water, lily flower water, chamomile flower water, herba Verbenae flower water, orange flower water, lavender flower water, and lotus flower water.
The invention also provides a preparation method of the oil control essence, which comprises the following steps:
adding water into an emulsifying pot, heating to 75-85 ℃, adding a humectant and a chelating agent, and stirring until the water is dissolved and transparent;
cooling to 63-68 deg.c, adding preservative and pH regulator and stirring;
cooling to 43-48 ℃, adding skin conditioner, rutin hydroxy cinnamate, french willow leaf and saccharomycete zinc fermentation complex and aromatic, preserving heat and stirring at 35-45 ℃, and filtering to obtain the oil control essence liquid.
The invention has the beneficial effects that: according to the invention, the Frietschet willow leaf, the saccharomycete zinc fermentation complex and the hydroxy cinnamic acid rutin ester are added into the oil control precision liquid to realize synergistic effect, and through a certain proportion, 5 alpha reductase can be effectively inhibited, sebaceous gland cell division and proliferation can be regulated, so that the oil control effect is optimized.
The features and advantages of the present invention will be described in detail by way of example with reference to the accompanying drawings.
Drawings
Fig. 1 is a flowchart of a process for preparing an essence according to an embodiment of the present invention.
FIG. 2 is a graph showing the comparison of OD values after use of various reagents for sebaceous cells according to examples of the present invention.
FIG. 3 is a flow chart of a process for preparing rutin hydroxycinnamate in accordance with an embodiment of the present invention.
FIG. 4 is a schematic representation of the structural formula of rutin hydroxycinnamate ester of an embodiment of the present invention.
FIG. 5 is a flow chart of a process for preparing a fermentation complex of French willow herb and yeast zinc in an embodiment of the invention.
FIG. 6 is a schematic representation of the structural formula of the fermentation complex of French willow herb and yeast zinc in the example of the present invention.
Detailed Description
The invention provides an oil control essence, which comprises the following components in percentage by mass: 1 to 5 percent of rutin hydroxycinnamate, 1 to 13 percent of Leucasian willow leaf and saccharomycete zinc fermentation compound, 1 to 17 percent of humectant, 1 to 9 percent of aromatic, 0.1 to 0.3 percent of chelating agent, 0.1 to 0.6 percent of preservative, 0.1 to 3.9 percent of skin conditioner, 0.1 to 0.3 percent of pH regulator and the balance of water, wherein the rutin hydroxycinnamate is generated by the fermentation reaction of rutin and hydroxycinnamate through a first saccharomycete, and the Leucasian willow leaf and saccharomycete zinc fermentation compound is generated by the reaction of evening primrose element B, a second saccharomycete and zinc compound.
The humectant comprises at least one of polyethylene glycol-32, glycerol polyether-26, allantoin, octyl hydroxamic acid, phytosphingosine, panthenol ethyl ether, glycerol, butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 2-hexanediol, 1, 2-pentanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, 2, 3-butanediol, propylene glycol, hexanediol, C20-22 alcohol, hyaluronic acid, acetylated sodium hyaluronate, hydrolyzed hyaluronic acid, and tremella polysaccharide, and the chelating agent comprises at least one of disodium glutamate diacetate, trisodium EDTA, tetrasodium EDTA, disodium EDTA calcium, tripotassium EDTA, dipotassium EDTA, trisodium HEDTA, hydroxyethyl ethylenediamine triacetic acid, and hydroxyethyl diphosphate.
The preservative comprises at least one of octanoyl hydroxamic acid, phenoxyethanol, sodium benzoate, potassium sorbate, sorbic acid, sodium sorbate, p-hydroxyacetophenone, ethylhexyl glycerol, and dehydroacetic acid, the pH regulator comprises at least one of citric acid, arginine, sodium citrate, potassium citrate, succinic acid, tartaric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sebacic acid, the skin conditioner comprises at least one of glyceroglycosides, herba Portulacae extract, rhizoma Polygonati Odorati extract, rosewood seed extract, semen Caesalpiniae extract, neem leaf extract, neem flower extract, lactobacillus fermentation product, rhizoma Zingiberis recens extract, and herba Salvia officinalis leaf extract, and the aromatic comprises at least one of jasmine flower water, egyptian blue water lily flower water, white flower chamomile flower water, herba Verbenae flower water, bitter orange flower water, lavender flower water, and lotus flower water.
Referring to fig. 3 and 4, the above rutin hydroxycinnamate is specifically prepared by the following preparation method:
s01, drying plants containing rutin and hydroxycinnamic acid components at the temperature of 60-100 ℃, and crushing;
s02, placing plant powder into a subcritical fluid extraction device, adding water and polyalcohol, extracting at 40-60 ℃ and under the pressure of 0.3-1.0 MPa, and filtering to obtain an extract containing rutin and hydroxycinnamic acid;
s03, adding first saccharomycetes into the extracting solution, fermenting, and filtering to obtain rutin hydroxycinnamate.
Wherein the plant is buddleia, the mass ratio of water to polyol is 1:1-2, the mass ratio of plant powder to water is 1:6-12, the polyol is at least one of 1, 2-butanediol, 1, 2-hexanediol, 1, 2-pentanediol, 1, 3-propanediol, 1, 5-pentanediol, butanediol, propanediol, hexanediol, 1, 6-hexanediol and 2, 3-butanediol, and the extraction time is 20-60 min.
The first saccharomycete is at least one of beer yeast, grape juice yeast, schizosaccharomyces, roux yeast, combined yeast and hansenula yeast, the mass ratio of the first saccharomycete to the extracting solution is 1:90-100, the fermentation is carried out at the temperature of 10-40 ℃ for 10-50 h.
Subcritical extraction device carries out subcritical fluid extraction to buddleia flower, and subcritical fluid adopts polyol aqueous solution (polyol and water mixed solution), and polyol aqueous solution is as extractant, and according to the principle that organic matter is similar to be compatible, through buddleia flower and the molecular diffusion process of polyol aqueous solution in the soaking process, active ingredient rutin and hydroxycinnamic acid in buddleia flower leaf are transferred to liquid polyol aqueous solution, finally realizes the high-efficient extraction of rutin and hydroxycinnamic acid. Subcritical extraction has the following advantages: is nontoxic, harmless, environment-friendly, pollution-free, and can retain active components of flos Buddlejae extract (rutin and hydroxycinnamic acid) without destruction.
The subcritical fluid extraction process is adopted to extract plants containing rutin and hydroxycinnamic acid components, and the subcritical fluid adopts a polyalcohol aqueous solution, so that the yield of rutin and hydroxycinnamic acid can be effectively improved, and the bioactivity is reserved; the rutin and the hydroxy cinnamic acid are prepared into hydroxy cinnamic acid rutin ester by adopting a biological fermentation technology, and the molecular synergistic effect of the hydroxy cinnamic acid rutin ester is utilized to reduce the quantity of sebum, improve the quality of sebum and reduce skin inflammation, so that the skin oil control effect is good.
Referring to fig. 5 and 6, the above-mentioned fermentation complex of the willow leaf and the yeast zinc is specifically prepared by the following preparation method:
s01, drying the Fulai willow herb and crushing;
s02, placing the powder of the salix volvatus into a pressurized extraction device, adding water and polyalcohol, extracting at the temperature of 90-140 ℃ and under the pressure of 0.5-1.0 MPa, and filtering to obtain an extract containing the evening primrose element B;
s03, adding a second saccharomycete and a zinc compound into the extracting solution, fermenting, and filtering to obtain a willow leaf and saccharomycete zinc fermentation compound;
wherein the zinc compound is at least one of zinc amino acid, zinc sulfate, zinc chloride, zinc nitrate, zinc citrate, zinc gluconate, zinc stearate, zinc laurate and zinc myristate, and the mass ratio of the zinc compound to the extracting solution is 1:80-99.
Wherein the mass ratio of the powder of the salix volvatus to the water is 1:100-200, the mass ratio of the water to the polyalcohol is 1-2:5, the extraction time is 0.5-4 h, and the polyalcohol is at least one of 1, 2-butanediol, 1, 2-hexanediol, 1, 2-pentanediol, 1, 3-propanediol, 1, 5-pentanediol, butanediol, propanediol, hexanediol, 1, 6-hexanediol and 2, 3-butanediol.
The second saccharomycete is at least one of beer saccharomycete, grape juice saccharomycete, schizosaccharomyces, roux saccharomycetes, combined saccharomycete and hansenula polymorpha, the mass ratio of the second saccharomycete to the extracting solution is 1:99-200, the fermentation is carried out at the temperature of 10-40 ℃ for 10-50 h.
The pressurizing extraction process is adopted to extract the salix volvulus, so that the yield of the evening primrose element B in the extracting solution is effectively improved; the method comprises the steps of mixing the oenothera philoxeroides extract containing the evening primrose element B, saccharomycetes and zinc compounds, and performing biological fermentation reaction to obtain the oenothera philoxeroides and saccharomycetes zinc fermentation compound.
Referring to fig. 1, the invention further provides a preparation method of the oil control essence, which comprises the following steps:
s01, adding water into an emulsifying pot, heating to 75-85 ℃, adding a humectant and a chelating agent, and stirring until the water is dissolved and transparent;
s02, cooling to 63-68 ℃, adding a preservative and a pH regulator, and uniformly stirring;
s03, cooling to 43-48 ℃, adding skin conditioner, rutin hydroxycinnamate, fuleyball willow herb and saccharomycete zinc fermentation complex and aromatic, preserving heat and stirring at 35-45 ℃, and filtering to obtain the oil control essence liquid.
The invention is further illustrated by the following specific examples, which are given solely for the purpose of illustration and are not intended to be limiting:
example 1
The embodiment provides an oil control essence, which comprises the following components in percentage by mass: 1% of rutin hydroxycinnamate, 1% of a fermentation compound of the salix volvulus and saccharomycete zinc, 1% of glycerol, 1% of jasmine flower water, 0.1% of tetrasodium glutamate diacetate, 0.1% of octanoyl hydroxamic acid, 0.1% of purslane extract, 0.1% of citric acid and 95.6% of water, wherein the rutin hydroxycinnamate is generated by the fermentation reaction of rutin and hydroxycinnamate by a first saccharomycete, and the fermentation compound of the salix volvulus and saccharomycete zinc is generated by the reaction of evening primrose element B, a second saccharomycete and a zinc compound.
In this embodiment, the preparation method of the oil control essence comprises the following steps:
s01, adding water into an emulsifying pot, heating to 85 ℃, then adding glycerol and tetrasodium glutamate diacetate, and stirring until the water is dissolved and transparent;
s02, cooling to 65 ℃, adding octanoyl hydroxamic acid and citric acid, and stirring for 5min until uniform;
s03, cooling to 45 ℃, adding purslane extract, rutin hydroxycinnamate, fulai willow herb and saccharomycete zinc fermentation complex, and jasmine flower water, preserving heat and stirring for 10 minutes at the temperature of 45 ℃, and filtering to obtain the oil control essence.
Example 2
The embodiment provides an oil control essence, which comprises the following components in percentage by mass: 5% of rutin hydroxycinnamate, 13% of a fermentation compound of the salix volvulus and the microzyme zinc, 17% of 1, 2-butanediol, 9% of water of Egyptian blue water lily, 0.3% of EDTA disodium, 0.3% of succinic acid, 3.9% of glyceroglycosides, 0.6% of phenoxyethanol and 50.9% of water, wherein the rutin hydroxycinnamate is generated by the fermentation reaction of rutin and hydroxycinnamate by a first microzyme, and the fermentation compound of the salix volvulus and the microzyme zinc is generated by the reaction of evening primrose element B, a second microzyme and a zinc compound.
In this embodiment, the preparation method of the oil control essence comprises the following steps:
s01, adding water into an emulsifying pot, heating to 75 ℃, then adding 1, 2-butanediol and EDTA disodium, and stirring until the water is dissolved and transparent;
s02, cooling to 65 ℃, adding phenoxyethanol and succinic acid, and stirring for 30min until uniformity;
s03, cooling to 45 ℃, adding glyceroglycosides, rutin hydroxycinnamate, french willow herb and saccharomycete zinc fermentation complex and Egypt blue water lily flower water, preserving heat and stirring for 30 minutes at 35 ℃, and filtering to obtain the oil control essence.
Example 3
The embodiment provides an oil control essence, which comprises the following components in percentage by mass: 3% of rutin hydroxycinnamate, 7% of Fullechesnea and saccharomycete zinc fermentation compound, 9% of 1, 2-pentanediol, 5% of lily water, 0.2% of EDTA trisodium, 0.2% of tartaric acid, 2% of polygonatum extract, 0.3% of sodium benzoate and 73.3% of water, wherein the rutin hydroxycinnamate is generated by the fermentation reaction of rutin and hydroxycinnamate by the first saccharomycete, and the Fullechesnea and saccharomycete zinc fermentation compound is generated by the reaction of evening primrose element B, the second saccharomycete and zinc compound.
In this embodiment, the preparation method of the oil control essence comprises the following steps:
s01, adding water into an emulsifying pot, heating to 80 ℃, then adding 1, 2-pentanediol and trisodium EDTA, and stirring until the solution is transparent;
s02, cooling to 65 ℃, adding sodium benzoate and tartaric acid, and stirring for 18min until uniform;
s03, cooling to 45 ℃, adding the polygonatum extract, the rutin hydroxycinnamate, the Fulai willow herb and saccharomycete zinc fermentation complex, and the lily water, preserving heat and stirring for 20 minutes at the temperature of 40 ℃, and filtering to obtain the oil control essence liquid.
The rutin hydroxycinnamates mentioned in examples 1 to 3 were prepared as follows:
s01, drying the buddleia flower leaves at the temperature of 60 ℃ and crushing;
s02, placing buddleia pollen powder into a subcritical fluid extraction device, adding water and 1, 2-butanediol, setting the temperature and pressure values of the subcritical fluid extraction device to be 40 ℃ and 1.0MPa respectively, extracting for 60 minutes under the temperature and pressure conditions, and filtering to obtain an extract containing rutin and hydroxycinnamic acid, wherein the mass ratio of buddleia pollen to water to 1, 2-butanediol is 1:8:16;
s03, adding beer yeast into the extracting solution, fermenting for 24 hours at the temperature of 40 ℃, and filtering to obtain a 1, 2-butanediol aqueous solution of the rutin hydroxycinnamate, wherein the mass ratio of the extracting solution to the beer yeast is 100:1.
The preparation method of the fermentation complexes of the Flemingian willow herb and the saccharomycete zinc mentioned in examples 1 to 3 comprises the following steps:
s01, drying flowers, leaves and stems of the salix volvulus at 60 ℃ and crushing;
s02, placing the powder of the salix fraxinus into a pressurized extraction device, adding water and 1, 2-butanediol according to a proportion, setting the temperature and pressure values of the pressurized extraction device to be 90 ℃ and 1.0MPa respectively, extracting for 0.5h under the temperature and pressure conditions, and filtering to obtain an extract containing the evening primrose extract B, wherein the mass ratio of the powder of the salix fraxinus, the water and the 1, 2-butanediol is 1:100:500;
s03, adding brewer's yeast and zinc amino acid into the extracting solution, fermenting for 50 hours at the temperature of 10 ℃, and filtering to obtain the fermentation compound of the willow leaf and the zinc saccharomycete, wherein the mass ratio of the extracting solution to the brewer's yeast to the zinc amino acid is 200:1:2.5.
Experiments on the effect of rutin hydroxycinnamate, salix fraichi and zymotic zinc complex on skin lipid content:
dividing human sebaceous gland cells into six groups, respectively using equivalent amounts of product A (purified water), product B (isotretinoin), product C (oil control essence containing rutin ester hydroxycinnamate, fu's willow leaf and yeast zinc fermentation complex), product D (oil control essence containing hydroxy cinnamic acid, rutin, fu's willow leaf and yeast zinc fermentation complex), product E (oil control essence containing rutin ester hydroxycinnamate complex) and product F (oil control essence containing Fu's willow leaf and yeast zinc fermentation complex), wherein product C, product D, product E and product F are oil control essence, and the rest components and proportion of the oil control essence are the same except the components in brackets are different, and then placing the six groups of cells at the same 37 ℃ and 5% CO 2 Biochemical culture is carried out for 24 hours under the condition, then PBS is used for cleaning, oil red O working solution is added, light-shielding dyeing is carried out for 15min, PBS is used for washing for 2 times, the oil red O dyeing working solution is removed, PBS is used for rinsing 3 times, isopropanol is added, an enzyme-labeled instrument is used for detecting absorbance, and OD values in each group of cells are recorded, wherein the specific detection results are shown in figure 2.
As can be seen from fig. 2, the OD value of the group of cells using isotretinoin is significantly lower than that of the group of cells using product a, and the lipid content is significantly reduced, which indicates that the positive control detection is effective;
the OD value of the four groups of cells using the oil control essence is lower than that of the group of cells using the product A, so that the lipid content is reduced, and the oil control essence can reduce lipid drop synthesis; the OD values of the cells of each group of products D, E, F and C are sequentially reduced, and compared with the oil control essence containing single components of the rutin hydroxycinnamate, the Fu's willow leaf and the yeast zinc fermentation complex, the oil control essence containing the rutin hydroxycinnamate, the Fu's willow leaf and the yeast zinc fermentation complex has better oil control effect than the traditional oil control essence (the rutin, the Fu's willow leaf and the yeast zinc fermentation product), so that the rutin hydroxycinnamate, the Fu's willow leaf and the yeast zinc fermentation complex have synergistic effect and improve the oil control effect.
The higher the OD in this experiment, the higher the lipid content.
OD is an abbreviation for optical density, which may also be referred to as absorbance. Absorbance refers to the use of the absorption spectrum specific to a substance to identify the substance or to determine the content of the substance, i.e., passing a beam of light of a specific wavelength through the object to be detected, which absorbs a portion of the light, and calculating the concentration of the object to be detected from the absorbance. Generally, the higher the concentration of the analyte, the higher the absorbance value. The detection object in the experiment is the lipid drop content of sebaceous gland cells, and the change condition of the OD value is the same as the change trend of the lipid drop content.
Isotretinoin is an isomer of all-trans retinoic acid, and has the main pharmacological activity of inhibiting sebaceous gland differentiation and sebum production, and is mainly used for treating acne, severe facial seborrhea, psoriasis and certain keratinized skin diseases clinically.
The above embodiments are illustrative of the present invention, and not limiting, and any simple modifications of the present invention fall within the scope of the present invention.
Claims (7)
1. An oil control essence liquid is characterized in that: the oil control essence consists of the following components in percentage by mass: 1-5% of rutin hydroxycinnamate, 1-13% of a fermentation compound of the leaf of Flemingiae and saccharomycete zinc, 1-17% of a humectant, 1-9% of a flavoring agent, 0.1-0.3% of a chelating agent, 0.1-0.6% of a preservative, 0.1-3.9% of a skin conditioning agent, 0.1-0.3% of a pH regulator and the balance of water, wherein the rutin hydroxycinnamate is generated by the fermentation reaction of rutin and hydroxycinnamate through a first saccharomycete, and the fermentation compound of the leaf of Flemingiae and saccharomycete zinc is generated by the reaction of evening primrose element B, a second saccharomycete and a zinc compound;
the rutin hydroxy cinnamate is prepared by the following steps:
drying plants containing rutin and hydroxycinnamic acid, and pulverizing;
placing plant powder into a subcritical fluid extraction device, adding water and polyalcohol, extracting at 40-60 ℃ and 0.3-1.0 MPa, and filtering to obtain an extract containing rutin and hydroxycinnamic acid;
adding a first saccharomycete into the extracting solution, fermenting and filtering to obtain rutin hydroxycinnamate;
the plant is buddleia, the mass ratio of the water to the polyalcohol is 1:1-2, the mass ratio of the plant powder to the water is 1:6-12, the polyalcohol is at least one of butanediol, propylene glycol, hexanediol, 1, 2-pentanediol and 1, 5-pentanediol, the extraction time is 20-60 min, the first saccharomycete is at least one of brewer's yeast, grape juice yeast, schizosaccharomyces, roux, saccharomyces cerevisiae and hansenula, the mass ratio of the first saccharomycete to the extract is 1:90-100, the fermentation is carried out at the temperature of 10-40 ℃ for 10-50 h;
the preparation method of the Fuleys willow leaf and saccharomycete zinc fermentation compound specifically comprises the following steps:
oven drying herba Salicariae Chamomillae, and pulverizing;
placing the powder of the salix volvatus into a pressure extraction device, adding water and polyalcohol, extracting at 90-140 ℃ and under the pressure of 0.5-1.0 MPa, and filtering to obtain an extract containing the evening primrose element B;
adding a second saccharomycete and a zinc compound into the extracting solution, fermenting, and filtering to obtain a willow leaf and saccharomycete zinc fermentation compound;
the zinc compound is at least one of zinc amino acid, zinc sulfate, zinc chloride, zinc nitrate, zinc citrate, zinc gluconate, zinc stearate, zinc laurate and zinc myristate, the mass ratio of the zinc compound to the extracting solution is 1:80-99, the mass ratio of the Fulai willow powder to water is 1:100-200, the mass ratio of water to polyalcohol is 1-2:5, the extracting time is 0.5-4 h, and the polyalcohol is at least one of 1, 2-pentanediol, 1, 5-pentanediol, butanediol, propanediol and hexanediol; the second saccharomycete is at least one of beer yeast, grape juice yeast, schizosaccharomyces, roux yeast, combined yeast and hansenula yeast, the mass ratio of the second saccharomycete to the extracting solution is 1:99-200, the fermentation is carried out at the temperature of 10-40 ℃ for 10-50 h.
2. The oil control concentrate of claim 1, wherein: the butanediol adopted in the preparation of the rutin hydroxycinnamate is 1, 2-butanediol or 2, 3-butanediol, the propylene glycol is 1, 3-propanediol, and the hexanediol is 1, 2-hexanediol or 1, 6-hexanediol.
3. The oil control concentrate of claim 1, wherein: the butanediol adopted in the preparation of the Leisha ferox and microzyme zinc fermentation complex is 1, 2-butanediol or 2, 3-butanediol, the propylene glycol is 1, 3-propanediol, and the hexanediol is 1, 2-hexanediol or 1, 6-hexanediol.
4. The oil control concentrate of claim 1, wherein: the humectant comprises at least one of polyethylene glycol-32, glycereth-26, allantoin, octyl hydroxamic acid, phytosphingosine, panthenol ethyl ether, glycerin, butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 9-nonanediol, propylene glycol, hexanediol, C20-22 alcohol, hyaluronic acid, sodium hyaluronate, hydrolyzed hyaluronic acid and tremella polysaccharide, and the chelating agent comprises at least one of tetrasodium glutamate diacetate, disodium EDTA, trisodium EDTA, tetrasodium EDTA, disodium calcium EDTA, tripotassium EDTA, dipotassium EDTA, trisodium HEDTA, hydroxyethyl ethylenediamine triacetic acid and hydroxyethyl diphosphate.
5. The oil control concentrate of claim 4, wherein: the propylene glycol adopted in the humectant is 1, 3-propylene glycol, the butanediol is at least one of 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol or 2, 3-butanediol, and the hexanediol is 1, 2-hexanediol or 1, 6-hexanediol.
6. The oil control concentrate of claim 1, wherein: the preservative comprises at least one of octanoic acid, phenoxyethanol, sodium benzoate, potassium sorbate, sorbic acid, sodium sorbate, p-hydroxyacetophenone, ethylhexyl glycerol, dehydroacetic acid, the pH regulator comprises at least one of citric acid, arginine, sodium citrate, potassium citrate, succinic acid, tartaric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, sebacic acid, the skin conditioner comprises at least one of glyceroglycosides, purslane extract, rhizoma Polygonati Odorati extract, rosewood seed extract, saw palmetto extract, neem leaf extract, neem flower extract, lactobacillus fermentation product, ginger root extract, and sage leaf extract, and the aromatic comprises at least one of jasmine flower water, egypt blue water lily flower water, chamomile flower water, verbena flower water, bitter orange flower water, lavender flower water, and lotus flower water.
7. A process for preparing the oil control concentrate according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
adding water into an emulsifying pot, heating to 75-85 ℃, adding a humectant and a chelating agent, and stirring until the water is dissolved and transparent;
cooling to 63-68 deg.c, adding preservative and pH regulator and stirring;
cooling to 43-48 ℃, adding skin conditioner, rutin hydroxy cinnamate, french willow leaf and saccharomycete zinc fermentation complex and aromatic, preserving heat and stirring at 35-45 ℃, and filtering to obtain the oil control essence liquid.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188517A (en) * | 1995-01-10 | 1996-07-23 | Kanebo Ltd | Sebum secretion inhibitor |
| BR102017003319A2 (en) * | 2017-02-17 | 2018-10-30 | Brainfarma Industria Quim E Farmaceutica S A | seborregulatory complex, topical composition, use of a seborregulatory complex and method of treating acne or dandruff |
| CN110711148A (en) * | 2019-11-03 | 2020-01-21 | 广州悦荟化妆品有限公司 | Face mask with skin oil balancing effect |
| CN111053728A (en) * | 2020-01-15 | 2020-04-24 | 广州极男化妆品有限公司 | Composition for regulating water-oil balance of skin and cosmetic thereof |
| CN111202700A (en) * | 2020-02-26 | 2020-05-29 | 广州环亚化妆品科技有限公司 | Composition for reducing skin purpurin and preparation method and application thereof |
| CN113116761A (en) * | 2019-12-30 | 2021-07-16 | 湖南御家化妆品制造有限公司 | Oil control composition, application thereof and oil control nursing membrane |
| CN113208960A (en) * | 2021-05-06 | 2021-08-06 | 科丝美诗(中国)化妆品有限公司 | Skin care composition for controlling oil and repairing skin barrier and preparation method and application thereof |
-
2022
- 2022-06-02 CN CN202210620976.3A patent/CN114886787B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188517A (en) * | 1995-01-10 | 1996-07-23 | Kanebo Ltd | Sebum secretion inhibitor |
| BR102017003319A2 (en) * | 2017-02-17 | 2018-10-30 | Brainfarma Industria Quim E Farmaceutica S A | seborregulatory complex, topical composition, use of a seborregulatory complex and method of treating acne or dandruff |
| CN110711148A (en) * | 2019-11-03 | 2020-01-21 | 广州悦荟化妆品有限公司 | Face mask with skin oil balancing effect |
| CN113116761A (en) * | 2019-12-30 | 2021-07-16 | 湖南御家化妆品制造有限公司 | Oil control composition, application thereof and oil control nursing membrane |
| CN111053728A (en) * | 2020-01-15 | 2020-04-24 | 广州极男化妆品有限公司 | Composition for regulating water-oil balance of skin and cosmetic thereof |
| CN111202700A (en) * | 2020-02-26 | 2020-05-29 | 广州环亚化妆品科技有限公司 | Composition for reducing skin purpurin and preparation method and application thereof |
| CN113208960A (en) * | 2021-05-06 | 2021-08-06 | 科丝美诗(中国)化妆品有限公司 | Skin care composition for controlling oil and repairing skin barrier and preparation method and application thereof |
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