阅读说明：本技术 一种生物质蜂窝状半透膜、保湿纳米明胶微球、口红及其制备方法 (Biomass honeycomb semipermeable membrane, moisturizing nano gelatin microspheres, lipstick and preparation method thereof ) 是由 王立惠 吴博竞 耿小红 陈同祥 吴迎港 于 2021-06-30 设计创作，主要内容包括：本发明提供了一种生物质蜂窝状半透膜、保湿纳米明胶微球、口红及其制备方法,所述生物质蜂窝状半透膜的制备方法包括以下步骤：(1)将成膜材料、分散剂、纳米碳酸钙粒子与溶剂混合得到混合溶液,之后脱泡后流延成膜；(2)将步骤(1)得到的膜固化,之后用酸浸泡、醇活化,放入标准蛋白质溶液中吸附,得到所述生物质蜂窝状半透膜。本发明提供的口红温和无刺激,无毒可食用,能够缓慢释放保湿剂,实现对唇部的长久保湿。(The invention provides a biomass cellular semipermeable membrane, moisturizing nano gelatin microspheres, lipstick and a preparation method thereof, wherein the preparation method of the biomass cellular semipermeable membrane comprises the following steps: (1) mixing a film-forming material, a dispersing agent, nano calcium carbonate particles and a solvent to obtain a mixed solution, defoaming, and then casting to form a film; (2) solidifying the membrane obtained in the step (1), then soaking with acid, activating with alcohol, and putting into a standard protein solution for adsorption to obtain the biomass cellular semipermeable membrane. The lipstick provided by the invention is mild, non-irritant, non-toxic and edible, and can slowly release the humectant to realize long-term moisture retention of lips.)

1. The preparation method of the biomass honeycomb semipermeable membrane is characterized by comprising the following steps of:

(1) mixing a film forming material, a dispersing agent, nano calcium carbonate particles and a solvent to obtain a mixed solution, defoaming, and then casting to form a film;

(2) solidifying the membrane obtained in the step (1), then soaking with acid, activating with alcohol, and putting into a standard protein solution for adsorption to obtain the biomass cellular semipermeable membrane.

2. The method for preparing a biomass honeycomb semipermeable membrane according to claim 1, wherein the membrane forming material of step (1) comprises any one of PVDF, PVA, PMMA, PES or PAN, preferably PVDF;

preferably, the mass fractions of the film forming material, the dispersing agent and the nano calcium carbonate particles in the mixed solution in the step (1) are respectively 8-12%, 0.5-2% and 2-8%;

preferably, the dispersant of step (1) comprises any one of PAAS, PVP or NNO, preferably PAAS;

preferably, the solvent of step (1) comprises any one of DMAC, DCM or DMF;

preferably, the mixing in the step (1) further comprises stirring, wherein the stirring temperature is 50-80 ℃;

preferably, the ultrasonic treatment is carried out after the stirring, and the ultrasonic treatment time is 1-3 h;

preferably, the step (2) further comprises soaking in water after curing, wherein the soaking time is 24-48 h;

preferably, the concentration of the standard protein solution in the step (2) is 5-10 mg/mL.

3. The biomass honeycomb semipermeable membrane produced by the production method for a biomass honeycomb semipermeable membrane according to claim 1 or 2.

4. The moisturizing nano gelatin microsphere is characterized by being prepared by a preparation method comprising the following steps:

(1') using the biomass honeycomb semipermeable membrane of claim 3 as a reaction medium, and reacting a carbonate ion solution with a calcium ion solution to prepare nano calcium carbonate balls;

(2 ') mixing the nano calcium carbonate balls obtained in the step (1') with water for ultrasonic treatment, then mixing and stirring the mixture with a gelatin solution, then mixing and stirring the mixture with olive oil for cooling, and collecting gelatin balls precipitated at the bottom;

and (3 ') mixing and soaking the gelatin globule obtained in the step (2') with a solvent, then carrying out acid washing and alkali washing, and then soaking in a moisture retention agent to obtain the moisture retention nano gelatin microsphere.

5. The moisturizing nanogel as claimed in claim 4, wherein the operation method of step (1') comprises:

the biomass honeycomb-shaped semipermeable membrane according to claim 3 is placed in a container, the container is divided into two independent spaces, carbonate ion solution and calcium ion solution are added into the two independent spaces of the container respectively to react, and then the mixture is centrifuged and washed to obtain the nano calcium carbonate ball.

6. The moisturizing nanogel as claimed in claim 4 or 5, wherein the solute of the carbonate ion solution of step (1') comprises any one of sodium carbonate, potassium carbonate or sodium bicarbonate;

preferably, the solute of the calcium ion solution in step (1') comprises any one of calcium chloride, calcium nitrate or calcium hydroxide;

preferably, the molar ratio of carbonate ions to calcium ions in the carbonate ion solution and the calcium ion solution in step (1') is (0.9-1.1): (0.9-1.1).

7. The moisturizing nanogel microspheres according to any one of claims 4 to 6, wherein the mass ratio of the nanocalcium carbonate spheres, the gelatin solution and the olive oil in step (2') is (0.8-1.2): (1.8-2.2): (12-16);

preferably, the mass fraction of the gelatin solution in the step (2') is 4-6%;

preferably, the humectant of step (3') comprises any one of water-soluble plants such as squalane, hyaluronic acid, glycerol or ethylhexyl palmitate.

8. A lipstick, characterized by comprising, by weight, 10-20 parts of a coagulant, 8-15 parts of honey, 45-50 parts of a lubricant, 10-20 parts of a softening agent, 3-6 parts of a colorant, 1-5 parts of an antioxidant, and 3-6 parts of the moisturizing nano gelatin microspheres according to any one of claims 4-7.

9. A lipstick according to claim 8 wherein said solidifying agent comprises beeswax;

preferably, the emollient includes cetearyl isooctanoate;

preferably, the colorant comprises a plant toner;

preferably, the antioxidant comprises tocopherol;

preferably, the lubricant comprises natural vegetable oil, wherein the natural vegetable oil comprises 25-35 parts of coconut oil, 5-15 parts of camellia seed oil and 6-12 parts of rose essential oil in parts by weight.

10. A process for the preparation of a lipstick according to claim 8 or 9, characterized in that it comprises the following steps: mixing and stirring the coagulant and the honey, then mixing and melting the mixture with the lubricant and the emollient, then adding the colorant and the antioxidant, mixing and stirring, cooling, then adding the moisturizing nano gelatin microspheres of any one of claims 4-7, stirring, cooling and forming to obtain the lipstick.

Technical Field

The invention belongs to the field of cosmetics, and particularly relates to a biomass cellular semipermeable membrane, a moisturizing nano gelatin microsphere and lipstick and a preparation method thereof, and particularly relates to a biomass cellular semipermeable membrane, a moisturizing nano gelatin microsphere and lipstick capable of keeping moisture for a long time and a preparation method thereof.

Background

Lipstick is also called as lipstick, and is a pasty lip cosmetic. The lipstick can be used for outlining the lip shape, moistening and softening the lip and protecting the lip from drying crack, and belongs to the cosmetic type with very common use and great consumption. However, the lipstick is spread on the lips, and is inevitably swallowed into the abdomen, and the existing lipstick mainly comprises oil, wax, grease, colorant, antioxidant, preservative and the like, and the lipstick swallowed into the human body is inevitably harmful to the health of the human body after long-term storage. And because the oil wax has complex components, the lip skin is thin and has no cuticle protection, and the symptoms such as lip crack, swelling, itching, peeling, slight pain and the like are easily caused when the oil wax is used for a long time. With the improvement of the attention of people to skin health, the selection of natural, safe and effective cosmetic raw materials and additives becomes the direction of more and more cosmetic researches, and health and moisture preservation also become two key production factors of lipstick.

CN111067821A discloses a moisturizing lipstick containing a polysaccharide humectant and a preparation method thereof, wherein the moisturizing lipstick comprises the following raw materials in parts by weight: 12-20 parts of beeswax; 35-60 parts of vegetable oil; 4-9 parts of plant polysaccharide; 5-12 parts of plant extract pigment; 0.8-1.3 parts of vitamin E; wherein the plant polysaccharide consists of peach gum polysaccharide and polygonatum polysaccharide according to the mass ratio of 1: 1.0-2.0; the moisturizing lipstick containing the polysaccharide humectant is safe and reliable in components, simple in preparation method, capable of protecting lip skin while keeping the lips moist, and capable of providing beautiful colors for the lips. However, the amount of wax oil additives is large, the greasy feeling of the lipstick is increased, the excessive oil can reduce the using feeling of the lipstick and reduce the moisture of the lip, and the effect of long-term moisture retention cannot be achieved.

CN110638685A discloses an edible lipstick and a preparation method thereof, which comprises the following raw materials in parts by weight: 14-26 parts of natural vegetable oil, 4-6 parts of natural farmhouse beewax, 1.5-2 parts of plant natural pigment, 1-2 parts of Chinese date extract, 0.1-0.5 part of vitamin E, 0.05-0.3 part of vitamin B and 0.5-1 part of vitamin C. The lipstick prepared by the invention is safe to use, does not contain toxic and harmful substances, can be eaten, and has a nourishing effect on lips. However, the formula mainly comprises oil and wax, and is lack of moisture-keeping components, and the oil and wax components are complex, so that the lip skin is thin and has no cuticle protection, and the symptoms such as lip chapping, swelling, itching, peeling, slight pain and the like are easily caused after the lip is used for a long time.

The use of the lipstick is seriously affected by symptoms such as lip dryness, swelling, itching, peeling, slight pain and the like caused by the current lipstick formula. Therefore, how to provide the edible lipstick capable of preserving moisture for a long time becomes a problem to be solved urgently.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a biomass cellular semipermeable membrane, a moisturizing nano-gelatin microsphere and a lipstick and a preparation method thereof, and particularly provides a biomass cellular semipermeable membrane, a moisturizing nano-gelatin microsphere and a lipstick capable of lasting moisturizing and a preparation method thereof. The lipstick provided by the invention is mild, non-irritant, non-toxic and edible, and can slowly release the humectant to realize long-term moisture retention of lips.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a method for preparing a biomass honeycomb semipermeable membrane, comprising the steps of:

(1) mixing a film forming material, a dispersing agent, nano calcium carbonate particles and a solvent to obtain a mixed solution, defoaming, and then casting to form a film;

(2) solidifying the membrane obtained in the step (1), then soaking with acid, activating with alcohol, and putting into a standard protein solution for adsorption to obtain the biomass cellular semipermeable membrane.

The biomass cellular semipermeable membrane prepared by the specific preparation method can control the aperture of the semipermeable membrane by controlling preparation parameters, and calcium carbonate is formed by utilizing the reaction of calcium ions adsorbed by surface free amino acid groups and carbonate ions in the pore canal of the biomass cellular semipermeable membrane, so that the particle size of the obtained nano calcium carbonate ball is controlled, and the particle size of the prepared nano calcium carbonate ball is more uniform.

Preferably, the film forming material in step (1) includes any one of PVDF (polyvinylidene fluoride), PVA (polyvinyl alcohol), PMMA (polymethyl methacrylate), PES (polyethersulfone) or PAN (polyacrylonitrile), preferably PVDF.

Preferably, the mass fractions of the film forming material, the dispersing agent and the nano calcium carbonate particles in the mixed solution in the step (1) are respectively 8-12%, 0.5-2% and 2-8%.

Preferably, the dispersant in step (1) comprises any one of PAAS (sodium polyacrylate), PVP (polyvinylpyrrolidone) or NNO (sodium salt of 2-naphthalenesulfonic acid formaldehyde polymer), preferably PAAS.

Preferably, the solvent of step (1) comprises any one of DMAC (dimethylacetamide), DCM (dichloromethane) or DMF (N, N-dimethylformamide).

Preferably, the mixing in step (1) further comprises stirring, and the stirring temperature is 50-80 ℃.

Preferably, the stirring in step (1) is further followed by ultrasonic treatment, and the ultrasonic treatment time is 1-3 h.

Preferably, the curing in step (2) further comprises soaking in water for 24-48 h.

Preferably, the concentration of the standard protein solution in the step (2) is 5-10 mg/mL.

Wherein the mass fraction of the film forming material may be 8%, 9%, 10%, 11%, or 12%, the mass fraction of the dispersing agent may be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%, the mass fraction of the nano calcium carbonate particles may be 2%, 3%, 4%, 5%, 6%, 7%, or 8%, the temperature may be 50 ℃, 60 ℃, 70 ℃, or 80 ℃, the time of sonication may be 1h, 1.5h, 2h, 2.5h, or 3h, the soaking time may be 24h, 30h, 35h, 40h, 45h, or 48h, the concentration of the standard protein solution may be 5mg/mL, 6mg/mL, 7mg/mL, 8mg/mL, 9mg/mL, or 10mg/mL, but not limited to the above-mentioned values, other values not listed in the above numerical ranges are equally applicable.

The specific parameters can control the aperture size of the biomass honeycomb-shaped semi-permeable membrane, and further control the particle size of the nano calcium carbonate spheres prepared by using the biomass honeycomb-shaped semi-permeable membrane.

In a second aspect, the invention provides the biomass honeycomb semipermeable membrane prepared by the preparation method of the biomass honeycomb semipermeable membrane.

In a third aspect, the invention provides a moisturizing nano gelatin microsphere, which is prepared by a preparation method comprising the following steps:

(1') using the biomass cellular semipermeable membrane as a reaction medium, and reacting a carbonate ion solution with a calcium ion solution to prepare the nano calcium carbonate ball;

(2 ') mixing the nano calcium carbonate balls obtained in the step (1') with water for ultrasonic treatment, then mixing and stirring the mixture with a gelatin solution, then mixing and stirring the mixture with olive oil for cooling, and collecting gelatin balls precipitated at the bottom;

and (3 ') mixing and soaking the gelatin globule obtained in the step (2') with a solvent, then carrying out acid washing and alkali washing, and then soaking in a moisture retention agent to obtain the moisture retention nano gelatin microsphere.

According to the preparation method, the biomass honeycomb semipermeable membrane is used for preparing the nano calcium carbonate spheres with uniform particle sizes, and the moisturizing nano gelatin microspheres obtained through a series of reactions have a honeycomb structure, can contain the humectant, realize slow release of the humectant and play a long-term moisturizing role on lips.

Preferably, the operation method of step (1') includes:

the biomass honeycomb semipermeable membrane is placed in a container, the container is divided into two independent spaces, carbonate ion solution and calcium ion solution are respectively added into the two independent spaces of the container to react, and then the nano calcium carbonate ball is obtained through centrifugation and washing.

Preferably, the solute of the carbonate ion solution in step (1') comprises any one of sodium carbonate, potassium carbonate or sodium bicarbonate.

Preferably, the solute of the calcium ion solution in step (1') comprises any one of calcium chloride, calcium nitrate or calcium hydroxide.

Preferably, the molar ratio of carbonate ions to calcium ions in the carbonate ion solution and the calcium ion solution in step (1') is (0.9-1.1): (0.9-1.1).

Preferably, the mass ratio of the nano calcium carbonate balls, the gelatin solution and the olive oil in the step (2') is (0.8-1.2): (1.8-2.2): (12-16).

Preferably, the mass fraction of the gelatin solution in the step (2') is 4-6%.

In the molar ratio of carbonate ions to calcium ions, the carbonate ions may be 0.9, 0.95, 1, 1.05 or 1.1, the calcium ions may be 0.9, 0.95, 1, 1.05 or 1.1, the nano calcium carbonate spheres may be 0.8, 0.9, 1, 1.1 or 1.2, the gelatin solution may be 1.8, 1.9, 2, 2.1 or 2.2, the olive oil may be 12, 13, 14, 15 or 16, the gelatin solution may be 4%, 5% or 6%, etc., but the above-mentioned values are not limited thereto, and other values not listed in the above-mentioned range are also applicable.

Preferably, the humectant of step (3') comprises any one of water-soluble plants such as squalane, hyaluronic acid, glycerol or ethylhexyl palmitate.

In a fourth aspect, the invention provides a lipstick, which comprises, by weight, 10-20 parts of a coagulant, 8-15 parts of honey, 45-50 parts of a lubricant, 10-20 parts of a softening agent, 3-6 parts of a colorant, 1-5 parts of an antioxidant and 3-6 parts of the moisturizing nano gelatin microspheres.

Wherein, the parts of the coagulant can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, the parts of the honey can be 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, the parts of the lubricant can be 45 parts, 46 parts, 47 parts, 48 parts, 49 parts or 50 parts, the parts of the emollient can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, the parts of the colorant can be 3 parts, 4 parts, 5 parts or 6 parts, the parts of the antioxidant can be 1 part, 2 parts, 3 parts, 4 parts or 5 parts, the parts of the moisturizing nano gelatin microspheres can be 3 parts, 4 parts, 5 parts or 6 parts, and the like, but not limited to, the above-listed numerical values, and other numerical values not listed in the above numerical range are also applicable.

The lipstick adopts specific raw materials, reduces stimulation to human body, and solves the problem that the human body is injured by eating the lipstick by mistake; the specific moisturizing nanometer gelatin microspheres play a role in slowly releasing the moisturizing agent and have a long-term moisturizing effect on lips.

Preferably, the solidifying agent comprises beeswax.

Preferably, the emollient comprises cetearyl isooctanoate.

Preferably, the colorant comprises a plant toner.

Preferably, the antioxidant comprises tocopherol.

Preferably, the lubricant comprises natural vegetable oil, wherein the natural vegetable oil comprises 25-35 parts of coconut oil, 5-15 parts of camellia seed oil and 6-12 parts of rose essential oil by weight, wherein the coconut oil can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts or 35 parts, the camellia seed oil can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, the rose essential oil can be 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts or 12 parts, and the like, but is not limited to the above-listed values, and other values in the above-mentioned value range are also applicable.

In a fifth aspect, the present invention also provides a method for preparing a lipstick as described above, comprising the steps of: mixing and stirring the coagulator and the honey, then mixing and melting the coagulator, the lubricant and the emollient, then adding the colorant and the antioxidant, mixing and stirring, cooling, then adding the moisturizing nano gelatin microspheres, stirring, cooling and molding to obtain the lipstick.

Compared with the prior art, the invention has the following beneficial effects:

(1) according to the biomass cellular semipermeable membrane prepared by the specific preparation method, the size of the aperture of the semipermeable membrane can be controlled by controlling preparation parameters, calcium ions and carbonate ions are adsorbed by surface free amino acid groups and react in the pore canal of the biomass cellular semipermeable membrane to form calcium carbonate, so that the particle size of the obtained nano calcium carbonate spheres is controlled, and the particle size of the prepared nano calcium carbonate spheres is more uniform;

(2) according to the invention, the biomass honeycomb semipermeable membrane is used for preparing the nano calcium carbonate spheres with uniform particle size, and then the moisturizing nano gelatin microspheres obtained through a series of reactions have a honeycomb structure, can contain the humectant, realize slow release of the humectant and play a long-term moisturizing role on lips;

(3) the invention also provides the lipstick, which reduces the stimulation to the human body and solves the problem that the human body is injured by eating the lipstick by mistake by adopting the specific raw materials; the specific moisturizing nano gelatin microspheres play a role in slowly releasing the moisturizing agent and moisturizing the lips for a long time.

Detailed Description

To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

In the following examples, PVDF is available from Macklin under model number P875313;

PVA from Macklin, model P875084;

PMMA was purchased from Macklin, model P821345;

PVP was purchased from Macklin, model P816205;

NNO was purchased from Macklin, model S885855;

PAAS was purchased from Macklin under model number S817809;

the nano calcium carbonate particles are purchased from Shandong high-gloss biological technology company Limited and are food-grade nano calcium carbonate;

the plant toner is purchased from Zhengzhou Pettt, and has a model number of 74-79-3.

Preparation example 1

The preparation example provides a biomass honeycomb semipermeable membrane, and the preparation method comprises the following steps:

PVDF, PAAS and nano calcium carbonate particles are dissolved in DMAC (10%, 1% and 5% by mass respectively), stirred for 2 hours in a water bath at 70 ℃, then dissolved and dispersed by ultrasonic for 2 hours, and cast into a film after standing and defoaming, and then placed into a gel bath for curing, and soaked in distilled water for 36 hours after the film is automatically stripped. And then putting the PVDF membrane into 1mol/L diluted hydrochloric acid solution to be soaked for 4h to etch calcium carbonate particles in the PVDF membrane, and washing with deionized water to obtain the porous PVDF membrane. Soaking the porous PVDF membrane in absolute ethyl alcohol for 2 hours, activating positively charged groups on the PVDF membrane, and then putting the PVDF membrane into a standard protein solution (7mg/mL) for adsorption to obtain the biomass cellular semipermeable membrane.

Preparation example 2

The preparation example provides a biomass honeycomb semipermeable membrane, and the preparation method comprises the following steps:

PVDF, PAAS and nano calcium carbonate particles are dissolved in DMAC (8%, 0.5% and 2% by mass respectively), stirred for 3 hours in a water bath at 50 ℃, then ultrasonically treated for 1 hour for dissolving and dispersing, and cast into a film after standing and defoaming, the film is placed into a gel bath for curing, and the film is soaked in distilled water for 24 hours after being automatically stripped. And then putting the PVDF membrane into 1mol/L diluted hydrochloric acid solution to be soaked for 2h to etch calcium carbonate particles in the PVDF membrane, and washing with deionized water to obtain the porous PVDF membrane. Soaking the porous PVDF membrane in absolute ethyl alcohol for 1h, activating positively charged groups on the PVDF membrane, and then putting the PVDF membrane into a standard protein solution (5mg/mL) for adsorption to obtain the biomass cellular semipermeable membrane.

Preparation example 3

The preparation example provides a biomass honeycomb semipermeable membrane, and the preparation method comprises the following steps:

PVDF, PAAS and nano calcium carbonate particles are dissolved in DMAC (12%, 2% and 8% by mass respectively), stirred for 1h in a water bath at 80 ℃, then dissolved and dispersed by ultrasonic for 3h, and cast into a film after standing and defoaming, and then placed into a gel bath for curing, and soaked in distilled water for 48h after the film is automatically stripped. And then putting the PVDF membrane into 1mol/L diluted hydrochloric acid solution to be soaked for 3h to etch calcium carbonate particles in the PVDF membrane, and washing with deionized water to obtain the porous PVDF membrane. Soaking the porous PVDF membrane in absolute ethyl alcohol for 3 hours, activating positively charged groups on the PVDF membrane, and then putting the PVDF membrane into a standard protein solution (10mg/mL) for adsorption to obtain the biomass cellular semipermeable membrane.

Preparation example 4

The preparation example provides a biomass honeycomb semipermeable membrane, and the preparation method is the same as the preparation example 1 except that PVDF is replaced by PVA with the same amount.

Preparation example 5

The preparation example provides a biomass cellular semipermeable membrane, and the preparation method is the same as the preparation example 1 except that PVDF is replaced by PMMA with the same amount.

Preparation example 6

The preparation example provides a biomass cellular semipermeable membrane, and the preparation method is the same as the preparation example 1 except that the same amount of PVP is replaced by PAAS.

Preparation example 7

This preparation example provides a biomass cellular semipermeable membrane, and the preparation method is the same as preparation example 1 except that PAAS is replaced with NNO of the same amount.

Preparation example 8

The preparation example provides a biomass honeycomb semipermeable membrane, and the preparation method comprises the following steps:

PVDF, PAAS and nano calcium carbonate particles are dissolved in DMAC (5%, 0.1% and 1% by mass respectively), stirred for 4 hours in a water bath at 45 ℃, then ultrasonically treated for 0.5 hour to dissolve and disperse, and cast into a film after standing and defoaming, the film is placed into a gel bath to be cured, and the film is soaked in distilled water for 20 hours after being automatically stripped. And then putting the PVDF membrane into 1mol/L diluted hydrochloric acid solution to be soaked for 4h to etch calcium carbonate particles in the PVDF membrane, and washing with deionized water to obtain the porous PVDF membrane. Soaking the porous PVDF membrane in absolute ethyl alcohol for 2 hours, activating positively charged groups on the PVDF membrane, and then putting the PVDF membrane into a standard protein solution (7mg/mL) for adsorption to obtain the biomass cellular semipermeable membrane.

Preparation example 9

The preparation example provides a biomass honeycomb semipermeable membrane, and the preparation method comprises the following steps:

PVDF, PAAS and nano calcium carbonate particles are dissolved in DMAC (respectively 15%, 3% and 10% in mass fraction), stirred for 0.5h in a water bath at 90 ℃, then ultrasonically treated for 4h to dissolve and disperse, and cast into a membrane after standing and defoaming, and then placed into a gel bath to be cured, and the membrane is soaked in distilled water for 55h after being automatically stripped. And then putting the PVDF membrane into 1mol/L diluted hydrochloric acid solution to be soaked for 4h to etch calcium carbonate particles in the PVDF membrane, and washing with deionized water to obtain the porous PVDF membrane. Soaking the porous PVDF membrane in absolute ethyl alcohol for 2 hours, activating positively charged groups on the PVDF membrane, and then putting the PVDF membrane into a standard protein solution (7mg/mL) for adsorption to obtain the biomass cellular semipermeable membrane.

Example 1

The embodiment provides a moisturizing nano gelatin microsphere, and the preparation method comprises the following steps:

the biomass honeycomb semipermeable membrane obtained in production example 1 was fixed to a reactor, the reactor was divided into two parts, and an equal amount of Na was added₂CO₃Solution and CaCl₂The solution is respectively placed on two sides of a biomass honeycomb semipermeable membrane and reacts for 48 hours at the temperature of 25 ℃. Separating the product by a centrifugal separator at the rotating speed of 4000r/min, and washing the product by deionized water and ethanol to obtain nano calcium carbonate balls;

and adding 5 parts of the nano calcium carbonate balls obtained in the previous step into 150mL of deionized water, and carrying out ultrasonic treatment for 2 hours to obtain a calcium carbonate dispersion liquid. Adding gelatin particles into a mixed solution (volume ratio is 10:1) of deionized water and absolute ethyl alcohol at 50 ℃ in a water bath condition, preparing 10 parts of gelatin solution with the mass fraction of 5%, ensuring that the solution is in a flowing state at 50 ℃, adding calcium carbonate dispersion liquid, and stirring to mix the calcium carbonate dispersion liquid and the gelatin solution to obtain the calcium carbonate-gelatin mixed solution. Heating 70 parts of olive oil to 70 ℃, stirring and shearing at the speed of 2000r/min by using a high-speed shearing machine, dropwise adding the calcium carbonate-gelatin mixed solution, and continuously stirring for 20min after all the dropwise adding is finished. Then, the mixture is rapidly cooled by an ice bath under the state of keeping stirring, and the gelatin globules precipitated at the bottom are collected. And (3) adding the gelatin beads into 50 parts of mixed solution (volume ratio is 1:1) of glacial acetone and ethanol, soaking for 5 hours, and washing for 5 times by using deionized water and absolute ethyl alcohol to obtain the calcium carbonate-gelatin nano microspheres. Adding the microspheres into 1mol/L dilute hydrochloric acid solution, standing for 5h, respectively carrying out centrifugal washing on the microspheres for 5 times by using 0.5mol/L NaOH solution, deionized water and absolute ethyl alcohol, putting the microspheres into water-soluble plant squalane, soaking for 2h, and naturally drying to obtain the moisturizing nano gelatin microspheres.

Example 2

The embodiment provides a moisturizing nano gelatin microsphere, and the preparation method comprises the following steps:

the biomass honeycomb semipermeable membrane obtained in production example 1 was fixed to a reactor, the reactor was divided into two parts, and an equal amount of Na was added₂CO₃Solution and CaCl₂The solution is respectively placed on two sides of a biomass honeycomb semipermeable membrane and reacts for 48 hours at the temperature of 25 ℃. Separating the product by a centrifugal separator at the rotating speed of 4000r/min, and washing the product by deionized water and ethanol to obtain nano calcium carbonate balls;

and adding 4 parts of nano calcium carbonate balls obtained in the previous step into 150mL of deionized water, and carrying out ultrasonic treatment for 2 hours to obtain a calcium carbonate dispersion liquid. Adding gelatin particles into a mixed solution (volume ratio is 10:1) of deionized water and absolute ethyl alcohol at 50 ℃ in a water bath condition, preparing 10 parts of gelatin solution with the mass fraction of 5%, ensuring that the solution is in a flowing state at 50 ℃, adding calcium carbonate dispersion liquid, and stirring to mix the calcium carbonate dispersion liquid and the gelatin solution to obtain the calcium carbonate-gelatin mixed solution. Heating 70 parts of olive oil to 70 ℃, stirring and shearing at the speed of 2000r/min by using a high-speed shearing machine, dropwise adding the calcium carbonate-gelatin mixed solution, and continuously stirring for 20min after all the dropwise adding is finished. Then, the mixture is rapidly cooled by an ice bath under the state of keeping stirring, and the gelatin globules precipitated at the bottom are collected. And (3) adding the gelatin beads into 50 parts of mixed solution (volume ratio is 1:1) of glacial acetone and ethanol, soaking for 5 hours, and washing for 5 times by using deionized water and absolute ethyl alcohol to obtain the calcium carbonate-gelatin nano microspheres. Adding the microspheres into 1mol/L dilute hydrochloric acid solution, standing for 5h, respectively carrying out centrifugal washing on the microspheres for 5 times by using 0.5mol/L NaOH solution, deionized water and absolute ethyl alcohol, putting the microspheres into water-soluble plant squalane, soaking for 2h, and naturally drying to obtain the moisturizing nano gelatin microspheres.

Example 3

The embodiment provides a moisturizing nano gelatin microsphere, and the preparation method comprises the following steps:

the biomass honeycomb semipermeable membrane obtained in production example 1 was fixed to a reactor, the reactor was divided into two parts, and an equal amount of Na was added₂CO₃Solution and CaCl₂The solution is respectively placed on two sides of a biomass honeycomb semipermeable membrane and reacts for 48 hours at the temperature of 25 ℃. Separating the product by a centrifugal separator at the rotating speed of 4000r/min, and washing the product by deionized water and ethanol to obtain nano calcium carbonate balls;

and adding 6 parts of the nano calcium carbonate balls obtained in the previous step into 150mL of deionized water, and carrying out ultrasonic treatment for 2 hours to obtain a calcium carbonate dispersion liquid. Adding gelatin particles into a mixed solution (volume ratio is 10:1) of deionized water and absolute ethyl alcohol at 50 ℃ in a water bath condition, preparing 10 parts of gelatin solution with the mass fraction of 5%, ensuring that the solution is in a flowing state at 50 ℃, adding calcium carbonate dispersion liquid, and stirring to mix the calcium carbonate dispersion liquid and the gelatin solution to obtain the calcium carbonate-gelatin mixed solution. Heating 70 parts of olive oil to 70 ℃, stirring and shearing at the speed of 2000r/min by using a high-speed shearing machine, dropwise adding the calcium carbonate-gelatin mixed solution, and continuously stirring for 20min after all the dropwise adding is finished. Then, the mixture is rapidly cooled by an ice bath under the state of keeping stirring, and the gelatin globules precipitated at the bottom are collected. And (3) adding the gelatin beads into 50 parts of mixed solution (volume ratio is 1:1) of glacial acetone and ethanol, soaking for 5 hours, and washing for 5 times by using deionized water and absolute ethyl alcohol to obtain the calcium carbonate-gelatin nano microspheres. Adding the microspheres into 1mol/L dilute hydrochloric acid solution, standing for 5h, respectively carrying out centrifugal washing on the microspheres for 5 times by using 0.5mol/L NaOH solution, deionized water and absolute ethyl alcohol, putting the microspheres into water-soluble plant squalane, soaking for 2h, and naturally drying to obtain the moisturizing nano gelatin microspheres.

Examples 4 to 11

Examples 4 to 11 respectively provide moisturizing nano gelatin microspheres, and the preparation method was the same as example 1 except that the biomass honeycomb semipermeable membrane obtained in preparation example 1 was replaced with the biomass honeycomb semipermeable membranes obtained in preparation examples 2 to 9 respectively in the same amount.

Application example 1

The application example provides a lipstick which comprises the following components in parts by weight:

15 parts of beeswax, 12 parts of honey, 30 parts of coconut oil, 10 parts of camellia seed oil, 9 parts of rose essential oil, 15 parts of cetearyl isooctanoate, 4 parts of plant toner, 3 parts of tocopherol and 5 parts of the moisturizing nano gelatin microspheres provided in example 1.

The preparation method comprises the following steps:

placing natural beeswax and Mel in digital display constant temperature water bath at 70 deg.C, stirring at 1100r/min for 10min to obtain mixture, adding oleum Cocois, oleum Camelliae Japonicae, oleum Rosae Rugosae and cetearyl isooctanoate into the mixture, and stirring until the mixture is completely melted. Sieving the plant toner with a fine mesh sieve, adding into the mixture, stirring for 3min, adding tocopherol, and stirring. And (3) cooling the mixture prepared in the step to 55 ℃, finally adding the moisturizing nano gelatin microspheres provided in the embodiment 1, stirring for 8min, and rapidly cooling and forming the liquid lipstick under the ice bath condition to obtain the lipstick.

Application example 2

The application example provides a lipstick which comprises the following components in parts by weight:

10 parts of beeswax, 15 parts of honey, 25 parts of coconut oil, 8 parts of camellia seed oil, 12 parts of rose essential oil, 20 parts of cetearyl isooctanoate, 3 parts of plant toner, 5 parts of tocopherol and 3 parts of the moisturizing nano gelatin microspheres provided in example 1.

The preparation method was the same as in application example 1.

Application example 3

The application example provides a lipstick which comprises the following components in parts by weight:

15 parts of beeswax, 8 parts of honey, 35 parts of coconut oil, 9 parts of camellia seed oil, 6 parts of rose essential oil, 10 parts of cetearyl isooctanoate, 6 parts of plant toner, 1 part of tocopherol and 3 parts of the moisturizing nano gelatin microspheres provided in example 1.

The preparation method was the same as in application example 1.

Application examples 4 to 13

Application examples 4 to 13 respectively provide a lipstick, the composition of which is identical to that of application example 1 except that the moisturizing nano gelatin microspheres provided in example 1 are replaced with the moisturizing nano gelatin microspheres provided in examples 2 to 11 respectively.

The preparation method was the same as in application example 1.

Comparative application example 1

The comparative application example provides a lipstick, which comprises the following components in parts by weight:

5 parts of beeswax, 60 parts of honey, 15 parts of coconut oil, 20 parts of camellia seed oil, 3 parts of rose essential oil, 25 parts of cetearyl isooctanoate, 1 part of plant toner, 8 parts of tocopherol and 1 part of moisturizing nano gelatin microspheres provided in example 1.

The preparation method was the same as in application example 1.

Comparative application example 2

The comparative application example provides a lipstick, which comprises the following components in parts by weight:

20 parts of beeswax, 35 parts of honey, 40 parts of coconut oil, 2 parts of camellia seed oil, 15 parts of rose essential oil, 5 parts of cetearyl isooctanoate, 10 parts of plant toner, 0.5 part of tocopherol and 10 parts of moisturizing nano gelatin microspheres provided in example 1.

The preparation method was the same as in application example 1.

Comparative application example 3

This comparative application example provides a lipstick, the composition of which is identical to that of application example 1 except that the moisturizing nano gelatin microspheres provided in example 1 are replaced with the same amount of water-soluble plant squalane.

The preparation method refers to application example 1.

And (3) stability verification:

and (3) carrying out stability test on the lipsticks provided by the application examples 1-13, respectively taking three products of each group, respectively placing the three products in environments of-10 ℃, 20 ℃ and 45 ℃ for 3 months, and then taking out the products to observe the surface appearance change of the paste body. The adverse phenomena of collapse, cracking and the like are not found in all groups, and the original shape can be kept well. The lipstick provided by the invention has high stability and can meet the daily requirements of people.

Moisture retention test:

selecting 80 female volunteers, wherein the female volunteers are 18-60 years old and randomly divided into 16 groups, using the lipstick provided by application examples 1-13 and comparative application examples 1-3 for five persons in each group, using the lipstick once a day for 30 days continuously, and scoring the moisture retention of the women volunteers according to the following scoring standard:

0	dry texture, very poor moisture, no moisture retention.
		1	Dry texture, very poor moisture retention, poor moisture retention.
2	Poor moistening degree and moisture retention, and dry by pouring.
		3	Poor moisture retention and poor moisture retention.
4	Has certain moistening effect and poor moisture retention.
		5	Has certain moistening effect, good moisture retention and quick reduction of the moisture retention effect.
6	Has certain moistening effect and good moisture retention.
		7	Has good moistening effect.
8	Has excellent moisture degree and good moisture retention.
		9	Has excellent moisture degree and moisture retention property.
10	Can ensure long-term moistening and moisture retention without drawing out.

The average was calculated and the results were as follows:

group of	Score value	Group of	Score value	Group of	Score value
						Application example 1	9.6	Application example 7	7.6	Application example 13	4.4
Application example 2	9.2	Application example 8	7.4	Comparative application example 1	5.6
						Application example 3	9.0	Application example 9	7.0	Comparative application example 2	5.4
Application example 4	8.6	Application example 10	6.4	Comparative application example 3	5.0
						Application example 5	8.2	Application example 11	6.0
Application example 6	8.0	Application example 12	4.8

The results show that the product provided by the invention has excellent moisturizing effect compared with the product directly added with the moisturizing agent by adding the moisturizing nano gelatin microspheres; compared with application examples 1 and 8-11, the nano calcium carbonate spheres prepared by the biomass cellular semi-permeable membrane prepared by using the specific raw materials have more uniform particle size, and the moisturizing nano gelatin microspheres and lipstick prepared by using the nano calcium carbonate spheres have better moisturizing effect.

And (3) testing the slow release effect:

20g of each of the lipsticks provided in application examples 1 to 13 and comparative application examples 1 to 3 was placed in a dialysis bag, sealed with a stopper and placed in a 500mL beaker containing 200mL of deionized water, and samples were taken (2h, 4h, 6h, 8h, 10h, 12h) at the scheduled time and 200mL of deionized water was replaced. And detecting the content of the effective components of the sample by using instruments such as a spectrophotometer and the like, and counting the release amount of the sample.

A statistical formula is as follows:

wherein: s-percent release; m-total mass (g) of effective moisture retention components in the sample; v-sampling volume per time, 100 mL; c-effective moisture content concentration (g/mL) of each sampling;

the results are reported as follows:

the results show that the product provided by the invention has good lasting moisturizing effect and good humectant slow-release effect. Compared with application examples 1 and 8-11, the nano calcium carbonate spheres prepared from the biomass cellular semi-permeable membrane prepared from the specific raw materials have more uniform particle size, and the moisturizing nano gelatin microspheres and the lipstick humectant prepared from the nano calcium carbonate spheres have better sustained-release effect and can moisturize for a long time.

The applicant states that the present invention is illustrated by the above examples of the biomass honeycomb semipermeable membrane, the moisturizing nano gelatin microspheres, the lipstick and the preparation method thereof, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.