CN100528091C - Cosmetic skin needle, its manufacturing method and use - Google Patents
Cosmetic skin needle, its manufacturing method and use Download PDFInfo
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- CN100528091C CN100528091C CNB2004100654242A CN200410065424A CN100528091C CN 100528091 C CN100528091 C CN 100528091C CN B2004100654242 A CNB2004100654242 A CN B2004100654242A CN 200410065424 A CN200410065424 A CN 200410065424A CN 100528091 C CN100528091 C CN 100528091C
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Abstract
An epidermal needle device for beautifying skin is composed of a sheet-type bearing body and a needle array on said bearing body. Said needles can pass through the horny layer of skin but not in dermis layer, and are prepared from monosilicon material through etching, or from high-molecular material or other materials. With said device, the skin-beautifying nutrients, such as collagen, elastin, coenzyme Q10, etc, can be percutaneously absorbed by skin.
Description
Technical field
The present invention relates to a kind of percutaneous medium is introduced the apparatus of human body, be specifically related to a kind of epidermis needle that is used to improve looks, the present invention relates to manufacture method of this epidermis needle and uses thereof simultaneously.
Background technology
Anyone can not escape old and feeble destiny, and smoking and ultraviolet radiation can be accelerated the skin aging process, and along with the raising of people's living standard, beautifying skin more and more is subjected to people's attention.Though the intrinsic factor of skin aging are not clear fully as yet, proved that the minimizing of collagen protein and the loss of moisture content are the major reasons of skin aging.
The collagen elastic fiber can keep the elasticity and the toughness of skin, when collagen protein begins to reduce gradually, skin with regard to attenuation, become fragile, be easy to chap, these variations cause the generation of symptoms such as wrinkle, eye pouch, augnathus.People's health is to have hundreds of gal4 amino acids to constitute, and wherein collagen protein accounts for 30% and 40%, more contains the collagen protein more than 70% in the skin, and along with the minimizing of collagen protein, skin will produce catabiosis.Although also have many not sure factors at present, identifiable is that the wrinkle of skin surface is that collagen protein has best moisture retention because the corium collagen protein is aging formed, is to make skin histology keep the main matter of elasticity and austerity.
Glass acid extensively is present in the human body with the form of salt, is the main component that constitutes intercellular matrix and extracellular matrix, the straight chain polymer mucopolysaccharide of being made up of for disaccharidase unit glucuronic acid-N-n acetylglucosamine n.Preserving moisture is its unique effect, because its molecular structure can carry the moisture content of volume more than 1,000 times own, is responsible for the supply dermal tissue and keeps skin elasticity.Hyaluronic acid sodium is the inherent biological substance of skin, uses the cosmetics that contain hyaluronic acid sodium can replenish the endogenic hyaluronic acid sodium of skin, promotes the supply of skin-nourishing and the drainage of refuse, thereby can prevent skin aging that skin care plays effects of beautification and nourishing face.
Many beautifying nourishing materials, comprise that collagen protein, hyaluronic acid sodium, elastin laminin, coenzyme Q10, vitamin sugar esters bioactivator, botulinum toxin (as Botox), hyaluronic acid (as Restylane) wait other nutritional labeling, because molecular weight ratio is big or hydrophilic is more intense, be made into unguentum, water preparation or general patch when using, the content that effective ingredient penetrates into skin seldom can not effectively be brought into play the function of these nutrient substance.Therefore many beautifying nourishing materials are made into the injection use, and are inconvenient but injection uses, the personnel operation that needs Special Training to cross, and also user has pain.
Therefore, seeking does not a kind ofly have pain, makes the beautifying nourishing material can break through the means that skin barrier is utilized by human body, can satisfy the demand of people to beauty treatment.
Summary of the invention
The object of the invention provides a kind of cosmetic skin needle, can the transdermal horny layer, beautifying nourishing material percutaneous is introduced, and realize not having pain and effective beautifying skin.
Another object of the present invention provides the preparation method of this cosmetic skin needle.
A further object of the present invention provides the purposes of this cosmetic skin needle.
For achieving the above object, the technical solution used in the present invention is: a kind of cosmetic skin needle, constitute by laminar supporting mass and the needle body array that is distributed on the supporting mass, each needle body tip in the described needle body array is 10 nanometers～20 micron, the bottom is 20～200 microns, highly is 50～400 microns.
In the technique scheme, described needle body array and supporting mass can constitute by single crystal silicon material is integrally formed, and the shape of described needle body is selected from taper shape, polygonal taper.
Perhaps, described needle body array and supporting mass also can constitute by macromolecular material is integrally formed, and the shape of described needle body is selected from taper shape, polygonal taper.
For obtaining above-mentioned cosmetic skin needle, the present invention obtains the needle body array based on Micrometer-Nanometer Processing Technology by modes such as photoetching, wet method or dry etchings.Its preparation technology is:
A kind of preparation method of cosmetic skin needle, employing monocrystal silicon is raw material, comprises the following steps:
(1) generates protecting film
With the silicon chip after purifying through 800～1100 ℃ of high-temperature thermal oxidations, at superficial growth one layer thickness of silicon chip be
Silicon dioxide film;
(2) photoetching
Coat the layer of even photoresist on the silicon dioxide film of one side, prebake covers a mask that has a needle body arranged in arrays pattern on the silicon chip that scribbles photoresist and exposes, and develops then and dries, and forms required pattern;
(3) remove silicon dioxide film
Etching is carried out in exposure place, till being removed to the silicon dioxide layer of exposure place;
(4) form the needle body array with etching method
Monocrystal silicon to exposure place is etched to desired depth, again needle body further is etched to needle point less than 10 microns, obtains the needle body array;
(5) the thing compatibility of looking unfamiliar is handled to the needle body tabulation, promptly obtains required monocrystal silicon cosmetic skin needle.
In the technique scheme, the method that adopts in each step is prior art, usually, silicon chip adopts the silicon single crystal wafer of twin polishing, thickness is 350～750 microns, can adopt standard cleaning liquid RCA1 (water: ammonia: the mol ratio of hydrogen peroxide is 5: 1: 1) and RCA2 (water: hydrochloric acid: the mol ratio of hydrogen peroxide is 5: 1: 1) to clean, with deionized water wash clean and dehydrate; During photoetching, on silica coating, evenly be coated with the photoresist of one deck 1～10 micron thickness with spin-coating method, 60～130 ℃ of preliminary dryings 1～20 minute, with have design the mask silicon chip that covers photoresist expose 1～100 second (exposure place is a pattern), develop then and 60～150 ℃ of oven dry, form required pattern, pattern can be the filled circles that is arranged in array, square, triangle, rhombus or rectangle etc.; Corrosive liquid that adopts in etching process and the corrosion inhibiter that adds wherein all are known technologies for a person skilled in the art; The length of the epidermis needle needle body that obtains is decided by etching depth, generally between 50～400 microns.
Further technical scheme, the mixed liquor that is etched to ammonium fluoride and Fluohydric acid. in the described step (3) carries out wet etching silicon dioxide to exposure place, and mixed liquor (BOE solution) can adopt the 49% Fluohydric acid. preparation of 40% ammonium fluoride and 1 weight portion of 6 weight portions.
Perhaps, being etched to fluoroform or tetrafluoromethane in the described step (3) carried out dry etching silicon dioxide to exposure place; Also can adopt ion beam that etching is carried out in exposure place and form required pattern.
In the technique scheme, etching method in the described step (4) is, obtain the needle body of the vertex of a cone and solid epidermis needle array earlier with deep ion reaction isotropism and anisotropic etching process, the needle point that further is etched to needle body again is less than 10 microns, obtain miniature solid silicon pin array chip, one of following technology is adopted in described further etching: with the mixed liquor wet etching of Fluohydric acid., nitric acid and glacial acetic acid; Use the potassium hydroxide solution wet etching; Mix use with wet etching with the etching of deep ion reaction isotropism technology.
In the technique scheme, the described surface biological compatibility is treated to, and utilizes low-pressure chemical vapor deposition systems approach (LPCVD method) deposition one deck silicon nitride film on the needle body surface that obtains, and perhaps utilizes sputtering method to form layer of metal titanium thin film.
The present invention provides the preparation method of another kind of cosmetic skin needle simultaneously, is master tooling with the cosmetic skin needle that obtains in the technique scheme, obtains the nickel mould by electrocasting, and reuse injection moulding or pressure sintering obtain the cosmetic skin needle of macromolecular material.Electrocasting wherein can be, plate one deck conductive layer such as golden film at monocrystalline silicon surface, utilize the plating of standard or chemical plating at the metallic nickel of monocrystal silicon epidermis needle superficial growth one layer thickness then greater than 1.5 millimeters, above-mentioned electroforming thing is boiled removal monocrystal silicon in 30%～50% potassium hydroxide solution, promptly obtain the nickel mould.
The invention provides the application of a kind of cosmetic skin needle in macromole beauty and make-up nutriment transdermal absorption system.
Its adoptable method is:
(1) adsorbing the biocompatibility macromolecule solution film forming agent that contains nutrient substance in right amount on the epidermis needle, natural drying is made the thin film paster.
(2) epidermis needle separates use with nutrient substance, at first penetrates keratodermatitis in the place that needs supply nutrition with epidermis needle, forms the provisions passage, and gel, unguentum or the water preparation that will contain nutrient substance then smoothen in epidermis needle does exhausted place.
Biocompatibility macromolecule polymer wherein, be the excipient substance that in pharmacopeia, allows use, as carbomer (Carbomer), chitosan (chitosan), the basic cellulose of carboxylic second (third), chitin, glucosan, b-cyclodextrin, Poly-L-lactic acid, xanthan gum, polyvinylpyrrolidone, polyaminoester etc.
In the technique scheme, described beauty and make-up nutriment comprises collagen protein, hyaluronic acid sodium, elastin laminin, coenzyme Q10, vitamin sugar esters bioactivator, botulinum toxin (as Botox), hyaluronic acid (as Restylane), improves the nutriment (as Rogaine) of alopecia; Described beauty and make-up nutriment can be attached on the cosmetic skin needle and be used in combination with cosmetic skin needle, also can be made into unguentum, water preparation or general patch and use on the skin after the cosmetic skin needle processing.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
(1) the present invention allow strong being difficult to of beautifying nourishing material such as collagen protein, glass acid and macromole or hydrophilic see through skin diffusion material (as, protein, polypeptide, polysaccharide etc.) import in the skin effectively.The epidermis needle preparation has solved in present beautifying nourishing material and the drug transdermal release tech because the key issue of the material Transdermal absorption difficulty that the barrier action of epiderm skin mesocuticle causes.During use, epidermis needle only penetrates drug diffusion is played the keratodermatitis of barrier action and do not penetrate skin corium, syringe needle does not touch the skin corium of abundant nerve and blood capillary, and nutrient mass-energy is diffused into the skin depths rapidly, can bring into play the effect that nutrient substance is preserved moisture and improved looks effectively.The epidermis needle preparation not only can make low-molecular-weight nutrient substance transmit effectively, the more important thing is that the material that can make macromole beautifying nourishing material and strong being difficult to of hydrophilic see through skin diffusion also can transmit effectively.The epidermis needle preparation has solved in the present nutrient substance transdermal release technology because the key issue of the material Transdermal absorption difficulty that the barrier action of epiderm skin mesocuticle causes.
Different with ejection preparation, the epidermis needle preparation does not almost have misery, does not generally need to do hypersensitive test, more can accept for consumers in general.This method more can promote beautifying nourishing material Transdermal absorption than general beauty and make-up unguentum, water preparation or general patch, and not only cheap but also safety.
(2) technology of the present invention is simple, and is cheap, is suitable for producing in batches, and the epidermis needle ruggedness is good, is specially adapted to the transdermal release of nutrient substance such as cosmetics.
Description of drawings
Accompanying drawing 1 is the monocrystal silicon cosmetic skin needle array scanning Electronic Speculum figure of the embodiment of the invention one;
Accompanying drawing 2 is the processing technology flow process diagram signal of monocrystal silicon epidermis needle array shown in the present;
Accompanying drawing 3 is the macromolecular material cosmetic skin needle array scanning Electronic Speculum figure of the embodiment of the invention two;
Accompanying drawing 4: with bovine serum albumin and botulinum toxin is the rats in vitro transdermal release curve of model nutrient substance, wherein, and ■, bovine serum albumin; ▲, botulinum toxin
Accompanying drawing 5: the different occupation modes of cosmetic skin needle are to the influence of transdermal, wherein, *, epidermis needle and nutrient substance separate the gel of use; ■, nutrient substance are adsorbed on the epidermis needle surface
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: the making of tapered solid monocrystal silicon cosmetic skin needle
Shown in accompanying drawing 1 and accompanying drawing 2, the monocrystal silicon of single-sided polishing＜100〉type, 500 micron thickness are raw material.At first with containing 5 parts of deionized waters, the cleanout fluid of a 30wt% hydrogen peroxide and a 30wt% ammonia cleans up under near 80 ℃ condition monocrystal silicon, then 150 ℃ of dryings 10 minutes.The silicon dioxide layer of about 1.5 micron thickness through 900～1100 ℃ of high-temperature thermal oxidations in monocrystal silicon＜100 the type superficial growth forms; On silicon dioxide film, coat the Shipley1818 photoresist of layer of even 1～2 micron thickness with spin-coating method, 90 ℃ of preliminary dryings (soft baking) 5 minutes, forming 80 * 80 arrays, diameter with one in 1 square centimeter unit is that 150 microns, spacing are that the mask of 200 microns filled circles (uses quartz glass in the semiconductor standard processes, be coated with the chromium film above, the mask material is general) cover monocrystal silicon＜100 that have photoresist〉the type substrate exposed 4 seconds, develop then and 120 ℃ of oven dry about 30 minutes; Utilize ion(ic) etching (RIE) technology that the etch silicon dioxide film is carried out in exposure place, keep residual photoresist, do to carve (DRIE) with dark reactive ion and carry out etching silica-based.After obtaining the vertex of a cone, the deep reactive ion anisotropic process (Bosch technology) of the smooth treatment of migrating again continues etching silicon substrate to the degree of depth and stops etching after 200 microns, this silicon chip is carried out oxidation at 1100 ℃, form the silicon dioxide film of about 1 micron thickness of one deck at silicon face, again silicon chip is placed on etching in 25 ℃ the BOE solution and obtained epidermis needle (top is that sharp cone distal, needle body are columniform) in 8～10 minutes, as the aciculiform of accompanying drawing 1 as nail shape.Utilize vacuum sputtering to plate the thick Titanium of one deck 20nm on the surface of silicon pin then and form cosmetic skin needle with biocompatibility.
Embodiment two: the making of macromolecular material cosmetic skin needle
The monocrystal silicon cosmetic skin needle that obtains with embodiment one is a master mold, plate one deck gold film on its surface as conductive layer, utilize then and electroplate at the about 1.5 millimeters metallic nickel of monocrystal silicon epidermis needle superficial growth one bed thickness, above-mentioned electroforming thing is boiled removal monocrystal silicon in 30%～50% potassium hydroxide solution, obtain the nickel mould.
Adopt macromolecular material, use the vacuum injection method, utilize above-mentioned nickel mould to prepare the cosmetic skin needle of macromolecular material, as shown in Figure 3.
Embodiment three: be the rats in vitro transdermal release curve of model nutrient substance with bovine serum albumin and botulinum toxin
Bovine serum albumin and botulinum toxin solution are as the model nutrient substance.
Remove one of mao big Corium Mus, horny layer upwards places the diffusion cell mouth, solid epidermis needle with embodiment one preparation (has 400 pins on 4 square millimeters of areas, spacing between the pin is 200 microns) put thereon, make it on skin, prick out micropore with have gentle hands by epidermis needle, but transdermal not, (concentration of each material of supply chamber is 0.1mM to keratodermatitis towards the medicine supply chamber, 1ml), skin corium is towards medicine receiving chamber, in receiving chamber, fill it up with the phosphate buffer (pH7.4) that is heated to 37 ℃ in advance, and with sealing the film phonograph seal sample tap, be placed in 37 ℃ the constant temperature water bath.Under continue stirring, take out 0.2mL at interval respectively in certain hour and accept medium and measure nutrient concentrations, and replenish isopyknic phosphate buffer immediately, with supply chamber not the phosphate buffer of Ensure Liquid material be contrast.Carry out the big Corium Mus permeability test of pore-free simultaneously.This tests triplicate, and experimental result as shown in Figure 4.When skin did not have epidermis pinprick hole, bovine serum albumin and botulinum toxin almost can not see through skin, and behind epidermis pinprick hole, the accumulation permeability of nutrient substance reaches 34% and 28% respectively in the time of 24 hours.
Embodiment four: the different occupation modes of epidermis needle are to the influence of nutrient substance percutaneous transmitance
(medical board animal science portion of Beijing University) is animal model with new zealand white rabbit, the labelling bovine serum albumin (F: P=1.3) be dissolved in be mixed with in 1% chitosan (pH 5) solution contain the 2.86mg/ml bovine serum albumin mixed liquor as the nutrient substance model, adopt the epidermis needle paster of 1200 pin/0.5 square centimeter, every agreement that contracts a film or TV play to an actor or actress contains 180 μ g labelling bovine serum albumins. study its Transdermal absorption situation under the micropin effect.Paster one is bovine serum albumin/chitosan to be added to epidermis needle surface natural drying at room temperature make the macromolecule membrane epidermis needle preparation that contains bovine serum albumin.Paster two is that epidermis needle separates use with bovine serum albumin/chitosan, and bovine serum albumin/chitosan is made into gel paster, removes epidermis needle after at first epidermis needle being acted on skin, then gel paster is sticked.Accompanying drawing 5 was presented at the paster effect in the time of 24 hours, and the permeability of epidermis needle preparation is 12%, and the permeability of gel paster is 29%.Therefore can be made into the epidermis needle dosage form of different demands as required.
Claims (6)
1. the preparation method of a cosmetic skin needle, employing monocrystal silicon is raw material, comprises the following steps:
(1) generates protecting film
With the silicon chip after purifying through 800～1100 ℃ of high-temperature thermal oxidations, be 1000 at superficial growth one layer thickness of silicon chip～
Silicon dioxide film;
(2) photoetching
Coat the layer of even photoresist on the silicon dioxide film of one side, prebake covers a mask that has a needle body arranged in arrays pattern on the silicon chip that scribbles photoresist and exposes, and develops then and dries, and forms required pattern;
(3) remove silicon dioxide film
Etching is carried out in exposure place, till being removed to the silicon dioxide layer of exposure place;
(4) form the needle body array with etching method
Monocrystal silicon to exposure place is etched to desired depth, again needle body further is etched to needle point less than 10 microns, obtains the needle body array;
(5) the thing compatibility of looking unfamiliar is handled to the needle body tabulation, promptly obtains required monocrystal silicon cosmetic skin needle.
2. the preparation method of cosmetic skin needle according to claim 1, it is characterized in that: the mixed liquor that is etched to ammonium fluoride and Fluohydric acid. in the described step (3) carries out wet etching silicon dioxide to exposure place.
3. the preparation method of cosmetic skin needle according to claim 1, it is characterized in that: being etched to fluoroform or tetrafluoromethane in the described step (3) carried out dry etching silicon dioxide to exposure place.
4. the preparation method of cosmetic skin needle according to claim 1, it is characterized in that: the etching method in the described step (4) is, obtain the needle body of the vertex of a cone and solid epidermis needle array earlier with deep ion reaction isotropism and anisotropic etching process, the needle point that further is etched to needle body again is less than 10 microns, obtain miniature solid silicon pin array chip, one of following technology is adopted in described further etching: with the mixed liquor wet etching of Fluohydric acid., nitric acid and glacial acetic acid; Use the potassium hydroxide solution wet etching; Mix use with wet etching with the etching of deep ion reaction isotropism technology.
5. the preparation method of cosmetic skin needle according to claim 1, it is characterized in that: the described surface biological compatibility is treated to, utilize low-pressure chemical vapor deposition systems approach deposition one deck silicon nitride film on the needle body surface that obtains, perhaps utilize sputtering method to form layer of metal titanium thin film, thickness is 0.05～1 micron.
6. the preparation method of a cosmetic skin needle is characterized in that: the cosmetic skin needle that obtains with the arbitrary method in the claim 1 to 5 is a master tooling, obtains the nickel mould by electrocasting, and reuse injection moulding or pressure sintering obtain the cosmetic skin needle of macromolecular material.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830496A (en) * | 2006-04-10 | 2006-09-13 | 清华大学 | '-'-shaped structure three-dimensional micre solid, hollow silicone meedle orknife |
| CN102765695B (en) * | 2012-08-06 | 2015-05-13 | 中北大学 | Method of manufacturing wafer-level low-dimensional nano-structure based on self-focusing of electrostatic field singular-point |
| CN102931070B (en) * | 2012-11-09 | 2015-06-10 | 天水天光半导体有限责任公司 | Silicon substrate isotropic wet etching process |
| US11083515B2 (en) | 2013-12-18 | 2021-08-10 | Novoxel Ltd. | Methods and devices for thermal tissue vaporization and compression |
| CN104587567B (en) * | 2015-01-05 | 2018-01-05 | 华南师范大学 | A kind of preparation method of micro hollow silicon needle |
| CN112399908B (en) * | 2018-06-25 | 2023-04-07 | 考里安公司 | Method of forming master mold, casting mold, and method of making microstructure array |
| CN110962258A (en) * | 2019-12-10 | 2020-04-07 | 维沃移动通信有限公司 | Manufacturing method of injection mold, processing equipment of shell and shell of electronic equipment |
| CN111329833A (en) * | 2020-03-04 | 2020-06-26 | 苏州纳生微电子有限公司 | Application of physical transdermal technology in auxiliary nutrition supplement |
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Assignee: Suzhou Natong Biological Nanometer Technology Co., Ltd. Assignor: Nasheng Microelectronics (Suzhou) Co., Ltd. Contract record no.: 2010320000513 Denomination of invention: Cosmetic skin needle, its manufacturing method and use Granted publication date: 20090819 License type: Exclusive License Open date: 20050608 Record date: 20100504 |