CN106901996A - Fibroin albumen that is a kind of stealthy and can taking off nurses film substrate and preparation method thereof - Google Patents
Fibroin albumen that is a kind of stealthy and can taking off nurses film substrate and preparation method thereof Download PDFInfo
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- CN106901996A CN106901996A CN201710088689.1A CN201710088689A CN106901996A CN 106901996 A CN106901996 A CN 106901996A CN 201710088689 A CN201710088689 A CN 201710088689A CN 106901996 A CN106901996 A CN 106901996A
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
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- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/35—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
- A61K31/352—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom condensed with carbocyclic rings, e.g. methantheline
- A61K31/353—3,4-Dihydrobenzopyrans, e.g. chroman, catechin
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- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/35—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
- A61K31/352—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom condensed with carbocyclic rings, e.g. methantheline
- A61K31/353—3,4-Dihydrobenzopyrans, e.g. chroman, catechin
- A61K31/355—Tocopherols, e.g. vitamin E
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- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/365—Lactones
- A61K31/375—Ascorbic acid, i.e. vitamin C; Salts thereof
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- A61K31/7028—Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages
- A61K31/7034—Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages attached to a carbocyclic compound, e.g. phloridzin
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- A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
- A61K31/726—Glycosaminoglycans, i.e. mucopolysaccharides
- A61K31/728—Hyaluronic acid
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- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/48—Fabaceae or Leguminosae (Pea or Legume family); Caesalpiniaceae; Mimosaceae; Papilionaceae
- A61K36/484—Glycyrrhiza (licorice)
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- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/88—Liliopsida (monocotyledons)
- A61K36/896—Liliaceae (Lily family), e.g. daylily, plantain lily, Hyacinth or narcissus
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- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/42—Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0204—Specific forms not provided for by any of groups A61K8/0208 - A61K8/14
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
- A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/60—Sugars; Derivatives thereof
- A61K8/602—Glycosides, e.g. rutin
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/67—Vitamins
- A61K8/676—Ascorbic acid, i.e. vitamin C
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/67—Vitamins
- A61K8/678—Tocopherol, i.e. vitamin E
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/735—Mucopolysaccharides, e.g. hyaluronic acid; Derivatives thereof
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- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
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Abstract
Fibroin albumen application field of the present invention, more particularly to fibroin albumen that is a kind of stealthy and can taking off nurses film substrate and preparation method thereof;Nursing film substrate includes well mixed fibroin albumen, NMF and thickener, wherein the mass fraction of the fibroin albumen is 0.5 5%, the mass fraction of the NMF is 5 50%, and the mass fraction of the thickener is 1% 6%, balance of water;Its preparation method is comprised the following steps:S1, NMF is added in silk fibroin protein solution in proportion, and well mixed turn into mixed liquor;S2, thickener is added in mixed liquor, it is well mixed after obtain nursing film substrate;Fibroin albumen that is of the invention stealthy and can taking off nurses film and preparation method thereof, raw material is pure natural, preparation method and step simple, substrate uniform application in 10min 15min or so on skin can the one layer formed in situ stealthy film with aesthetic effect, the approximate skin of film material, peel off it is convenient, in addition this substrate have preferable compatibility with active material.
Description
Technical field
The present invention relates to fibroin albumen application field, more particularly to fibroin albumen nursing film substrate that is a kind of stealthy and can taking off
And preparation method thereof.
Background technology
By natural polymer amount (>100KDa) material that fibroin albumen is made has good biocompatibility, can be biological
Degraded, it is nontoxic, and have preferable filming performance, various fibroin albumen base biomaterials can be prepared.Fibroin Films moisture absorption is saturating
Gas is good, is applied to organizational project and drug controlled release system, such as artificial skin etc..For fibroin albumen,
It is the natural polymer fibrin extracted from silk, content accounts for the 70%~80% of silk, containing 18 kinds of amino acid, its
Middle glycine (gly), alanine (ala) and serine (ser) account for more than the 80% of total composition, and wherein leucine can accelerate carefully
The metabolism of born of the same parents, serine, threonine can delay skin aging, tryptophan, tyrosine can absorb ultraviolet, because of fibroin albumen
With prominent structure and composition, its film that is made extremely similar to human skin, the laudatory title for having human body " Second Skin ", relatively
For, silk care product has a extensive future, and meets the green consumption idea of the new century mankind.
It is understood that the physiological structure of skin is complicated, and it is the maximum organ of human body, human body can be avoided to be subject to bacterium and dirt
Invasion and attack, play a part of to protect and maintain body homeostasis, but normal skin can be included exposed to the external world
Ultraviolet, sharp implements, environmental pollution, bacterium the metabolism aging that interior all kinds of factors are threatened and skin is spontaneous influence,
Skin injury infection or Skin Cell is set to lack flexibility and relax, wrinkle occurs in skin and coarse grade is existing while fat secretion is reduced
As unlike young skin exquisiteness is glossy, so wanting the skin of young fine and smooth health, skin nursing is particularly important.
The species and form of the product of skin nursing in the market are very more, such as whitening, anti-wrinkle, moisturizing, skin
Powder, liquid or the gel spread product such as repair, and be affixed on the self-stick notes of skin, the taking off such as dressing sticks material and beautifying apparatus
Beautifying medical apparatus that structure is used etc..Now, with the improvement of people ' s living standards with allegro life and people to U.S.
Pursuit, the skin care item of disposable taking off seem important in daily nursing and hospitalize.To taking off product, greatly
Part be apply treatment repair class nursing in terms of, and in terms of daily nursing be mainly facial mask, have traditional hygenic towelette facial mask and
Stripable board facial mask (gel, spraying or creams form strippable film after smearing face).
Present material facing challenges, selection green, and cause allergy non-stimulated to skin.In terms of properties of product, it is desirable to
Possess following characteristics:1) smear:The formula of formation easy film on skin comes, and forms one layer of film of safety;
2) breathable moisture permeability:After smearing is opened, combined closely with skin, but to ensure to smear the skin energy eupnea of position simultaneously, with
External environment keeps certain and breathes freely and permeable;3) mechanical property:Mechanical property with original skin will match, with certain
Strength and resilience, it is ensured that normal skin activity;4) aesthetic properties:Simulation normal skin will not at least change original skin
Skin type, while to possess generality, and also the skin quality of people several greatly is suitable for using;5) tearable:Can be with when unwanted
Easily peel, it is not necessary to washing removal, equivalent to another plus one layer of skin outside human body skin.
In terms of taking off care product is prepared, there is following several preparation methods:1) the first is conventional method, first
It is to prepare flaky material, such as non-woven material then again in flaky material above in conjunction with functional materials, or is inhaled according to physics
Flaky material is soaked in preparation general duty nursing product in functional materials by attached principle, or continues coating preparation with specific use
Compound rest, it is exactly before the use a kind of product of shaping to be the characteristics of this material is most obvious, and patch is only needed to when using
The effect of nursing, such as facial mask can be played in privileged site, and the product of class is repaired in other some treatments, is still relied upon and is used
Cumbersome wrapping dressing, is often applied in combination with external-applied ointment, because patient compliance is poor, often fails.2) it is for second
Freeze film, it is exactly the facial mask that with the addition of the colloids such as Kappa mother, aloe to freeze film, can be put on as late frost and slept on the face, second day
Wash off, but after being applied on the face, skin-protection product major part is easily sticked on pillow or bed clothes, using not being very square
Just.3) the third is a kind of gel or fluid product be easy to and smear and carry, and film can be gradually formed after smearing and to skin
Skin plays a protective role, and for example Chinese patent CN201410537752.1 and CN201610601512.2 disclose strippable face
Film.Chinese patent CN201410537752.1 discloses a kind of peelable mask matrix based on aqueous polyurethane dispersion system,
The matrix is that, with aqueous polyurethane dispersion as main component, and it is multiple to be equipped with thickener, emulsifying agent, grease, preservative, essence etc.
With forming, this matrix is fitted completely with skin, into transparent membrane after parching, is not fallen off, with the skin that compacts, Exfoliating Scrub dirt
Effect, but can be removed, it is necessary to be soaked with water when peeling off, and the Material synthesis of polyurethane are complicated, middle extraction step
Using the volatile organic solvent such as acetone, residue easily produces harmful effect to skin.Chinese patent
CN201610601512.2 disclose it is a kind of peel off facial mask, formula is made up of A agent and B agent, and A agent is by that can obtain blue glue, glycerine, transparent
Matter acid sodium and water composition, and B agent is to be formulated to obtain a kind of spray by trehalose and water, and A agent is applied into face when using, and is made
It forms uniform film, and B agent then is sprayed on into A agent surface, is peeled off after 15-20min, and the film moistening effect is good, water lock
Ability is strong, and tearing will not be caused to skin during stripping, however it is necessary that two steps, complex operation, and A, B agent are indispensable, A agent with
Both bad controls of ratio during the use of B agent, without commonly using property, using cumbersome.
In addition to the above methods, the researchers such as also Massachusetts Institute Technology Robert Langer team, Betty Yu grind
One kind " Second Skin " XPL is made, mainly there are two steps, the first step has smeared flowable, and with skin conformality, reactivity is poly-
Silicone gel.Second step platinum catalysis polysiloxanes produces crosslinking, also makes the surface of the XPL that light diffusing particles are deposited on, and makes skin
Polysiloxanes on skin is crosslinked, and the film for so being formed can be just pasted onto on the skin at face or other positions of body,
Confirmed according to research, this layer film of formation can be fitted tightly on skin more than 16 hours.Concrete principle is surface optical grain
Son and bottom cross linking polysiloxane network generation minute surface and scattered reflection can approach the outward appearance of young skin, form artificial leather
Skin.Subsequent clinical test shows that this " Second Skin " can effectively recover the original mechanical property of skin, can be effective
Eliminate the pouch of user face.At the same time, the presence of polysiloxane film can also preferably help skin moisture-keeping, can be used for
Skin care item or cosmetics, apply also for medical skin, but in the formula of the first step and second step, raw material is complicated, two steps
Method operation is also comparatively laborious, and need to smear when smearing ground floor it is uniform after, be further continued for smearing the second layer, than relatively time-consuming, most
Good scheme is that one-step method can just prepare this film-formable material.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of raw material is pure natural, preparation method and step letter
List, the approximate skin of material, stripping are conveniently and active material has the stealthy of preferable compatibility and the fibroin albumen nursing film base that can be taken off
Bottom and preparation method thereof.
First aspect present invention provides fibroin albumen nursing film substrate that is a kind of stealthy and can taking off, including well mixed silk
Fibroin, NMF and thickener, wherein the mass fraction of the fibroin albumen is 0.5-5%, the quality point of the NMF
Number is 5-50%, and the mass fraction of the thickener is 1%-6%, balance of water.
Further, the mass fraction of the fibroin albumen is 1-3%.
Further, also including functional activity material, the functional activity material includes that vitamin E, vitamin C, table do not have
Infanticide catechin and gallate, licorice, ursin, Bulbus Allii Cepae extract, seaweed extracted liquor, one kind of hyaluronic acid or
It is various.
Further, the NMF includes PEG400, polyethylene glycol 200, Liquid Macrogol, polyethylene glycol
600th, one or more in glycerine, 1-3 butanediols, sorbierite, hyaluronic acid.
Further, the thickener includes hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethylcellulose calcium, Huang
One or more in virgin rubber, Kappa mother.
Further, the nursing film substrate is paste, spray or jelly.
Further, also including crosslinking agent, the crosslinking agent includes polyvinyl alcohol, sodium alginate, calcium chloride, cation hydroxyl
One or more in ethyl cellulose.
A kind of stealth of second aspect present invention offer and the preparation method of the fibroin albumen nursing film substrate that can be taken off, including with
Lower step:
S1, NMF is added in silk fibroin protein solution in proportion, and well mixed turn into mixed liquor;
S2, thickener is added in mixed liquor, it is well mixed after obtain nursing film substrate.
Wherein, it should be noted that HMW (>100KDa) preparation method of silk fibroin solution should include various, bag
Include but be not limited to be obtained by lithium bromide method or denaturant dialysis, wherein,
The lithium bromide method is comprised the following steps:
The boiled-off silk of degumming is infiltrated into the heating for dissolving in the LiBr solution of 9.3M and obtains fibroin albumen stoste, then should
Fibroin albumen stoste is poured into bag filter and dialysed with deionized water, and dialysis is centrifuged removal insoluble matter impurity and obtains fibroin egg after terminating
The step of white solution;
The denaturant dialysis are comprised the following steps:
Boiled silk is dissolved using chloride containing calcium ternary solution and obtain fibroin albumen stoste, use protein denaturation agent solution
After the fibroin albumen stoste as described in concentration gradient dialysis treatment successively from high to low, reuse water dialysis treatment and obtain fibroin albumen
Solution.
Further, functional activity material is also added with the step S1, the functional activity material includes vitamin E
(VE), vitamin C (VC), Epigallo-catechin gallate (EGCG) (EGCG), licorice, ursin, Bulbus Allii Cepae extract,
One or more of seaweed extracted liquor, hyaluronic acid.
Functional activity material is mixed into step sl, it is necessary to consider that the outward appearance after film forming, the film forming of substrate is not received simultaneously
Influence, and active material content.For VC, VE, it is belonging to water miscible, is commonly used in skin care item, content can be with
3-20% is accounted for, after concentration increases, VC's is active unstable, so active material need to be in step sl mixed into, because fibroin egg
There are certain protective effect (literature reference Luo T, Lei Y, Wu J, et al.Stabilization of to such activity in vain
Natural Antioxidants by Silk Biomaterials[J].Acs Applied Materials&
Interfaces, 2016.), to improve bioavilability.EGCG (0.01%-3%) plays critically important in terms of radiation proof
, can be mixed into EGCG in step S1 by effect, can prepare it is a kind of have the taken off nursing film of certain protective action to radiation, it is and sweet
Careless extract (0.001-3%), alpha-arbutin (1-7%), Bulbus Allii Cepae extract (0.01%-5%), seaweed extracted liquor (0.5-
5%), the material such as hyaluronic acid (0.05%-0.1%), can directly add, and can obtain whitening suppression scar class nursing film substrate.
Further, the NMF includes PEG400, polyethylene glycol 200, Liquid Macrogol, polyethylene glycol
600th, one or more in glycerine, 1-3 butanediols, sorbierite, hyaluronic acid.
Further, the thickener includes hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethylcellulose calcium, Huang
One or more in virgin rubber, Kappa mother.
Further, the nursing film substrate is paste, spray or jelly.
Further, be also mixed with crosslinking agent in the step S1, the crosslinking agent include polyvinyl alcohol, sodium alginate,
One or more in calcium chloride, cationic hydroxyethyl cellulose.It should be noted that nursing film base prepared by above-mentioned steps
Bottom, smears after film forming on skin, meets water capacity malleable shape, partly starts molten mistake, in order to expand use ring of the invention
Border, in the case of especially meeting water, can be mixed into crosslinking agent to improve this phenomenon, but can not change the fine and smooth sense of substrate, apply
Smear performance, filming performance and film forming hidden property.This crosslinking agent can be shitosan, polyvinyl alcohol, sodium alginate, chlorination
Calcium or cationic hydroxyethyl cellulose.However, when shitosan is mixed into substrate, being belonging to water-insoluble, therefore use preceding needs
Shitosan is configured to solution, typically the shitosan glacial acetic acid of 1-2% is dissolved.Content of the shitosan in total substrate is accounted for
The 0.1%-2% of whole substrate, polyvinyl alcohol accounts for the 1-20% of whole substrate, sodium alginate (0.1%-10%), cation hydroxyl
Ethyl cellulose (2-5%).
By such scheme, the present invention at least has advantages below:
1) raw material is pure natural fibroin albumen, source green, and whole preparation process environmental protection can be mass-produced;2) substrate
Preparation method and step it is simple;3) substrate for preparing be applied on skin only need a step just can be with, after smearing the short time into
Film, and the film for being formed can stop more than 12h on skin;4) film for being formed is transparent, and glossy, it appears that
Approximating anatomy's skin, while blocking ultraviolet;5) film can be peeled off smoothly, skin will not be caused during stripping tear
Draw;5) film has the mechanical property close to human body skin;6) addition fibroin albumen can play moistening effect, the fibroin egg of addition
In vain due to there is many hydrophilic radicals in its side chain, therefore have certain water lock moistening effect to skin;7) this matrix and active matter
Matter has preferable compatibility, and whitening and anti-aging isoreactivity material or medicine can be added in the substrate, with good sustained release
Effect, and the fibroin material active material unstable to some has protective effect, and then active material can be improved
Bioavilability.The daily nursing field of other positions for skin of the bodies such as face, neck can be smeared or be sprayed on to this substrate
And some nursing care of decubitus ulcer, anti-ray radiation etc. field.
Described above is only the general introduction of technical solution of the present invention, in order to better understand technological means of the invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is three rheological data figures of sample in third embodiment of the invention;
Fig. 2 is the rheological data figure of the Second Skin xpl that masschusetts, U.S.A science and engineering is developed;
Fig. 3 is skin nursing film uvioresistant performance test result figure in fourth embodiment of the invention;
Fig. 4 is the ess-strain result figure of sample 1 in fifth embodiment of the invention;
Fig. 5 is the ess-strain result figure of sample 2 in fifth embodiment of the invention;
Fig. 6 is the observation of skin nursing film hidden property and tearable test result figure in sixth embodiment of the invention;
Fig. 7 is the stability observing result figure in skin nursing film water in eighth embodiment of the invention.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiment of the invention is described in further detail.Hereinafter implement
Example is not limited to the scope of the present invention for illustrating the present invention.
The preparation of the silk fibroin protein solution of embodiment 1
Weigh 30g raw silks to be put into the boiling water containing 0.02M natrium carbonicum calcinatums, boil 30min, every 5min stirrings once,
Then by the silk after degumming, five times are washed by rubbing with the hands afterwards with deionized water, is transferred to after fume hood dried overnight as boiled-off silk.
Dried boiled-off silk is pressed into bath raio 1g:4ml, in beaker of the immersion containing 9.3M lithium bromides, then in 60 DEG C of baking ovens
4h is shelved, period, per the solution in stirring beaker every other hour, finally can obtain the fibroin albumen mixed solution of 20% (w/v).
This solution is transferred in the bag filter of 3.5KDa, dialyse 48h in deionized water, then by silk fibroin protein solution
Press the speed of 9000r/min in 4 DEG C of centrifuge, centrifugation twice, each 20min, it is therefore an objective to get rid of it is undissolved other
Material.
Weigh the silk fibroin protein solution after 1ml centrifugations and record its mass value, be then placed in 60 baking ovens and dry to perseverance
Weight, quality after then dry with dry before mass percent value be exactly fibroin albumen concentration (mass percent,
MW%), the fibroin albumen concentration range for typically resulting in is 6-9% or so, and the silk fibroin protein solution that then will be obtained is diluted to 1-
20min is processed in autoclave sterilization pot after 5%, after after solution cooling, is placed in standby in 4 DEG C of refrigerators.
The softness of embodiment 2 can take off the preparation that fibroin albumen nurses film
The present embodiment provides a kind of softness and can take off the preparation method that fibroin albumen nurses film, comprises the following steps:
S1, the silk fibroin protein solution obtained according to embodiment 1 prepare 3% silk fibroin protein solution;
S2, the PEG400 that configuration quality fraction is 60% (400 represent the molecular weight of PEG, and PEG ranks are medical rank);
S3, the ratio in each composition shown in table 1, take the stirring mixing of silk fibroin protein solution, PEG400 solution and pure water, then
(hydroxyethyl cellulose, Tao Shi celluloses are bought in the Guangzhou plumage limited public affairs of tawny daylily biotechnology to add QP100 in toward mixed liquor respectively
Department), after waiting stirring completely, it is possible to obtain the fibroin albumen nursing substrate of different filming performances.It is applied on the back of the hand, observation refers to
Mark:Ductility, gas permeability, compactness, tearable and film forming (weak difference in dividing five grades excellent).
A, ductility:Matrix is applied on the back of the hand skin, if can smoothly smear and come, if form continuous thin
Film, whether there is skewness;
B, gas permeability:Matrix is applied on the back of the hand skin, after film forming, experience substrate whether there is on skin it is sticky sense and not
Ventilative sense.
C, compactness:Matrix is applied on the back of the hand skin, after film forming, experiences substrate whether there is tight sense on skin
Feel.
D, film forming:Matrix is applied on the back of the hand skin, seeing whether can be with film forming, and whether institute's film forming is transparent.
E, tearable:Matrix is applied on the back of the hand skin, after film forming, if smoothly can be peeled from skin, if
It is tightly combined with skin, whether skin has uncomfortable sensation when taking off.
Table 1:Softness can take off fibroin albumen nursing film preparation in each composition mixed proportion
Sample | 3%SF (ml) | 60%PEG (ml) | QP100(g) | Water (ml) |
1 | 1 | 1 | 0.12 | 4 |
2 | 1 | 2 | 0.15 | 3 |
3 | 1 | 3 | 0.18 | 2 |
4 | 2 | 1 | 0.15 | 3 |
5 | 2 | 2 | 0.18 | 2 |
6 | 2 | 3 | 0.12 | 1 |
7 | 3 | 1 | 0.18 | 2 |
8 | 3 | 2 | 0.12 | 1 |
9 | 3 | 3 | 0.15 | 0 |
10 | 0 | 1 | 0.18 | 5 |
11 | 3 | 0 | 0.18 | 3 |
12 | 3 | 1 | 0 | 2 |
Result of the test is as shown in table 2:Result finds that in above-mentioned experiment, the substrate contacts no sticky feeling with skin, holds
Easily peel, and without residual on skin.SF, PEG, QP100 three will must have, and one is needed between three
Fixed ratio coordinates.
The softness of table 2 can take off fibroin albumen nursing film test result statistics
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | |
Ductility | It is excellent | It is good | It is good | It is excellent | It is good | In | It is good | It is good | It is good | It is good | In | It is excellent |
Gas permeability | It is good | It is good | It is good | It is good | It is good | It is good | It is excellent | It is good | It is good | It is good | In | It is good |
Compactness | It is weak | In | It is good | In | It is good | In | It is excellent | It is good | It is excellent | It is weak | It is weak | Difference |
Film forming | It is weak | In | It is good | It is weak | It is excellent | In | It is excellent | It is good | It is good | It is good | It is weak | Difference |
Row can be taken off | Difference | It is weak | It is good | It is weak | It is excellent | In | It is excellent | In | It is good | It is weak | It is weak | Difference |
Spreading property (ductility) test of the skin nursing film of embodiment 3
The present embodiment provides a kind of method that softness can take off spreading property (ductility) test of fibroin albumen nursing film, bag
Include following steps:
S1, the silk fibroin protein solution obtained according to embodiment 1 prepare 3% silk fibroin protein solution;
S2, the PEG400 that configuration quality fraction is 60% (400 represent the molecular weight of PEG, and PEG ranks are medical rank);
S3, the ratio in each composition shown in table 3, take silk fibroin protein solution PEG400 solution and pure water stirring mixing, then
(hydroxyethyl cellulose, Tao Shi celluloses are bought in the Guangzhou plumage limited public affairs of tawny daylily biotechnology to add QP100 in toward mixed liquor respectively
Department), after waiting stirring completely, it is possible to obtain the fibroin albumen nursing substrate with different spreading properties.
S4, three kinds of ductility of substrate in test table 3 on rheometer.
Use instrument:Rheometer (AR2000, TA instrument companies of the U.S.), uses parameter:Cone-plate diameter 20mm, 1 ° of cone angle,
Heating-up temperature:37 DEG C, tested viscosity changes from 0.1-100 (1/s) with the change of shear rate, speed.
Table 3:Each composition mixed proportion when the spreading property of skin nursing film is tested
Sample | 3%SF (ml) | 60%PEG (ml) | QP100(g) | Water (ml) |
1 | 3 | 1 | 0.18 | 2 |
2 | 3 | 2 | 0.18 | 1 |
3 | 3 | 3 | 0.18 | 0 |
Result as shown in figure 1, be the present embodiment provide sample 1,2 and 3 viscosity with the data of shear rate change,
1,2,3 represent sample 1,2 and 3 in picture, and with the increase of shear rate (abscissa), viscosity (ordinate) reduces, and illustrates this
The substrate of invention is shear shinning matrix, easily smears and opens, with good thixotropy, and PEG the fewer (sample of content
1), easier smearing comes;As shown in Fig. 2 being the Second Skin xpl rheological datas of masschusetts, U.S.A science and engineering development, skin of the present invention
The rheological data and the similar (literature reference of its result of skin nursing film:Yu,B.,et al."An elastic second skin."
Nature Materials 15.8(2016).),
In addition to above-mentioned mixed proportion, spreading property can also be carried out in terms of the content of hydroxyethyl cellulose QP100
Optimization, the content of hydroxyethyl cellulose QP100 is more, and quality is more sticky, and in the present invention, scope selects the model in 1%-3%
Within enclosing, experiment in addition shows, the regulation and control (1%-4%) to fibroin albumen (SF) content, finds the content of fibroin albumen to applying
The no hydroxyethyl cellulose QP100 of influence of smearing property is obvious.
The uvioresistant performance test of the skin nursing film of embodiment 4
The present embodiment provides a kind of method that softness can take off the uvioresistant performance test of fibroin albumen nursing film, including following
Step:
S1, the silk fibroin protein solution obtained according to embodiment 1 prepare 3% silk fibroin protein solution;
S2, the PEG400 that configuration quality fraction is 60% (400 represent the molecular weight of PEG, and PEG ranks are medical rank);
S3, the ratio in each composition shown in table 4, take silk fibroin protein solution PEG400 solution and pure water stirring mixing, then
(hydroxyethyl cellulose, Tao Shi celluloses are bought in the Guangzhou plumage limited public affairs of tawny daylily biotechnology to add QP100 in toward mixed liquor respectively
Department), after waiting stirring completely, it is possible to obtain the fibroin albumen nursing substrate of different filming performances.
Each composition mixed proportion when the uvioresistant performance of the skin nursing film of table 4 is tested
Sample | 3%SF (ml) | 60%PEG (ml) | QP100(g) | Water (ml) |
1 | 3 | 1 | 0.18 | 2 |
2 | 0 | 1 | 0.18 | 5 |
Sun-proof performance instrument test (in vitro method):Sun care preparations is applied on quartz slide, using ultraviolet spectrometry
The absorbance of photometer measuring method determination sample, this is the general principle of domestic and international all appts determination method at present, in this implementation case
In example, the instrument for using is UV, visible light near infrared spectrometer (Cary 5000, Agilent, the U.S.), and experimental procedure is such as
Under:
A, substrate is uniformly filled on quartz slide (25mm*25mm), during smearing, application area is identical, smear 3
Individual different-thickness, in view of thickness weighs inconvenient, therefore uses slide and substrate gross weight value indirect reaction thickness in the present invention,
That smears is thicker, and comparatively weight can increase.In this programme, with reference to the material of substrate, weigh 20mg (A), 50mg (B) and
In on slide, every group of weight sets five Duplicate Samples to the substrate of 100mg (C), and three weight amount to 15 samples.During smearing,
The sample remained on slide must be again weighed because finger can take away a part of substrate, after smearing, when weighing, substrate and glass is weighed
The gross weight of piece, after then subtracting the weight of initial slide, we obtain substrate residual quantity (A1, A2, A3, A4, A5, B1,
B2, B3, B4, B5, C1, C2, C3, C4, C5), then the sample of each thickness determine respectively wavelength 285nm, 290nm,
Absorbance (Abs) at 300nm, 310nm, 315nm, 320nm, by taking A thickness as an example, under each wavelength, can obtain A thick
Five absorbances of Duplicate Samples of degree, then the average of the lower five Duplicate Samples absorbances of each wavelength is calculated, can obtain Abs
(285nm, A), Abs (290nm, A) Abs (300nm, A) Abs (310nm, A) Abs (315nm, A) Abs (320nm, A) then will
The summation of the average Abs (wavelength, A) of absorbance removes 6 under 6 wavelength of the A thickness for obtaining, it is possible to used as final A thickness
Absorbance, for evaluating sun-proof result.The same A of computational methods of B and C.
Absorbance < 1.0:Without sun-proof result.
Absorbance=1.0:Rudimentary sun-proof result.
Absorbance > 1.0, and < 2.0:Intermediate sun-proof result.
Absorbance > 2.0:Senior sun-proof result.
Result is as shown in figure 3, for the absorption values that the uvioresistant performance of the skin nursing film in the present embodiment is tested (are tried
Sample 1 and sample 2), abscissa represents substrate residual quantity (14mg, the 37mg in slide for weighing 20mg, 50mg and 100mg in Fig. 3
And 87.5mg), ordinate represents the final absorbance Abs under each thickness, and the difference of sample 1 and sample 2 is that sample 2 is free of
Fibroin.As seen from the figure, with the addition of after fibroin albumen (sample 1), the numerical value of absorbance does not add fibroin significantly greater than
The sample (sample 2) of albumen, and when smearing thickness it is thick some when (during 87.5mg), absorbance can be more than 1, the implementation case
In, the concentration of fibroin albumen is relatively low, when the concentration of fibroin albumen is improved, equivalent to smearing thickness is improved, so as to will play
More preferable sun-proof result.
The Mechanics Performance Testing of the skin nursing film of case study on implementation 5
The present embodiment provides a kind of method that softness can take off the Mechanics Performance Testing of fibroin albumen nursing film, including following step
Suddenly:
S1, the silk fibroin protein solution obtained according to embodiment 1 prepare 3% silk fibroin protein solution;
S2, the PEG400 that configuration quality fraction is 60% (400 represent the molecular weight of PEG, and PEG ranks are medical rank);
S3, the ratio in each composition shown in table 5, take silk fibroin protein solution, PEG400 solution and pure water stirring mixing, then
QP100 (hydroxyethyl cellulose is bought in Guangzhou Yu Xuan bio tech ltd) is added in toward mixed liquor respectively, is waited and has been stirred
Quan Hou, it is possible to obtain the fibroin albumen nursing substrate of different mechanical properties after film forming.
S4, sample making:Substrate is applied into 4cm × 1.27cm, and (equivalent 4cm × 0.5 inch, is referred to Massachusetts science and engineering big
Learn research and development Second Skin XPL testing standard, American Standard ASTMD5083) sample cell in, each sample survey 5 Duplicate Samples, etc.
Peeled after having done and do test, test environment:25 DEG C of temperature, relative humidity:Under 65% standard environment.
Instrument selected by S5, the test of mechanical property is that (INSTRON-3365, U.S. INSTRON are public for Material Testing Machine
Department, the U.S.)
Major parameter during test:Folder away from:20mm;Draw speed:20mm/min;Pre-tension:0.2CN;Sample Width:
0.5 inch.
Each composition mixed proportion during the Mechanics Performance Testing of the skin nursing film of table 5
Sample | 3%SF (ml) | 60%PEG (ml) | QP100(g) | Water (ml) |
1 | 3 | 1 | 0.18 | 2 |
2 | 3 | 2 | 0.18 | 1 |
The ess-strain value of normal skin be 0.5-1.95MPa and 140%-180% (literature reference .Annaidh,
A.N.et al J.Mech.Behav.Biomed.Mater.5,139148(2012).).Massachusetts Polytechnics Second Skin XPL
Ess-strain value be (literature reference Yu, B., et al. " the An elastic second of 0.51 ± 0.01MPa and 250 ± 82%
Skin. " Nature Materials 15.8 (2016)) in the present embodiment sample 1 and sample 2 ess-strain value respectively as schemed
Shown in 4 and Fig. 5, abscissa 10% and 20% represents the shared ratios in whole substrate of PEG in sample respectively in picture, wherein
The ess-strain value of sample 2 be 1.08 ± 0.55MPa and 91.89 ± 18.5%, stress value close to human body skin, so by this
After substrate is applied on skin, there is preferable compliance with skin, will not feel under the weather.The strain value of No. 1 sample reaches
83.38 ± 43.98%, 6.64 ± 3MPa of stress value, strain value is larger, after being fitted with normal skin, there is tight feeling, has to wrinkle
Certain occlusion effect.Aforementioned proportion is the part test of present case, and tested number 1 and 2, there is certain mechanical property after film forming
Can, we are matched so as to enter one by optimizing fibroin albumen (1-4%), PEG (10-50%) and QP100 (1.5-3.5%) whereby
Walk and provide basis to optimize the mechanical property of skin nursing film.
The stealthy performance test of the skin nursing film of case study on implementation 6
The present embodiment provides a kind of method that softness can take off the uvioresistant performance test of fibroin albumen nursing film, including following
Step:
S1, the silk fibroin protein solution obtained according to embodiment 1 prepare 3% silk fibroin protein solution;
S2, the PEG400 that configuration quality fraction is 60% (400 represent the molecular weight of PEG, and PEG ranks are medical rank);
S3, the ratio in each composition shown in table 6, take silk fibroin protein solution, PEG400 solution and pure water stirring mixing, then
QP100 (hydroxyethyl cellulose is bought in Guangzhou Yu Xuan bio tech ltd) is added in toward mixed liquor respectively, is waited and has been stirred
Quan Hou, it is possible to obtain the fibroin albumen nursing substrate of different stealthy performances.
S4, the substrate that will be prepared are applied to skin, wait done it is later observation film it is whether stealthy.
Each composition mixed proportion during the stealthy performance test of the skin nursing film of table 6
Sample | 3%SF (ml) | 60%PEG (ml) | QP100(g) | Water (ml) |
1 | 2 | 1 | 0.18 | 3 |
2 | 3 | 1 | 0.18 | 2 |
3 | 1 | 1 | 0.18 | 4 |
4 | 2 | 2 | 0.18 | 2 |
5 | 3 | 2 | 0.18 | 1 |
6 | 1 | 2 | 0.18 | 3 |
7 | 2 | 3 | 0.18 | 1 |
8 | 3 | 3 | 0.18 | 0 |
9 | 1 | 3 | 0.18 | 2 |
Result is as shown in fig. 6, be the hidden property observation and the (examination of tearable test result of the skin nursing film in the present embodiment
Sample 1), 20min after the first row and the second row skin that is respectively the substrate of sample 1 on the outside of the arm and inboard arm skin film forming in figure
Optical photograph and tearable test.Result of the test finds, on skin after smearing nursing substrate, meeting after general 10-15min
Film forming, can easily peel very much after film forming, to skin also without tearing.The substrate of sample 1 is substantially stealth on skin,
When uncovered with hand come when, it is found that have a thin layer of film, the sample 1 in the present embodiment, be belonging to stealth.And for special
Need, than being fitted in skin if desired for the long period, dependence test result of the present invention shows, stealthy can be fitted on skin
More than 12 hours, and smoothly peel, to skin also without tearing, period is also without uncomfortable sensation.It should be noted that its
His sample 2-9 is also belonging to tearable sample, and institute is into thin after PEG and the content of fibroin albumen (SF) mainly influence substrate film forming
The hidden property of film.PEG content is more, brighter.When the content of fibroin albumen (SF) increases, be conducive to the tearable of film.
The different thickeners of case study on implementation 7 prepare the research of nursing substrate
The present embodiment is provided during a kind of softness can take off fibroin albumen nursing film and adds interpretation of result method after different thickeners,
Comprise the following steps:
S1, the silk fibroin protein solution obtained according to embodiment 1 prepare 3% silk fibroin protein solution;
S2, the PEG400 that configuration quality fraction is 60% (400 represent the molecular weight of PEG, and PEG ranks are medical rank);
S3, the ratio in each composition shown in table 7, take the stirring mixing of silk fibroin protein solution, PEG400 solution and pure water, then
HPMC is added in toward mixed liquor, and (hydroxypropyl methyl cellulose, buys in Sangon Biotech (Shanghai) Co., Ltd., and height is viscous
Degree (H), middle viscosity (M), low viscosity (L)), (hydroxyethyl cellulose buys limited in raw work bioengineering (Shanghai) share to HEC
Company, high viscosity (H), middle viscosity (M), low viscosity (L)) and polyvinyl alcohol (pva) (1788 types, buy in Aladdin).
The difference of HEC and QP100 is that purity is different with viscosity, it is necessary to explanation, in present case, purity is to this substrate
Influence very little, viscosity influence is larger, so in order to further inquire into performance impact of the different thickeners to substrate, in the present embodiment
Use hydroxyethyl cellulose (HEC), hydroxypropyl first class cellulose (HPMC) and hydroxyethyl cellulose (QP100).In addition,
Because polyvinyl alcohol is a kind of good film forming agent, the present embodiment also introduces polyvinyl alcohol with existing substrate to compare.
S4, etc. stirring completely after, it is possible to obtain different filming performances fibroin albumen nursing substrate.
S5, the substrate that will be prepared are applied on the back of the hand, observation index:Ductility, gas permeability, compactness, tearable and
Film forming etc. (weak difference in dividing five grades excellent), it is specific to judge the standard that content refers to case study on implementation 2.
Each composition mixed proportion table and its result of the test in the skin nursing film of table 7
Base Formula in table 7, selected cellulose is three kinds of viscosity, and select concentration be between 3%-5% due to
When viscosity is too high, concentration cannot be too high, not so can not smoothly disperse in water and be stirred.As a whole,
QP100, HPMC and HEC film forming are good, and HMPC film forming needs the time shorter than HEC and QP100, is also easy to film forming, but
After film forming, moisture absorption is very fast, and the phenomenon for turning white a little dry and cracked soon occurs, and is similar to scurf, adds the substrate of PVA,
Also the phenomenon of white bits occurs, but adds being considered to be worth doing in vain without appearance for HEC and QP100, if so to reach stealthy attractive in appearance
Film, preferably QP100 or HEC.
Case study on implementation 8 is nursed film and is studied in water stability
The present embodiment provides a kind of softness and can take off fibroin albumen nursing film in water stability result, comprises the following steps:
S1, the silk fibroin protein solution obtained according to embodiment 1 prepare 3% silk fibroin protein solution;
S2, the PEG400 that configuration quality fraction is 60% (400 represent the molecular weight of PEG, and PEG ranks are medical rank);
S3, the glacial acetic acid solution (including 3% shitosan) for preparing 2%, are then mixed into shitosan by the mixed proportion of table 8
Solution, (hydroxyethyl cellulose is bought in the Guangzhou plumage limited public affairs of tawny daylily biotechnology to be then blended into hydroxyethyl cellulose QP100
Department), after being well mixed, you can obtain nursing substrate.
After S4, the substrate that will be obtained are applied on the outside of inboard arm skin and arm on skin, etc. film forming after, film is taken off
After getting off, it is placed with the culture dish of water, stable case of the timing observation film in water.
The skin nursing film of table 8 each composition mixed proportion when water stability is tested
Sample | 3%SF (ml) | 60%PEG (ml) | QP100(g) | 3% shitosan (ml) | Water (ml) |
1 | 1 | 3 | 0.18 | 1.5 | 0.5 |
2 | 2 | 1 | 0.18 | 0 | 3 |
Stability observing result of the skin nursing film in water in the implementation case with the addition of as shown in fig. 7, result shows
After shitosan, film substantially becomes relatively to stablize in water, stabilization time>5h.In addition to shitosan is added, it is also an option that addition
Cationic hydroxyethyl cellulose (JR400 is bought in Guangzhou Shi Ming Chemical Co., Ltd.s), sprays alcohol, addition sodium alginate, chlorine
Change calcium etc., can partly solve water solubility problems, wherein addition cationic cellulose JR400, the film prepared by substrate is in water
Middle 40min or so will be collapsed and meeting molten mistake completely after 90min, it is impossible to keep original shape, final result is last with accompanying drawing 7
One pictures, spraying alcohol, addition sodium alginate, calcium chloride etc. can also solve part aqueous sex chromosome mosaicism, but be when stablizing
Between all without shitosan and JR400 cationic hydroxyethyl celluloses persistently, so prioritizing selection shitosan or JR400 cation hydroxyls
Ethyl cellulose.
The above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, on the premise of the technology of the present invention principle is not departed from, can also make it is some improvement and
Modification, these are improved and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. fibroin albumen nursing film substrate that is a kind of stealthy and can taking off, it is characterised in that:Including the fibroin albumen, the guarantor that are well mixed
Humectant and thickener, wherein the mass fraction of the fibroin albumen is 0.5-5%, the mass fraction of the NMF is 5-
50%, the mass fraction of the thickener is 1%-6%, balance of water.
2. fibroin albumen nursing film substrate that is according to claim 1 a kind of stealthy and can taking off, it is characterised in that:The silk
The mass fraction of fibroin is 1-3%.
3. fibroin albumen nursing film substrate that is according to claim 1 a kind of stealthy and can taking off, it is characterised in that:Also include
Functional activity material, the functional activity material includes vitamin E, vitamin C, Epigallo-catechin gallate (EGCG), sweet
Careless extract, ursin, Bulbus Allii Cepae extract, seaweed extracted liquor, one or more of hyaluronic acid.
4. fibroin albumen nursing film substrate that is according to claim 1 a kind of stealthy and can taking off, it is characterised in that:The guarantor
Humectant includes PEG400, polyethylene glycol 200, Liquid Macrogol, Macrogol 600, glycerine, 1-3 butanediols, sorb
One or more in alcohol, hyaluronic acid.
5. fibroin albumen nursing film substrate that is according to claim 1 a kind of stealthy and can taking off, it is characterised in that:The increasing
Thick dose of one kind or many included in hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethylcellulose calcium, xanthans, Kappa mother
Kind.
6. fibroin albumen nursing film substrate that is according to claim 1 a kind of stealthy and can taking off, it is characterised in that:The shield
Reason film substrate is paste, spray or jelly.
7. fibroin albumen nursing film substrate that is according to claim 1 a kind of stealthy and can taking off, it is characterised in that:Also include
Crosslinking agent, the crosslinking agent includes the one kind or many in polyvinyl alcohol, sodium alginate, calcium chloride, cationic hydroxyethyl cellulose
Kind.
8. the fibroin albumen that is a kind of stealthy and can taking off according to any one of claim 1 to 7 nurses the preparation side of film substrate
Method, it is characterised in that:Comprise the following steps:
S1, NMF is added in silk fibroin protein solution in proportion, and well mixed turn into mixed liquor;
S2, thickener is added in mixed liquor, it is well mixed after obtain nursing film substrate.
9. preparation method according to claim 8, it is characterised in that:Functional activity thing is also added with the step S1
Matter, the functional activity material includes vitamin E, vitamin C, Epigallo-catechin gallate (EGCG), licorice, bear
Fruit glycosides, Bulbus Allii Cepae extract, seaweed extracted liquor, one or more of hyaluronic acid.
10. preparation method according to claim 8, it is characterised in that:Crosslinking agent is also mixed with the step S1, it is described
Crosslinking agent includes one or more in polyvinyl alcohol, sodium alginate, calcium chloride, cationic hydroxyethyl cellulose.
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CN108464952A (en) * | 2018-04-27 | 2018-08-31 | 花安堂生物科技集团有限公司 | A kind of film-forming composition and its cosmetics of application and its composition |
CN109395061A (en) * | 2018-12-12 | 2019-03-01 | 广州汇朗无纺制品有限公司 | A kind of composite membrane for the nursing of skin lesions of pemphigus vulgaris position |
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CN107673337A (en) * | 2017-11-02 | 2018-02-09 | 福州大学 | A kind of method that two-dimension nano materials are prepared using fibroin albumen stripping |
CN107673337B (en) * | 2017-11-02 | 2019-08-09 | 福州大学 | A method of two-dimension nano materials are prepared using fibroin albumen removing |
CN107951732A (en) * | 2017-12-26 | 2018-04-24 | 湖南御家化妆品制造有限公司 | Rectorite tearing slurry mask |
CN107951732B (en) * | 2017-12-26 | 2020-10-30 | 湖南御家化妆品制造有限公司 | Rectorite tearing slurry mask |
CN108464952A (en) * | 2018-04-27 | 2018-08-31 | 花安堂生物科技集团有限公司 | A kind of film-forming composition and its cosmetics of application and its composition |
CN109395061A (en) * | 2018-12-12 | 2019-03-01 | 广州汇朗无纺制品有限公司 | A kind of composite membrane for the nursing of skin lesions of pemphigus vulgaris position |
CN111823569A (en) * | 2019-03-26 | 2020-10-27 | 复旦大学附属华山医院 | Biological scaffold based on silk fibroin 3D printing and preparation method and application thereof |
CN111714679A (en) * | 2020-06-18 | 2020-09-29 | 广东景兴健康护理实业股份有限公司 | Preparation method and application of silk fibroin skin-beautifying sanitary towel or pad nursing base material |
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