CN1717306A - Microprotrusion structure and process for producing the same - Google Patents
Microprotrusion structure and process for producing the same Download PDFInfo
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- CN1717306A CN1717306A CN 200380104124 CN200380104124A CN1717306A CN 1717306 A CN1717306 A CN 1717306A CN 200380104124 CN200380104124 CN 200380104124 CN 200380104124 A CN200380104124 A CN 200380104124A CN 1717306 A CN1717306 A CN 1717306A
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Abstract
Hydrophobic organic solvent solution containing dissolved polymer is poured on a baseplate, and the organic solvent is evaporated in the atmosphere containing hygroscopic water; the hygroscopic water contained in the atmosphere on the surface of the poured solution is condensed and dews into fine drops on the surface of the poured solution; the fine drops are dispersed on the surface of the poured solution or in the poured solution to form the thickest interstitial texture; the dew and the fine drops dispersed on the surface of the poured solution or in the poured solution are evaporated to get multihole honeycomb structures with drops as molds; subsequently, each of the structure is divided into at least two parts in the direction of thickness by means of stripping to get fine lug bosses regularly arranged on the stripping face or membrane structures of anisotropic fine lug bosses. As the structures are provided with unique fine structures on the surfaces, compared with the membranoid substance without fine structures or structures with irregular lug bosses, the structures have unique surface characteristics, and feel remarkable by hands. The structures are expected to have special functions. The invention is applicable for various fields, and makes great contributions to technological advance.
Description
Technical field
The present invention relates to presenting the microprotrusion structure of extremely special surface state, porous membrane structure and the manufacture method thereof that to be ultramicrofine projection arrange with given interval rule ground at substrate surface.Further relating to ultramicrofine projection arranges with given interval rule ground and has the porous membrane structure and a manufacture method thereof of hydrophobic surface or hydrophilic surface at substrate surface.Generally speaking, relate to following microprotrusion structure, because the specificity of its surface configuration, with do not have object micro crowning or the scrambling raised structures and compare, by the excellent effect of expectation performance, be expected to thus to use and be used in and cultivate various technical fields such as semiconductor that engineering, medical timbering material are representative, recording materials, screen, isolator, amberplex, battery diaphragm material, display, optical material, waveguide, acoustic instrument material with cell.
Background technology
Recently, be the center with the biochemical field, as the cell engineering, cultivate the timbering material in the engineering, propose and delivered the base material that the formation of rule of surface ground is being listed as fine hole etc. side by side in succession at various academic documents, technical report etc. as hereinafter described.
Each base material that these are suggested, owing to have special surface texture, so not only in medical field, but also studying application, be applicable to various technical fields, comprise that for example semiconductor, advanced low-k materials, electronic console are studied with multi-purpose uses such as base material, application with scattering layer, magnetic recording material, photonic crystal, cell cultivation, it is gazed at by the people as one of promising material.
But, if make this structure that is arranged with minute aperture regularly, then there is the problem of aspect as described below with common Micrometer-Nanometer Processing Technology, thus very difficult, see the suitable method of can not saying so really from real angle.For example, as the known processing method that employing lithography and laser are arranged of fine machining method, but for these methods, not only be confined to its machinable material, and to form a great deal of even can be described as countless fine and closely woven microfabrication and form operation such as microfabrication regularly be difficulty very.Even undertaken by suitable skilled person, many, the considerable time of needs of its manufacturing procedure also not hard to imagine.Certainly also need expensive.
With respect to this, the also known method that has so-called employing phase separation method to form fine pattern, but the gained surface state is existing problems aspect repeated, and what obtain is uneven pattern, and therefore the fine pattern formation technology as the structure that obtains having ad hoc rules is inadequate.
Generally speaking, use these Surface Machining of fine pattern technology in the past, need very high-caliber technology, many problems such as existence can't be produced in a large number, cost height.
With respect to as mentioned above, recently in various documents report have by at the thin solution of solid substrate top-pour polymer injection, can form the method for patterning of fine rule fairly simplely.The seminar that comprises inventor etc. has also proposed this method (with reference to non-patent literature 1).This method is by cast thin solution of macromolecule and evaporating solvent, forms point (projection) pattern of fine structure on high molecular polymer.But, according to the method in this motion, can not control the arrangement of its projection and form the fine point of tool systematicness, therefore abundant inadequately.
In addition, as fine structure, also proposed to form perforated membrane (non-patent literature 2, non-patent literature 3) with fine honeycomb-like pattern.This method is to utilize to have from the strong part of cohesive force simultaneously and show the particular polymer of the part of flexibility, and this polymer dissolution in hydrophobicity organic solution, and is formed corresponding pattern by pouring into a mould.
For this method, seminar such as the inventor also concentrate on studies, consequently, by selecting particular polymers as the polymer of pouring into a mould, successfully make microstructure, and its result is delivered and be reported in (non-patent literature 4, non-patent literature 5) on the technical papers with distinctive alveolate texture.
Promptly, constituent as this polymer, use with hydrophilic acrylamide polymer as main chain backbone and have simultaneously as the dodecyl of hydrophobic side chains with as lactose base or the amphipathic nature polyalcohol of carboxyl or the ionic complex compound of anionic polysaccharide such as heparin and dextran sulfate and long chain alkyl ammonium salt of hydrophilic side-chains, the porous membrane that successfully obtains having the honeycomb-like pattern structure.
The inventor finds that also the porous honeycomb structure film of being made by various Biodegradable polymer is very promising material as the cell culture medium material, has applied for patent (with reference to patent documentation 1) based on this.
In this application patent, the preparation method that the inventor proposes is, the casting film that carries out the hydrophobicity organic solution that over-richness regulates is blowed the air of high humility, perhaps just be placed on the high humility making of getting off, this method be extremely easy and aspect manufacturing cost the also technology of gainful excellence.
At this moment, become the drop diameter of the mold in hole, can therefore can be described as the motion that is imbued with very much unique excellence in the aperture of the scope control perforated membrane of 0.1～100 μ m by change.
Non-patent literature 1:Chemistry Letters, 821,1996.
Non-patent literature 2:Science, 283,373,1999.
Non-patent literature 3:Nature, 369,387,1994.
Non-patent literature 4:Thin Solid films, 327,829,1998.
Non-patent literature 5:Moleculer Cryst.Liq.Cryst.322,305,1998.
Patent documentation 1: the spy opens the 2001-157574 communique
The present invention is exactly based on above-mentioned research, motion, and it is further developed, the object with special surface state that presents novel fine structure is provided, promptly not merely presents alveolate texture and also be formed with the structure of micro crowning on its surface with extremely simple method.
And then, provide with extremely simple method to make this raised structures have anisotropic structure, be imbued with hydrophobic microprotrusion structure and be imbued with hydrophilic microprotrusion structure.
Summary of the invention
Therefore, the result that the inventor will concentrate on studies, above-mentioned technology are prerequisite, and further develop, consequently, successfully obtain having disparate surfaces characteristic up to now, be micro crowning structure arranged body regularly.Promptly, hydrophobic organic solvent solution from polymer, obtain porous membrane as the alveolate texture of intermediate, again by strip operation with this intermediate at its thickness direction two parts that are divided into two, thereby successfully make structure with extremely special micro crowning.
The present invention carries out with regard to the opinion that obtains during being based on this success and hitting pay dirk, and finishes by adopting following formation.
(1) a kind of microprotrusion structure is characterized in that, is arranged with micro crowning regularly at substrate surface.
(2) a kind of microprotrusion structure with hydrophobic surface is characterized in that, is arranged with micro crowning regularly at substrate surface, and has hydrophobicity.
(3) microprotrusion structure on a kind of possess hydrophilic property surface is characterized in that, is arranged with micro crowning regularly at substrate surface, and by hydrophilicity-imparting treatment and possess hydrophilic property.
(4) according to any described microprotrusion structure in above-mentioned (1)～(3), it is characterized in that described base material and micro crowning are made of polymer, and contain material modified as required.
(5) according to any described microprotrusion structure in above-mentioned (1)～(4), it is characterized in that, described base material and micro crowning thereof are by being presoma to contain polymer and to contain material modified porous honeycomb structure body as required, this presoma are peeled off at thickness direction obtain.
According to above-mentioned (5) described microprotrusion structure, it is characterized in that (6) described presoma and the base material that is obtained by this presoma are the film shape.
According to any described microprotrusion structure in above-mentioned (1)～(5), it is characterized in that (7) described micro crowning is that the length of 0.1～50 μ m, tip portion is that 0.01～20 μ m, projection are spaced apart 0.1～100 μ m and arrange with length.
According to above-mentioned (4) or (5) described microprotrusion structure, it is characterized in that (8) described polymer contains hydrophobicity or Biodegradable polymer, and contains amphipathic nature polyalcohol.
(9) according to above-mentioned (8) described microprotrusion structure, it is characterized in that, containing of described hydrophobic polymer and/or Biodegradable polymer and amphipathic nature polyalcohol proportionally be, hydrophobicity and/or Biodegradable polymer are 50～99%, and remainder is an amphipathic nature polyalcohol.
(10) according to above-mentioned (8) or (9) described microprotrusion structure, it is characterized in that,, use polyester, poly-(methyl) acrylate, Merlon or polystyrene as described hydrophobicity or Biodegradable polymer.
(11) according to any described microprotrusion structure in above-mentioned (1)～(10), it is characterized in that, to be dissolved with the hydrophobic organic solvent solution casting of polymer on substrate, containing this organic solvent of evaporation under the atmosphere of hygroscopic moisture, make that contained hygroscopic moisture becomes small water droplet in this potting syrup surface condensation, dewfall in this potting syrup surface atmosphere, in this potting syrup surface or potting syrup, be dispersed into the closeest interstitital texture; Then with this dewfall and be dispersed in small water-drop evaporation in potting syrup surface or the potting syrup, obtaining with the water droplet is the porous honeycomb structure body of mold; Then by this structure is peeled off and is separated into two parts at least at thickness direction, obtain being separated in the honeycomb molded body that release surface formed and be arranged with micro crowning regularly according to described.
According to any described microprotrusion structure in above-mentioned (1)～(11), it is characterized in that (12) any direction beyond the described micro crowning directed in orthogonal direction is set to and has anisotropy.
(13) according to above-mentioned (12) described microprotrusion structure, it is characterized in that, the fine projection of described anisotropy is when thickness direction is peeled off porous honeycomb structure body as the micro crowning presoma, and any direction that points to beyond the thickness direction for the micro crowning that makes generation obtains by the lift-off processing that contains crosscut stress.
According to above-mentioned (3) described hydrophilic fine raised structures body, it is characterized in that (14) described hydrophilicity-imparting treatment is any one or these the combination in chemical sex modification processing, ozone Oxidation Treatment, the alkali treatment.
(15) a kind of manufacture method of microprotrusion structure, it is characterized in that, to be dissolved with the hydrophobic organic solvent solution casting of polymer on substrate, containing this organic solvent of evaporation under the atmosphere of hygroscopic moisture, make that contained hygroscopic moisture becomes small water droplet in this potting syrup surface condensation, dewfall in this potting syrup surface atmosphere, in this potting syrup surface or potting syrup, be dispersed into the closeest interstitital texture; Then with this dewfall and be dispersed in small water-drop evaporation in potting syrup surface or the potting syrup, obtaining with the water droplet is the porous honeycomb structure body of mold; Then, obtain being arranged with regularly the honeycomb molded body of micro crowning thus in release surface by this structure is peeled off and is separated into two parts at least at thickness direction.
According to the manufacture method of above-mentioned (15) described microprotrusion structure, it is characterized in that (16) described polymer is made of hydrophobicity or Biodegradable polymer and amphipathic nature polyalcohol, and is mixed with material modified as required.
(17) according to the manufacture method of above-mentioned (16) described microprotrusion structure, it is characterized in that, the proportion of composing of described hydrophobicity or Biodegradable polymer and amphipathic nature polyalcohol is, hydrophobicity or Biodegradable polymer are 50～99%, and remainder is an amphipathic nature polyalcohol.
According to the manufacture method of above-mentioned (16) or (17) described microprotrusion structure, it is characterized in that (18) described hydrophobicity or Biodegradable polymer are to be the polymer formation of polyester, poly-(methyl) acrylate or polystyrene by basic framework.
According to the manufacture method of above-mentioned (15) described microprotrusion structure, it is characterized in that (19) the described atmosphere that contains hygroscopic moisture is that to be adjusted to relative humidity be 50～95% atmosphere.
According to the manufacture method of above-mentioned (15) or (19) described microprotrusion structure, it is characterized in that (20) described atmosphere is common atmosphere.
According to the manufacture method of above-mentioned (15) described microprotrusion structure, it is characterized in that (21) mode of operation of the described organic solvent of evaporation is to be undertaken by the atmosphere that the evaporating surface to organic solvent blows high humility under the described atmosphere that contains hygroscopic moisture.
According to the manufacture method of above-mentioned (15) described microprotrusion structure, it is characterized in that (22) strip operation is to be undertaken by gluing bringing.
According to the manufacture method of above-mentioned (15) described microprotrusion structure, it is characterized in that (23) strip operation is to be undertaken by the dissolving of polymer.
According to the manufacture method of above-mentioned (15) described microprotrusion structure, it is characterized in that (24) strip operation is to be undertaken by ultrasonic irradiation.
(25) according to the manufacture method of any described microprotrusion structure in above-mentioned (15)～(24), it is characterized in that described micro crowning is to be that the length of 0.1～50 μ m, tip portion is that 0.01～20 μ m and pitch density are that 0.1～100 μ m forms and arranges with length.
According to the manufacture method of any described microprotrusion structure in above-mentioned (15)～(25), it is characterized in that (26) described micro crowning is set to the anisotropy with directed in orthogonal direction any direction in addition.
(27) according to the manufacture method of above-mentioned (26) described microprotrusion structure, it is characterized in that, described to have anisotropic micro crowning be to peel off when generating micro crowning as the porous honeycomb structure body of micro crowning presoma at thickness direction, and any direction that points to beyond the thickness direction for the micro crowning that makes generation carries out lift-off processing and obtains by applying crosscut stress.
The present invention is by obtaining having the film of the fine regular pattern of alveolate texture to the solid substrate as mold, with the thin solution casting of polymer with steam, again it is peeled off at thickness direction, thereby be provided at the brand-new new material that micro crowning was arranged and be formed with to the film release surface regularly, because its surface characteristic has remarkable characteristic when tool rule micro crowning structure, so in following listed field etc., brought into play special effect by expectation.Promptly waited in expectation and be used for chemical valve, the DNA chip, protein-chip, the cyto-diagnosis chip, cell is cultivated engineering, medical timbering material, semiconductor, recording materials, isolator, amberplex, battery diaphragm material, display, optical materials such as optical waveguide, catalyst carrier, the cell culture medium material, anisotropic solid, conductive material, fluid channel etc., because the mobile biochip surface that is controlled at fixed-direction that is suitable for material can be provided, only reduce the surface on low frictional resistance surface etc. of the resistance of air or water, thereby bring into play special effect at fixed-direction.This effect is a part only, because raised structures can also be used for various operations such as gas-liquid contact reaction or liquid liquid haptoreaction, being waited in expectation promotes the contact effect or help evaporation of liquid, dry lock out operation etc. greatly.
Also have, owing to be formed at the hole and the connected micro crowning on surface, the liquid that flows through non-raised sides surface can be discharged to space outerpace through via hole and micro crowning, it is also conceivable that according to this phenomenon to be used for distinctive stream etc.Promptly act on the medical material of designer worker's blood vessel, artificial kidney etc. except using, by the control micro crowning, can produce artificial ciliary movement, so it is also conceivable that the motion class material that is used for small scale robot or small-sized biorobot etc. etc. based on effects such as at random making the projection activity.And then, in filter operation,, therefore can be used for the little filter of design pressure loss etc. because above-mentioned formation can make the discharge of liquid advantageously carry out.Also have,, can be provided for multi-purpose strong new material as the material of various form owing to can freely make its shape.From now on, used and be used in the new material in the microtechnology field that comes to life along with the development of nanometer technology by waiting in expectation, and the special effect that produces because of the specificity of surface configuration of performance.
Particularly, for described microprotrusion structure,, require its technical field enlarging owing to require the demand of hydrophobic surface to strengthen in recent years with hydrophobic surface.About its trend with use and in various documents, to introduce, and introduce and enumerated varied application examples (for example, the 1. up-to-date trend of high hydrophobic technology-from the super hydrophobic material to the more recent application, eastern beautiful research center, calendar year 2001; 2. material is integrated, and calendar year 2001 14 is rolled up 10 monthly magazines).But processing method is up to now limited by machinable material all, and manufacturing procedure needs long-time and cost.(2) of the present invention and related invention thereof provide the new material corresponding to this demand, and can provide with simple formation means, are waited in expectation from now on to be extensive use of in various fields, for development is contributed.
To hydrophobic demand, requirement is also improving with the demand of the compatibility of water in certain fields with respect to above-mentioned.For example, in the design of filter for filtration, need to improve the separative efficiency of moisture, require material is set at hydrophily from the filter material surface.(3) of the present invention and the relevant invention that is set at the possess hydrophilic property surface thereof just provide the new material that is imbued with hydrophilic surface corresponding to having of this.
Description of drawings
Fig. 1 carries out the image that SEM observes to embodiment 1 described porous honeycomb structure body (film) that obtains and surface thereof on the experiment ware.
Fig. 2 be embodiment 1 described porous honeycomb structure body the SEM image (on) and the expression its three-dimensional structure SEM image (descending).
Fig. 3 is that the SEM that observes from tilted direction of the microprotrusion structure of the embodiment 1 that obtains after peeling off observes image.
Fig. 4 is the SEM image by the porous honeycomb structure body (film) of embodiment 2 described various polymer making.
Fig. 5 is the SEM image of microprotrusion structure that the porous honeycomb structure body (film) of embodiment 2 is made by tape stripping.
Fig. 6 is the SEM image of the microprotrusion structure of embodiment 3.
Fig. 7 is the SEM image of the microprotrusion structure that is obtained by the polymer dissolution method of embodiment 4.
Fig. 8 is the SEM image of the microprotrusion structure that is obtained by the ultrasonic irradiation method of embodiment 5.
Fig. 9 is the SEM image of the fine raised structures body of the anisotropy of embodiment 6.
Figure 10 (a) be the fine raised structures body of the anisotropy of embodiment 7 from directly over the SEM image observed, Figure 10 (b), (c) are the SEM images of 55 ° of observations of tilting.
The specific embodiment
Microprotrusion structure of the present invention is the operation making that promptly obtains the operation of porous honeycomb structure body and peel off it by two stage procedures, and it as mentioned above.Put down in writing its a succession of operation briefly at this operation below.
At first, be modulated at the material that has dissolved hydrophobicity or Biodegradable polymer and amphipathic nature polyalcohol in the hydrophobic organic solvent, it is cast on the substrate, relative humidity more than or equal to 50% atmosphere under slow this organic solvent of evaporation, perhaps come evaporating solvent by liquid level being blowed the high humility atmosphere gas, because its evaporation latent heat is at this potting syrup surface meeting condensation hygroscopic moisture, dewfall becomes small water droplet, is dispersed into the state of close interstitital texture thereby form water droplet in potting syrup surface or potting syrup; Then evaporate this dewfall and be dispersed in small water droplet in potting syrup surface or the potting syrup, obtaining with the water droplet is the porous honeycomb structure body of mold; Then this honeycomb molded body that obtains is pasted adhesive tape,, obtain being divided on the two-part release surface with this honeycomb molded body separated into two parts by stripping means such as stretchings owing to the alveolate texture micro crowning that the forms structure arranged body regularly that breaks.
Furthermore, obtain in the technology of porous honeycomb structure in the last period as mold with water droplet, by at potting syrup surface condensation and the small water droplet of dewfall, in potting syrup surface or potting syrup, be dispersed into the closeest interstitital texture, evaporate this water droplet again, the minute aperture that obtains having diameter and be 0.1～100 μ m has carried out the structure of close filling, has been the film like structures body of alveolate texture.In addition, as mentioned above, this technology is suggested based on particular polymers self, and be applied patent, but notice among the present invention, the honeycomb molded body (Fig. 1) that forms according to above-mentioned technology since with small water droplet as mold, so have the structure that a hole by 6 shore supports, its pillar has the structure (Fig. 2) that attenuates at the center.
Promptly, obtain extremely regular state and the structure that forms of fitly arranging of micro crowning structure on the plane of fracture of peeling off generation according to it by peeling off this porous honeycomb structure body.
The present invention's segment process after the technology of foregoing the last period further continues is finished, and by one section strip operation thereafter alveolate texture is broken, and obtains forming with given interval the structure of the micro crowning of given length based on this.
Fig. 1 represents to be created on the porous honeycomb structure body of the state in the experiment ware and it is enlarged twice state in proportion; Fig. 2 represents it with the further scale-up image of electron microscope (SEM) with represent the ideograph of this structure with three-dimensional structure.
Here, as hydrophobicity of using among the present invention or Biodegradable polymer, consider from dissolubility angle, be preferably Biodegradable aliphatic polyesters such as PLA, lactic acid ethanol copolymer, poly butyric, polycaprolactone, polyethylene glycol adipate, poly adipate succinic acid ester organic solvent; Aliphatic acid ester carbonates such as polymerized thylene carbonate butyl ester, polymerized thylene carbonate ethyl ester etc.; Polystyrene, polysulfones, poly-methyl cetyl siloxanes, polyvinylcarbazole, polymethylacrylic acid tetrahydrochysene chaff ester, polybutyl methacrylate, polymethyl methacrylate, Merlon etc.
As being used for amphipathic nature polyalcohol of the present invention, be not particularly limited, but consider preferred polyethylene/polypropylene glycol block copolymer from the angle of easy acquisition, be main chain backbone with the acrylamide polymer and have simultaneously as the dodecyl of hydrophobic side chains with as the lactose base of hydrophilic side-chains or the amphipathic nature polyalcohol of carboxyl, or with the ionic complex compound of anionic macromolecules such as heparin and nucleic acid such as dextran sulfate DNA or RNA and long chain alkyl ammonium salt, gelatin, collagen, albumin etc. with water soluble protein as amphipathic nature polyalcohol of hydrophily base etc.
When making becomes the porous honeycomb structure body thin film of microprotrusion structure of the present invention, must on polymer solution, form small water droplet particle, so need to use water-insoluble solvent as organic solvent.And, must be the material that can dissolve each polymer that uses.And then, preferably easily evaporation and by evaporation latent heat easily with the material of hygroscopic moisture condensation.
Then need not special restriction as long as possess these character, certainly preferably can simply obtained nontoxic material.Can enumerate as halogen such as chloroform, carrene, dichloroethanes specifically is organic solvent; Aromatic hydrocarbons such as benzene,toluene,xylene; Ester such as ethyl acetate, butyl acetate class; Water-insoluble ketone such as methyl iso-butyl ketone (MIBK); Carbon disulfide etc.These organic solvents can use separately, perhaps also can use the mixed solvent of these solvents of combination.
The concentration of both polymer of adding up to that are dissolved in the hydrophobicity of these solvents or Biodegradable polymer and amphipathic nature polyalcohol is preferably 0.01～20wt%, 0.1～10wt% scope more preferably.If polymer concentration is lower than 0.01wt%, then the mechanical strength of gained film is not enough, and is therefore also not preferred.In addition, if greater than 20wt%, then polymer concentration becomes too high, can't obtain sufficient alveolate texture.In addition, the ratio of components of hydrophobicity or Biodegradable polymer and amphipathic nature polyalcohol is 99: 1～50: 50 (wt/wt).If amphipathic nature polyalcohol then can't obtain uniform loose structure than less than 1, and, if it is the stability of the porous membrane that this ratio greater than 50, then obtains, especially mechanical stability are not good enough, therefore also not preferred.
Among the present invention, this polymer organic solvent solution is cast in makes porous membrane on the substrate.At this moment, as this substrate, the preferred organic solvent solution of the dissolve polymer that can avoid and the use material that dissolves mutually, corrode or react and its product brought the material of harmful effect such as pollution, chemical stabilization.Can enumerate the macromolecule of organic solvent resistance excellences such as inorganic material such as glass, metal, silicon chip, polypropylene, polyethylene, polyether-ketone, fluororesin.The substrate of more than enumerating is all illustrative to be with the situation of the surface of solids as substrate, but this substrate is not limited to the surface of solids.Promptly can also make liquid such as water, atoleine, liquid polyethers.After the beginning polymer solution is put on display on these liquid upper berths, with same operation, promptly under high humility atmosphere, evaporate organic solvent, obtaining with the water droplet is the porous honeycomb structure film of mold, adopts same strip operation to peel off this film then, forms micro crowning.When using liquid on the contrary as substrate, sprawl thereon polymer solution since its thickness can control by surface tension, so be preferred when making film.
For any substrate, can this structure be taken off from substrate separately and easily by the independence of performance as this porous honeycomb structure body thin film feature.
Among the present invention, can consider as follows about the mechanism that forms porous honeycomb structure.Owing to when hydrophobic organic solvent evaporates, capture latent heat, cause the temperature decline on casting film surface, condensate moisture makes small water droplet aggegation and attached to the polymer solution surface.By the effect of the hydrophilic parts in the polymer solution, the surface tension between water and the hydrophobic organic solvent reduces, and therefore is able to stabilisation when the aggegation of water particulate desire becomes one.Follow the solvent evaporation, be hexagonal drop and arrange with the closeest occupied state, last, water evaporates, and residual one-tenth polymer is with the form of the neat honeycomb arrangement of rule.Thereby as the environment of this film of modulation, preferred relative humidity is in 50～95% scopes.If less than 50%, then the dewfall on the casting film will be abundant inadequately; And if greater than 95%, then the control of environment becomes difficult, and not preferred.
Among the present invention, known in the explanation as described in front, so-called porous honeycomb structure body is meant and is the double-decker (with reference to Fig. 2) of two film overlaies up and down, pore is arranged between it regularly, each pore is by six roots of sensation shore supports, and its pillar has the state that attenuates at the center and the structure of structure.The structural reason that produces this complexity and rule is, make aerial moisture dewfall at the surperficial evaporation latent heat of the Polymer Solution of cast owing to solvent, with the fine and closely woven filling of water droplet of the fine and closely woven filling of hexagon, consequently the space beyond water droplet produces high molecular separating out.
Aperture and thickness for porous membrane, flow, temperature, the humidity of concentration, solvent types, liquid measure, atmosphere or institute's blow air by changing the liquid of pouring into a mould, be the evaporation rate of solvent or the control of combination of passing through to suit to dewfall speed, control the growth of the water droplet that will become the aperture mold, the evaporation rate of solvent, control aperture and other thus.So the aperture and the thickness of the porous membrane that will become the microprotrusion structure presoma that obtains are 0.1～100 μ m.
Be blown into the damp atmosphere on the film so long as airborne moisture is got final product in the humidity of film surface sweating, can be not limited to air for 20～100% relative humidity, also can use comparatively inert gasses such as nitrogen, argon gas according to temperature.
Be blown into the flow of the damp atmosphere on the film, so long as airborne moisture is got final product at the film surface sweating and the flow that can evaporate the solvent that is used to pour into a mould.
The temperature of the atmosphere when blowing damp atmosphere is so long as can evaporate the temperature of the solvent that is used to pour into a mould and get final product.
Method as peeling off the porous membrane surface is not particularly limited, and can enumerate as adhesive tape being sticked on this typical method of method that film surface is peeled off.The situation of this employing adhesive tape can both form same micro crowning structure in substrate-side and adhesive tape side, therefore can provide the method that also can form microprotrusion structure to the base material of bending.In addition strip operation can also be enumerated the strip operation that adopts ultrasonic irradiation and polymer dissolution.The microprotrusion structure that is formed at substrate-side can peel off easily as self-supporting film.
The porous honeycomb structure body thin film will become the presoma of micro crowning structure, so the interval of microprotrusion structure is relevant with the aperture of porous membrane, be about 0.1～100 μ m.And the height of microprotrusion structure is relevant with thickness, stripping means and the material of porous membrane with most advanced and sophisticated size, is about 0.1～100 μ m, 0.01～20 μ m separately.
So-called micro crowning structure is meant at interval and highly almost fixing a plurality of projection rules structure arranged fitly among the present invention.The cross section of projection is not particularly limited, and can be shapes such as circle, ellipse, hexagon, rectangle, square.
By forming this micro crowning, with do not have micro crowning or irregular comparing, remarkable proterties such as the frictional resistance that shows the surface in the nature of things reduces, hydrophobicity extremely improves, and by as be applied to the culture technique of cell, improve the cultivation rate of cell, played propagation and differentiation etc. as the excellent effect of cultivating base material by expectation thus.Certainly, also comprise its surface texture, integral body presents special micro-structural, is the novel base material that does not have fully in the past, and its meaning is very big.Not only design brings great influence to the material in various fields from now on, and to be expected for be the object with excellent effect, be sure of the object that industry development is contributed.
Embodiment
Specify the present invention based on accompanying drawing, embodiment below.But these embodiment disclose in order to understand the present invention easily, do not limit the present invention.
Embodiment 1
Polystyrene and amphipathic acrylamide (compound 1Cap with mean molecule quantity 200,000, formal name is called dodecyl acrylamide-ω-carboxyl hexyl acrylamide) chloroformic solution (counting 4mg/l) that mixes with the ratio of 10: 1 weight ratios with polymer concentration, on the glass experiment ware of diameter 10cm, pour into a mould 4ml, blow the damp atmosphere of relative humidity 70% with the flow of 2 liters of per minutes, make the chloroform solvent evaporation, make porous membrane (Fig. 1, Fig. 2) thus with honeycomb pattern structure.Then, adhesive tape is pasted the surface of the membranaceous coupons that obtains in the ware in experiment, make microprotrusion structure by peeling off at thickness direction.Adopt the result of electron microscope (below be called SEM) oblique view, find to make the extremely high microprotrusion structure of systematicness (Fig. 3) in adhesive tape side and glass experiment ware side.
Chemical formula 1:
The structural formula of Cap
Embodiment 2
Following 1～9 various macromolecules are 1: polystyrene, 2: polymethyl methacrylate, 3: Merlon, 4: polymethylacrylic acid tetrahydrochysene chaff ester, 5: poly-(6-caprolactone), 6: PLA, 7: poly-(glycolic-lactic acid) copolymer (ratio of components 50: 50), 8: polysulfones, 9: poly-methyl cetyl siloxanes, to mix amphipathic acrylamide (compound 1Cap: chloroformic solution (counting 4mg/l) dodecyl acrylamide-ω-carboxyl hexyl acrylamide) to its ratio with 10: 1 weight ratios with polymer concentration, on the glass experiment ware of diameter 10cm, pour into a mould 6ml, blow the damp atmosphere of relative humidity 70% with the flow of 3 liters of per minutes, make chloroform solvent evaporation, make thus that ultramicrofine pore arranges regularly, porous membrane (Fig. 4) with honeycomb pattern.Then, the result that it is peeled off similarly to Example 1 arranges around each pore regularly and the leg portion that is the state that supports pore is broken, and making is arranged with the microprotrusion structure (Fig. 5) of ultra tiny projection regularly thus.
Embodiment 3
The chloroformic solution (counting 4mg/l) that the polymethylacrylic acid tetrahydrochysene chaff ester of mean molecule quantity 200,000 and amphipathic acrylamide are mixed with the ratio of 10: 1 weight ratios with polymer concentration, be cast in quantitative change on the experiment ware of diameter 10cm and be 2.5,5,7.5,10ml, blow the damp atmosphere of relative humidity 70% with the flow of 2 liters of per minutes, make the chloroform solvent evaporation, make porous membrane thus with honeycomb pattern structure.Then, adhesive tape pasted the film surface after, make microprotrusion structure by peeling off at thickness direction.It is carried out the result that SEM observes, and the fluence of watering that affirmation can be made because of solvent makes the different at interval microprotrusion structure (Fig. 6) of projection.
Embodiment 4
With polystyrene and amphipathic acrylamide (compound 1Cap: the chloroformic solution (counting 4mg/l) that mixes with the ratio of (a) 10: 1, (b) 10: 2, (c) 10: 2.5, (d) 10: 3 weight ratios separately dodecyl acrylamide-ω-carboxyl hexyl acrylamide) with polymer concentration, on the glass experiment ware of diameter 10cm, pour into a mould 8ml, blow the damp atmosphere of relative humidity 70% with the flow of 3 liters of per minutes, make the chloroform solvent evaporation, make porous membrane thus with honeycomb pattern.With these porous membranes in the 1-propyl alcohol, flood dissolved in 10 minutes after, clean with ethanol.(Fig. 7) observed with SEM in dry back.Its result finds that each coupons all peels off, and obtains the structure that micro crowning or micro crowning pattern are arranged in release surface regularly.For relatively, represented to carry out the situation of tape stripping aside.Can know that thus the polymer dissolution method also is as the stripping means effective method.
Embodiment 5
With polystyrene and amphipathic acrylamide (compound 1Cap: the chloroformic solution (counting 4mg/l) that mixes with the ratio of 10: 1 weight ratios dodecyl acrylamide-ω-carboxyl hexyl acrylamide) with polymer concentration, on the glass experiment ware of diameter 10cm, pour into a mould 5ml, blow the damp atmosphere of relative humidity 70% with the flow of 3 liters of per minutes, make the chloroform solvent evaporation, make porous membrane with honeycomb pattern.Porous membrane to such making carries out 5 minutes ultrasonic irradiations (20KHz, 15W).Its result observes to confirm with the water droplet to be that the honeycomb molded body that mold forms breaks in its leg portion by SEM, obtains the structure that micro crowning protrudes, and confirms that as stripping means be effective (Fig. 8).
Merlon and amphipathic acrylamide (compound 1Cap with mean molecule quantity 2.9 ten thousand, formal name is called dodecyl acrylamide-ω-carboxyl hexyl acrylamide) chloroformic solution (counting 4mg/l) that mixes with the ratio of 10: 1 weight ratios with polymer concentration, on the glass experiment ware of diameter 10cm, pour into a mould 8ml, blow the damp atmosphere of relative humidity 70% with the flow of 2 liters of per minutes, make the chloroform solvent evaporation, make porous membrane (Fig. 9 (a)) with honeycomb pattern structure.Then, adhesive tape pasted the film surface after, peel off to make and have anisotropic microprotrusion structure (Fig. 9 (b), (c)) by applying crosscut stress.Adopt the result of SEM oblique view, find to make and have extremely high anisotropic microprotrusion structure in adhesive tape side and glass experiment ware side.
The chloroformic solution (counting 4mg/l) that the polystyrene of mean molecule quantity 1,000,000 and amphipathic acrylamide are mixed with the ratio of 10: 1 weight ratios with polymer concentration, on the glass experiment ware of diameter 10cm, pour into a mould 6ml, blow the damp atmosphere of relative humidity 70% with the flow of 3 liters of per minutes, make the chloroform solvent evaporation, make porous membrane (Figure 10 (a)) with honeycomb pattern structure.Then, adhesive tape pasted the film surface after, peel off to make and have anisotropic microprotrusion structure (Figure 10 (b), (c)) by applying crosscut stress.The result who adopts SEM to observe from tilted direction finds can both make in adhesive tape side and glass experiment ware side and has extremely high anisotropic microprotrusion structure.
Below be to be used for expression, in embodiment 8～13, the microprotrusion structure of being made by hydrophobic polymer of the present invention is compared with the honeycomb molded body that does not have micro crowning with the common film body of being made by identical material (below be called flat film), has hydrophobic surface.
Polystyrene (Aldrich) and amphipathic acrylamide (compound 1Cap: the chloroformic solution (counting 4mg/l) that mixes with the ratio of 10: 1 weight ratios dodecyl acrylamide-ω-carboxyl hexyl acrylamide) with polymer concentration with mean molecule quantity 200,000, on the glass experiment ware of diameter 10cm, pour into a mould 6ml, blow the damp atmosphere of relative humidity 80% with the flow of 3 liters of per minutes, make the chloroform solvent evaporation, make porous membrane with honeycomb pattern structure.Then, adhesive tape pasted the film surface after, make microprotrusion structure by peeling off.Then, 10 μ l distilled water are dropped onto the micro crowning body structure surface, measure the static contact angle of water after 30 seconds for these samples.Porous film surface, and the static contact angle of the flat film made by spin-coating method of the chloroformic solution that uses above-mentioned polystyrene and Cap (10: 1 weight ratios) of polystyrene are measured in contrast as a comparison.The static contact angle of water is shown in table 1.
Use the polystyrene of polymethyl methacrylate (Aldrich) the replacement embodiment 1 of weight average molecular weight 350,000, similarly make porous membrane, microprotrusion structure, flat film, measure the static contact angle of water with honeycomb pattern structure.Show the result in table 1.
Embodiment 10 (c) and comparative example 5,6
Use the polystyrene of the Merlon replacement embodiment 1 of weight average molecular weight 2.9 ten thousand, making similarly has the porous membrane of honeycomb pattern structure, each flat film of microprotrusion structure, measures the static contact angle of water.Show the result in table 1.
Use the polystyrene of the polymethylacrylic acid tetrahydrochysene chaff ester replacement embodiment 1 of weight average molecular weight 240,000, similarly make porous membrane, microprotrusion structure, flat film, measure the static contact angle of water with honeycomb pattern structure.Show the result in table 1.
Embodiment 12 (e) and comparative example 9,10
Use the polystyrene of poly-(6-caprolactone) (with the pure medicine of light Co., Ltd. system) replacement embodiment 1 of viscosity-average molecular weight 40,000, similarly make and have the porous membrane of honeycomb pattern structure, each flat film of microprotrusion structure, the static contact angle of mensuration water.Show the result in table 1.
Embodiment 13 (f) and comparative example 11,12
Poly-(glycolic-lactic acid) copolymer (ratio of components 50: 50) that uses weight average molecular weight 4～7.5 ten thousand (Aldrich) replaces the polystyrene of embodiment 1, similarly make and have the porous membrane of honeycomb pattern structure, each flat film of microprotrusion structure, the static contact angle of mensuration water.It is the results are shown in table 1.
Table 1
| Embodiment/(comparative example) | Polymer | The contact angle of comparative example | The contact angle of embodiment | |
| Flat film | Honeycomb | Micro crowning (pillar) | ||
| 1/(1、2) | Polystyrene | 98°±3° | 120°±2° | 159°±3° |
| 2/(3、4) | Polymethyl methacrylate | 96°±3° | 120°±2° | 158°±4° |
| 3/(5、6) | Merlon | 97°±3° | 122°±3° | 162°±3° |
| 4/(7、8) | Polymethylacrylic acid tetrahydrochysene chaff ester | 85°±3° | 121°±2° | 158°±2° |
| 5/(9、10) | Poly-(6-caprolactone) | 80°±3° | 120°±2° | 151°±1° |
| 6/(11、12) | Poly-(glycolic-lactic acid) 50: 50 | 91°±1° | 127°±3° | 164°±2° |
Be illustrated in below among the embodiment 14 the micro crowning surface that is made of polymer is suitable for hydrophilicity-imparting treatment, make wetability example good, that be imbued with hydrophilic microprotrusion structure.
Embodiment 14 (according to the finishing of titanium alkoxide)
PLA (PLLA) and Cap are mixed the chloroformic solution of modulation 2.0g/l with 1: 1 ratio.This solution casting of 3.0ml on the experiment ware of diameter 9cm, is blowed damp atmosphere and makes the honeycomb film.Peel off sticking with glue band above the film made, make pillar (projection) structure.
Each sample of making is dripped the MilliQ water of 10 μ l, measure after 30 seconds and the contact angle after 210 seconds.Experiment in contrast, flat film, the honeycomb pattern film of preparation same composition carry out same experiment.Measuring the result of contact angle of the water of each sample, is 101 ° ± 9 ° with respect to flat film, and honeycomb is 109 ° ± 2 °, raised structures be 138 ° ± 2 °.
Then each sample is immersed in the titanium alkoxide solution.Film whitens a little.This is to form the high titanium oxide gel of refractive index owing to the hydrolysis of titanium alkoxide on the surface, produces the cause of light scattering on the surface.The whiting of rinsing rear surface does not change yet.Be that titanium oxide gel can be described as and is fixed on the surface.Amphipathy macromolecule Cap polymer is owing to having carboxyl, so think with this carboxyl to be that support is at the superficial growth titanium oxide gel.
When forming titanium oxide gel on the surface, the contact angle of the water when water droplet is dropped onto behind the surface 30 seconds is, flat film is that 39 ° ± 10 °, honeycomb are that 19 ° ± 6 °, raised structures are 31 ° ± 10 °, confirms to be able to hydrophiling.
Also have, became lower later in 210 seconds behind this worthwhile drippage water droplet, flat film is that 28 ° ± 6 ° honeycombs and raised structures are then low for measuring the degree of contact angle.With flat film contact angle is compared more than being reduced to a certain degree, carry out structurized film and can considerably reduce contact angle, this is considered to be able to structuring by hydrophilic surface, produces capillary force, makes liquid be diffused in the cause of film surface gradually by capillary force.
If the general surface area (promptly forming concavo-convex) that increases of Wenzel report then plays the effect that strengthens surface nature.Apparent contact angle θ
wCan be expressed from the next.
cosθ
w＝rcosθ
In the following formula r be area during with flat film divided by the numerical value of the surface area of structured film, the contact angle when θ is flat film.Be that the big side of surface area strengthens surface nature.Think same phenomenon is also arranged this moment.
Embodiment 15 (according to the hydrophiling of ozone treatment)
(molecular weight is 280,000, Aldrich) mixes the solution of modulating 5.0g/l with 10: 1 ratio with Cap with polystyrene.This solution casting of 7.5ml to the experiment ware of the about 9cm of diameter, is blowed damp atmosphere and makes film.And, peel off sticking with glue band above the film part, make raised structures.Each film of making is measured contact angle.The contact angle of honeycomb, each film of raised structures is respectively done for oneself 114 ° ± 2 °, 158 ° ± 5 ° at this moment.
Then, the film made is handled with ozone clean machine (NL-UV253, Japanese electronic laser Co., Ltd.), whenever carried out 30 minutes ozone treatment and just measure contact angle on the film.Its result, contact angle descends gradually.But the contact angle of honeycomb film descends slowly, and the processing of carrying out 180 minutes also demonstrates the contact angle about 70 °.On the other hand, be to want during contact angle suppression ratio alveolate texture significantly to be about about 30 ° during raised structures when handling 180 minutes.The effect of surface configuration is more remarkable when this phenomenon can be thought ozone treatment.
Embodiment 16
Honeycomb film with poly-(glycolic-lactic acid) copolymer (ratio of components 50: 50) that uses weight average molecular weight 4～7.5 ten thousand (Aldrich) is made uses adhesive tape to peel off to thickness direction, makes raised structures.Protrusion surface, is cleaned with distilled water after 120 minutes with 1N sodium hydrate aqueous solution dipping.After the drying, measure behind 30 seconds behind the water droplet drippage and the static contact angle of the water droplet after 120 seconds.Its result is 164 ° ± 2 ° before the sodium hydrate aqueous solution dipping, but is 21 ° ± 5 ° (after 30 seconds), about 0 ° (after 120 seconds) behind the dipping.
Embodiment 17
The raised structures surface impregnation of making at embodiment 16 in the methanol solution of the 0.2w/v% of the water-insoluble hydrophilic macromolecule poly-(acrylic acid 2-methoxyl group ethyl ester) of weight average molecular weight 8.5 ten thousand, is carried out face coat.After the drying, measure behind 30 seconds behind the water droplet drippage and the static contact angle of the water droplet after 120 seconds.Its result is 164 ° ± 2 ° before the coating, but is 29 ° ± 4 ° (after 30 seconds), about 0 ° (after 120 seconds) after the coating.
Can know that from above result enough surface chemical modifications of energy and ozone oxidation make honeycomb and raised structures be able to hydrophiling.This film is applied to matrix material and diffusion barrier etc. by expectation.
Utilize possibility on the industry
The present invention is by film that to be mold with steam obtain having the fine regular pattern of alveolate texture to the solid substrate with the thin solution casting of polymer, employing is peeled off the formation of this uniqueness with it at thickness direction, be provided at the film release surface and arrange and form the brand-new new material of micro crowning regularly, because there is the micro crowning of arranging regularly in its surface, expected to use attentively in various fields from now on.About the possibility of utilizing of microprotrusion structure of the present invention, can enumerate as chemical valve, DNA chip, protein-chip, cyto-diagnosis and cultivate optical material, catalyst carrier, cell culture medium material, anisotropic solid, conductive material, fluid channel etc. such as engineering, medical timbering material, semiconductor, recording materials, isolator, amberplex, battery diaphragm material, display, optical waveguide with chip, cell.Especially since the existence of micro crowning and can providing be suitable for material mobile is controlled at the biochip surface of fixed-direction, only reduces the surface on low frictional resistance surface etc. of the resistance of air or water at fixed-direction, this embodiment, by giving anisotropy to micro crowning, make its effect further increase conspicuousness, can use carefully in various fields, be expected for the object that industry development is made a significant contribution.
Claims (27)
1. a microprotrusion structure is characterized in that, is arranged with micro crowning regularly at substrate surface.
2. the microprotrusion structure with hydrophobic surface is characterized in that, is arranged with micro crowning regularly at substrate surface, and has hydrophobicity.
3. the microprotrusion structure on a possess hydrophilic property surface is characterized in that, is arranged with micro crowning regularly at substrate surface, and passes through hydrophilicity-imparting treatment and possess hydrophilic property.
4. according to any described microprotrusion structure in the claim 1～3, it is characterized in that described base material and micro crowning are made of polymer, and contain material modified as required.
5. according to any described microprotrusion structure in the claim 1～4, it is characterized in that, described base material and micro crowning thereof are by being presoma to contain polymer and to contain material modified porous honeycomb structure body as required, this presoma are peeled off at thickness direction obtain.
6. microprotrusion structure according to claim 5 is characterized in that, described presoma and the base material that is obtained by this presoma are the film shape.
7. according to any described microprotrusion structure in the claim 1～5, it is characterized in that, described micro crowning with length be the length of 0.1～50 μ m, tip portion be 0.01～20 μ m and projection at interval 0.1～100 μ m arrange.
8. according to claim 4 or 5 described microprotrusion structures, it is characterized in that described polymer contains hydrophobicity or Biodegradable polymer, and contains amphipathic nature polyalcohol.
9. microprotrusion structure according to claim 8, it is characterized in that, containing of described hydrophobic polymer and/or Biodegradable polymer and amphipathic nature polyalcohol proportionally be, hydrophobicity and/or Biodegradable polymer are 50～99%, and remainder is an amphipathic nature polyalcohol.
10. according to Claim 8 or 9 described microprotrusion structures, it is characterized in that,, use polyester, poly-(methyl) acrylate, Merlon or polystyrene as described hydrophobicity or Biodegradable polymer.
11. according to any described microprotrusion structure in the claim 1～10, it is characterized in that, to be dissolved with the hydrophobic organic solvent solution casting of polymer on substrate, containing this organic solvent of evaporation under the atmosphere of hygroscopic moisture, make that contained hygroscopic moisture becomes small water droplet in this potting syrup surface condensation, dewfall in this potting syrup surface atmosphere, in this potting syrup surface or potting syrup, be dispersed into the closeest interstitital texture; Then with this dewfall and be dispersed in small water-drop evaporation in potting syrup surface or the potting syrup, obtaining with the water droplet is the porous honeycomb structure body of mold; Then by this structure is peeled off and is separated into two parts at least at thickness direction, obtain being separated in the honeycomb molded body that release surface formed and be arranged with micro crowning regularly according to described.
12. any described microprotrusion structure according in the claim 1～11 is characterized in that, any direction beyond the described micro crowning directed in orthogonal direction is set to and has anisotropy.
13. microprotrusion structure according to claim 12, it is characterized in that, the fine projection of described anisotropy is when thickness direction is peeled off porous honeycomb structure body as the micro crowning presoma, and any direction that points to beyond the thickness direction for the micro crowning that makes generation obtains by the lift-off processing that contains crosscut stress.
14. hydrophilic fine raised structures body according to claim 3 is characterized in that, described hydrophilicity-imparting treatment is any one or these the combination in chemical sex modification processing, ozone Oxidation Treatment, the alkali treatment.
15. the manufacture method of a microprotrusion structure, it is characterized in that, to be dissolved with the hydrophobic organic solvent solution casting of polymer on substrate, containing this organic solvent of evaporation under the atmosphere of hygroscopic moisture, make that contained hygroscopic moisture becomes small water droplet in this potting syrup surface condensation, dewfall in this potting syrup surface atmosphere, in this potting syrup surface or potting syrup, be dispersed into the closeest interstitital texture; Then with this dewfall and be dispersed in small water-drop evaporation in potting syrup surface or the potting syrup, obtaining with the water droplet is the porous honeycomb structure body of mold; Then, obtain being arranged with regularly the honeycomb molded body of micro crowning thus in release surface by this structure is peeled off and is separated into two parts at least at thickness direction.
16. the manufacture method of microprotrusion structure according to claim 15 is characterized in that, described polymer is made of hydrophobicity or Biodegradable polymer and amphipathic nature polyalcohol, and is mixed with material modified as required.
17. the manufacture method of microprotrusion structure according to claim 16, it is characterized in that, the proportion of composing of described hydrophobicity or Biodegradable polymer and amphipathic nature polyalcohol is, hydrophobicity or Biodegradable polymer are 50～99%, and remainder is an amphipathic nature polyalcohol.
18. the manufacture method according to claim 16 or 17 described microprotrusion structures is characterized in that, described hydrophobicity or Biodegradable polymer are to be the polymer formation of polyester, poly-(methyl) acrylate or polystyrene by basic framework.
19. the manufacture method of microprotrusion structure according to claim 15 is characterized in that, the described atmosphere that contains hygroscopic moisture is that to be adjusted to relative humidity be 50～95% atmosphere.
20. the manufacture method according to claim 15 or 19 described microprotrusion structures is characterized in that, described atmosphere is common atmosphere.
21. the manufacture method of microprotrusion structure according to claim 15 is characterized in that, the mode of operation of the described organic solvent of evaporation is to be undertaken by the atmosphere that the evaporating surface to organic solvent blows high humility under the described atmosphere that contains hygroscopic moisture.
22. the manufacture method of microprotrusion structure according to claim 15 is characterized in that, strip operation is to be undertaken by gluing bringing.
23. the manufacture method of microprotrusion structure according to claim 15 is characterized in that, strip operation is to be undertaken by the dissolving of polymer.
24. the manufacture method of microprotrusion structure according to claim 15 is characterized in that, strip operation is to be undertaken by ultrasonic irradiation.
25. manufacture method according to any described microprotrusion structure in the claim 15～24, it is characterized in that described micro crowning is that the length of 0.1～50 μ m, tip portion is that 0.01～20 μ m and pitch density are that 0.1～100 μ m forms and arranges with length.
26. the manufacture method according to any described microprotrusion structure in the claim 15～25 is characterized in that, described micro crowning is set to the anisotropy with directed in orthogonal direction any direction in addition.
27. the manufacture method of microprotrusion structure according to claim 26, it is characterized in that, described to have anisotropic micro crowning be to peel off when generating micro crowning as the porous honeycomb structure body of micro crowning presoma at thickness direction, and any direction that points to beyond the thickness direction for the micro crowning that makes generation carries out lift-off processing and obtains by applying crosscut stress.
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| CN102248736A (en) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | Method for preparing regular composite membrane and semi-spherical inorganic substance micro-nano particles |
| CN102713025A (en) * | 2009-08-07 | 2012-10-03 | 格尔德殿工业公司 | Debonding and transfer techniques for hetero-epitaxially grown graphene, and products including the same |
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| CN102713025A (en) * | 2009-08-07 | 2012-10-03 | 格尔德殿工业公司 | Debonding and transfer techniques for hetero-epitaxially grown graphene, and products including the same |
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| CN102248736A (en) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | Method for preparing regular composite membrane and semi-spherical inorganic substance micro-nano particles |
| CN102248736B (en) * | 2010-05-21 | 2014-03-12 | 中国科学院化学研究所 | Method for preparing regular composite membrane and semi-spherical inorganic substance micro-nano particles |
| CN104919095B (en) * | 2012-12-19 | 2017-06-30 | 加利福尼亚大学董事会 | Micro-pillar array for determining myelin formation |
| CN103454430A (en) * | 2013-08-28 | 2013-12-18 | 济南大学 | Preparation method of biomolecule microarray based on cellular porous membrane |
| CN103454430B (en) * | 2013-08-28 | 2014-08-13 | 济南大学 | Preparation method of biomolecule microarray based on cellular porous membrane |
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