CN106444275A - Roll-to-roll ultraviolet nano-imprinting device and method for preparing super-hydrophobic surface micro-structure by using roll-to-roll ultraviolet nano-imprinting device - Google Patents

Roll-to-roll ultraviolet nano-imprinting device and method for preparing super-hydrophobic surface micro-structure by using roll-to-roll ultraviolet nano-imprinting device Download PDF

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Publication number
CN106444275A
CN106444275A CN201610811891.8A CN201610811891A CN106444275A CN 106444275 A CN106444275 A CN 106444275A CN 201610811891 A CN201610811891 A CN 201610811891A CN 106444275 A CN106444275 A CN 106444275A
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China
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volume
roller
glue
platen
substrate film
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王智伟
吴天准
邹业兵
袁丽芳
凌世全
彭涛
彭智婷
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention discloses a roll-to-roll ultraviolet nano-imprinting device, which comprises a transmission device, a coating device, a first rolling device, a first ultraviolet curing device, a second rolling device and a second ultraviolet curing device. The invention further discloses a method for massively preparing a super-hydrophobic surface micro-structure by using roll-to-roll ultraviolet imprinting. The roll-to-roll ultraviolet nano-imprinting device is simple in structure, convenient to operate and low in manufacturing cost; and continuous mass production of the super-hydrophobic surface micro-structure can be achieved. According to the method disclosed by the invention, a super-hydrophobic material can be continuously and efficiently prepared at low cost.

Description

A kind of volume to volume ultraviolet nanometer imprinting apparatus and using its preparation super lyophoby surface micro- knot The method of structure
Technical field
The invention belongs to embossing forming device technical field, more particularly, to a kind of volume to volume ultraviolet nanometer imprinting apparatus and profit The method preparing super lyophoby surface micro-structure with it.
Background technology
In the special spherical or T-shaped micro nano structure of material surface processing, any drop all assumes height on super lyophoby surface Contact angle and low contact angle hysteresis, drop " suspension " in super lyophoby material surface and easily moves, and drop is logical while motion The surface tension crossing drop carries the automatically cleaning that pollutant realizes material secretly.Using the self-cleaning feature of super lyophoby material, glass, The adhesion of all kinds of dust, ice and snow, particulate matter can effectively be reduced on building wall, metal, outdoor equipment, and pass through rainwater, punching Wash and just can keep cleaning.In biological medicine industry, super lyophoby material can prevent the absorption of dirt, cell, have and preferably give birth to Thing compatibility.
The preparation of micro-structure surface is generally by the MEMS technology such as mode such as photoetching, etching, transfer.Photoetching is using some The for example photosensitive photoresist of special material issues in electromagnetic wave irradiation (ultraviolet, deep ultraviolet, extreme ultraviolet, X-ray, high energy particle etc.) The dissolubility of raw change physically or chemically, such as positive photoetching rubber material after irradiation increases, and negative photoresist is irradiating The dissolubility of material reduces afterwards.Figure on mask plate is generally transferred to base by photoresist (also known as photoresist) by photoetching Piece, soft lithographic is to be produced with hard mask version used in springform (being mostly PDMS material to make) replacement conventional lithographic techniques Raw micro-structural.Etching refers to peel off, remove the system of a class method of material by solution, reactive ion or other machinery mode Claim.Transfer is by modes such as heating, pressurizations, and the pattern of template surface, structure are transferred to the technology on other materials.Wherein The modes such as photoetching, etching are difficult to extensive batch and prepare, and are commonly used for preparing template.It is to be engraved by light that batch is prepared mostly Obtain template, then reverse is obtained by soft lithographic transfer, recycle transfer technique to carry out batch duplicating.
Nano impression is the technology transferred to the figure on mask plate by transfer medium on substrate, and its transfer medium is many Using thin polymer film (as PMMA, PDMS etc.).Nano-imprint process includes graph copying and figure shifts two big steps, by mould Plate is pressed in transfer medium liquid under the effect of the pressure, and after a period of time, nanometer pocket is sufficient filling with by transfer medium, it By modes such as heating or ultraviolet lightings, transfer medium liquid is solidified in template afterwards and release pressure carries out the demoulding therewith, Transition diagram can be formed on substrate.Current nano hot stamping technology is to environmental requirement harshness (as high temperature, high pressure), unfavorable Prepare in realizing batch.Ultraviolet nanometer impressing overcomes the shortcomings of nano-imprint process time length and experiment condition harshness, can To carry out at normal temperatures and pressures, its technical way is to make photoetching adhesive curing complete nanometer on resist using ultraviolet light The duplication of figure.
Volume to volume stamping technique is based on mechanical impressing allows polymeric material to be deformed realizing the transfer of structure equal proportion Principle, inherit Conventional nano impressing high-resolution speciality, on the other hand adopt running roller rotation continuity impressing mode, can It is obviously improved impressing speed.In traditional plane impressing mode, the large-area graphic structure of impressing needs very big impressing Power, this is easy to lead to the crushing of template or substrate, and template micro-structural is connect with the stamping structure large area on substrate glue-line Touch and can produce very big adhesion strength so that the demoulding becomes extremely difficult, and the knockout press producing is easily uneven, or even destroy pressure Print structure.Impressing is carried out by volume to volume mode and can avoid these defects.
Ultraviolet nanometer stamping technique apparatus expensive, the requirement to technique and environment is also very high；There is no the process heating, light Bubble in photoresist is difficult to discharge, and can cause defect to fine structure.In order to reach necessary complex resolution ratio, precision, coating Which kind of material uniformity, solidification release property and raising imprint lithography subsequent technique efficiency, select as uv-curable glue whole In nanoimprinting process technical process it is critical that.Currently used for the uv-curable glue of nano impression, to there is hardening time long It is unfavorable for the not superior impact solidification stripping result of improve production efficiency, machinery and physical property.
Additionally, super lyophoby surface need Surface Machining special hang micro-nano structure by the feet, such as mushroom header structure, T-type structure, Inverted trapezoidal structure etc., and carry out low-surface-energy process, but hang structure by the feet and be difficult to the demoulding it is impossible to be transferred with usual manner.
Publication No. is the Chinese patent application of " CN102515091 A "《For plastic functional micro-structure surface mass The method that the employing soft lithography producing replicates plastic functional micro-structure surface》Mother is obtained by pulse laser micro Process Mould.Under vacuum, high temperature and high pressure environment, replicated using soft lithographic and obtain elastomer PDMS polymer reverse, then pass through soft lithographic Template function and structure are transferred to plastic material surface by reproduction technology, realize thering is super-hydrophobicity plastic functional micro-structural table The mass production in face.Because the function and structure of PDMS reverse is transferred to plastics material to be copied using soft lithographic by this patent Material surface is to carry out under vacuum high-pressure environment, harsh to experiment condition, is unfavorable for inexpensive mass production.
Publication No. is the Chinese patent application of " CN 101943859 A "《A kind of volume to volume ultraviolet nanometer imprinting apparatus and side Method》Using volume to volume ultraviolet nanometer imprinting apparatus, make material to be imprinted along regulation path transmission, glue is carried out on material to be imprinted Liquid coats, and to glue precuring, crimped, strong cured obtains micro-nano graph.Separately install control parts additional, realize glue coating thickness Control, bias correcting in transmitting procedure for the material, control of transmission tension force etc..But have one due to after photoresist precuring Fixed intensity and toughness, then crimped do not ensure that now photoresist can penetrate in micro-nano structure chamber completely, especially institute , in nanoscale, its difficulty is bigger for the micro-nano structure that need to replicate.Therefore, the method preparation nano-scale patterns and such as T-shaped and mushroom During the complicated micro-nano pattern of type structure and inapplicable.
Existing document (can be found in：Yi H,et al.Continuous and Scalable Fabrication of Bioinspired Dry Adhesives via a Roll-to-Roll Process with Modulated Ultraviolet-Curable Resin [J] .ACS applied materials＆interfaces, 2014,6 (16)) utilize E-PUA glue obtains the dry glue with mushroom-shaped micro-nano structure by way of ultraviolet nanometer crimped prints.This document utilization PUA adds Modifying agent obtains viscosity enhanced e-PUA glue, with PET for material substrate to be imprinted, PUA imprint masters is attached to transparent On silicon mould, under ultraviolet environments, crimped e-PUA glue makes it solidify, and the demoulding after crimped obtains dry glue.But the technology in this document Suffer from the drawback that：(1) used by, micro-nano embossing template interruption separates it is impossible to complete the preparation of overlarge area super lyophoby film；(2) Film is transmitted using driving stepper motor, is also easy to produce overlay error and causes to produce accumulative displacement in moulding process, be unfavorable for micro-nano The raising of pattern forming rate；(3) no automatic deploying and retracting winding apparatus, though can use under experimental situation, are not suitable for industrialization, in batches Preparation super lyophoby material.
Content of the invention
It is an object of the invention to overcoming the weak point of prior art presence and providing a kind of volume to volume ultraviolet nanometer Imprinting apparatus, the volume to volume ultraviolet nanometer imprinting apparatus features simple structure of the present invention, easy to operate, low cost of manufacture, the company of can achieve Continuous batch production.
The technical solution used in the present invention is：A kind of volume to volume ultraviolet nanometer imprinting apparatus, described volume to volume ultraviolet nanometer Imprinting apparatus include：
Transmitting device, including let off roll and wind-up roll, for by the transmission route transferring substrate film setting；
Apparatus for coating, for being coated on described substrate film by uv-curable glue；
First rolling device, including the first roller platen and the first platen support roller, described first impressing roller surface has to be received The pattern of rice structure, described first platen support roller coordinates described first roller platen by the imprint patterns of this nanostructured to coating In the uv-curable glue on described substrate film；And
First ultra-violet curing device, for solidifying the uv-curable glue of described first rolling device impressing.
As the improvement further to technique scheme, described first ultra-violet curing device is located at described first roller platen Internal.
As the improvement further to technique scheme, described apparatus for coating includes upper glue roller, lower rubber roller, described lower glue Roller is immersed in glue groove, and the uv-curable glue in described glue groove carries to described upper glue roller through described lower rubber roller, is coated with by this upper glue roller On described substrate film.
As the further improvement to technique scheme, described apparatus for coating also includes scraper, described scraper located at After described upper glue roller, for removing unnecessary uv-curable glue.
As the improvement further to technique scheme, described volume to volume ultraviolet nanometer imprinting apparatus also include tension force control System processed, described tension control system includes tension controller, tension pick-up and magnetic controller, described tension pick-up inspection Survey the actual tension of described substrate film and using detected value as feedback signal back to described tension controller, this tension force Device feeds back the deviation between actual tension value and given tension value and outputs control signals to described magnetic controller, through current stabilization electricity Source drives this magnetic controller to be applied to described let off roll.
As the improvement further to technique scheme, described transmitting device also includes being distributed on described transmission route Auxiliary support roller, described Auxiliary support roller includes for the intermediate supports portion of transferring substrate film and is used for fixing this auxiliary and props up The fixed part of support roller, described fixed position is provided with ringwise in intermediate supports portion two ends, the two ends in described intermediate supports portion Rib, is used for preventing substrate film from producing left and right skew in the horizontal direction, rib stretch out perpendicular to intermediate supports portion and Its edge is provided with the flange preventing substrate film from producing skew in vertical direction.Passing through complicated film fortune existing device more Defeated deviation-rectifying system, and the present invention looks for another way, by arranging rib, you can effectively prevent the skew of substrate film, structure is more Simply, using convenient.
As the improvement further to technique scheme, the two ends of described first roller platen are fixed with T-shaped screw, T-shaped Screw can adjust the distance between the first roller platen and the first platen support roller；
Described volume to volume ultraviolet nanometer imprinting apparatus are additionally provided with pressure sensor and pressure control apparatus, pressure sensor bag Include a flexible member with free end, the free end of flexible member can produce position under the control of described pressure control apparatus Move；Described pressure sensor is for detecting the pressure between described first roller platen and the first platen support roller and being fed back to Described pressure control apparatus, this pressure control apparatus is compared and according to comparative result control with setting pressure to feedback pressure Whether described flexible member free end produces displacement to promote described first roller platen or the first platen support roller in vertical direction Upper generation is moved, thus controlling the pressure between described first roller platen and the first platen support roller.
As the improvement further to technique scheme, the diameter of described first roller platen is not less than 60mm.
As the improvement further to technique scheme, described first roller platen and the first platen support roller adopt servo Motor in synchrony drives.
As the improvement further to technique scheme, described volume to volume ultraviolet nanometer imprinting apparatus also include film table Face processing meanss, for strengthening the lyophobicity that impressing has the uv-curable glue of nanostructured.
As the improvement further to technique scheme, described film surface processing meanss are heating fumigating room, are used for Fluorination treatment is carried out to the substrate film after impressing.
As the improvement further to technique scheme, described volume to volume ultraviolet nanometer imprinting apparatus also include：
Second rolling device, after described first rolling device, including the second roller platen and the second platen support roller, Described second impressing roller surface smooths, and described second platen support roller coordinates described second roller platen to have nanostructured to impressing Uv-curable glue is extruded so that nanostructured occurs default deformation；
Second ultra-violet curing device, located at described second roller platen inside or outside, for solidifying described ultraviolet further Solidification glue.
As the improvement further to technique scheme, described second ultra-violet curing device is located at described second roller platen Internal.
As the improvement further to technique scheme, the two ends of described second roller platen are provided with T-shaped screw, T-shaped spiral shell The other scale being configured with for showing its displacement of nail, understands the second roller platen by observing reading on scale for the T-shaped head of screw The distance between with the second platen support roller, be can adjust between the second roller platen and the second platen support roller by T-shaped screw Distance, realizes the rough control of two roll gap pressures.
As the improvement further to technique scheme, described second roller platen and the second platen support roller adopt servo Motor in synchrony drives.
On the other hand, present invention also offers a kind of volume to volume ultraviolet stamping mass prepares super lyophoby surface micro-structure Method, comprises the following steps：
1) described volume to volume ultraviolet nanometer imprinting apparatus are provided；
2) extract out continuous from described let off roll for substrate film and along fixed course transmission；
3) using described apparatus for coating, uv-curable glue is coated on described substrate film；
4) using described first rolling device, the substrate film being coated with uv-curable glue is imprinted, make described first The imprint patterns of the nanostructured on roller platen are to described uv-curable glue；
The uv-curable glue having the pattern of nanostructured using described first ultra-violet curing device to impressing carries out solidification cause It is fully cured, and the uv-curable glue after being subsequently fully cured departs from from described first roller platen；
5) substrate film after impressing is wound by wind-up roll.
As the improvement further to technique scheme, described uv-curable glue comprises the group of following weight/mass percentage composition Point：Aliphatic urethane acrylate：20%～90%, bisphenol A epoxy acrylate：0～20%, reactive diluent：10% ～50%, light trigger：1%～15%, levelling defoamer：0～5%.
As the further improvement to technique scheme, described uv-curable glue comprises following weight/mass percentage composition Component：Aliphatic urethane acrylate：78%～85%, Ethoxylated bisphenol A (10EO) dimethylacrylate：10%～ 15%th, tripropylene glycol diacrylate：4%～6%, 2- hydroxy-2-methyl -1- phenyl -1- acetone：2%～5%, wherein, second Epoxide bisphenol-A (10EO) dimethylacrylate and tripropylene glycol diacrylate are reactive diluent, 2- hydroxyl -2- first Base -1- phenyl -1- acetone is light trigger.
As the further improvement to technique scheme, described aliphatic urethane acrylate is bifunctionality fat At least one in fat race urethane acrylate oligomer and 4 degree of functionality aliphatic urethane acrylate oligomer.
As the improvement further to technique scheme, coating on described substrate film for the described uv-curable glue is thick Spend for 100～1500 μm, described uv-curable glue is solidified and caused it to be fully cured required uv agent amount is 100- 2500mW/cm2.
As the improvement further to technique scheme, the uv power of described first ultra-violet curing device is 300- 2000mJ/cm2；A diameter of 60-200mm of described first roller platen；Painting on described substrate film for the described uv-curable glue Cloth thickness is 100～1500 μm；Described substrate film transfer rate is 5～100mm/s.
As the improvement further to technique scheme, methods described also includes：Step 6) to the thin substrates after impressing Film carries out strengthening the surface treatment of its lyophobicity.
As the improvement further to technique scheme, described surface treatment refers to the substrate film after impressing is carried out Fluorination treatment.
In technique scheme, the volume to volume ultraviolet stamping mass of the present invention prepares the side of super lyophoby surface micro-structure Method is fully cured, using uv-curable glue coating, the technique that the demoulding is surface-treated again, and solidification and knockout course utilize same dress Put and carry out simultaneously, solve the problems, such as that ultra-violet curing glue can not penetrate in super lyophoby surface micro-nano structure chamber completely, optimize Volume to volume nano-imprint process.
Another aspect, present invention also offers a kind of volume to volume ultraviolet stamping mass prepares super lyophoby surface micro-structure Method, comprises the following steps：
1') provide described volume to volume ultraviolet nanometer imprinting apparatus；
2') extract out continuous from described let off roll for substrate film and along fixed course transmission；
3') using described apparatus for coating, uv-curable glue is coated on described substrate film；
4') using described first rolling device, the substrate film being coated with uv-curable glue is imprinted, make described The imprint patterns of the nanostructured on one roller platen are to described uv-curable glue；
The uv-curable glue being had the pattern of nanostructured using described first ultra-violet curing device to impressing is carried out once admittedly Change, subsequently the uv-curable glue in semi-cured state departs from from described first roller platen；
5') extruded so that nano junction using the uv-curable glue that described second rolling device has nanostructured to impressing There is default deformation in structure；
Secondary solidification is carried out to the uv-curable glue after deformation using described second ultra-violet curing device, is subsequently fully cured Uv-curable glue afterwards departs from from described second roller platen；
6') substrate film after impressing is wound by wind-up roll.
In technique scheme, the uv-curable glue of semi-cured state refer to be in can the demoulding but be not yet fully cured In the state of uv-curable glue, be not fully cured be beneficial to later-stage secondary impressing.
As the improvement further to technique scheme, described uv-curable glue comprises the group of following weight/mass percentage composition Point：Aliphatic urethane acrylate：20%～90%, bisphenol A epoxy acrylate：0～20%, reactive diluent：10% ～50%, light trigger：1%～15%, levelling defoamer：0～5%.
As the further improvement to technique scheme, described uv-curable glue comprises following weight/mass percentage composition Component：Aliphatic urethane acrylate：78%～85%, Ethoxylated bisphenol A (10EO) dimethylacrylate：10%～ 15%th, tripropylene glycol diacrylate：4%～6%, 2- hydroxy-2-methyl -1- phenyl -1- acetone：2%～5%, wherein, second Epoxide bisphenol-A (10EO) dimethylacrylate and tripropylene glycol diacrylate are reactive diluent, 2- hydroxyl -2- first Base -1- phenyl -1- acetone is light trigger.
As the further improvement to technique scheme, described aliphatic urethane acrylate is bifunctionality fat At least one in fat race urethane acrylate oligomer and 4 degree of functionality aliphatic urethane acrylate oligomer.
As the improvement further to technique scheme, coating on described substrate film for the described uv-curable glue is thick Spend for 100～1500 μm, uv-curable glue is solidified and caused the uv agent amount needed for its semi-solid preparation to be 80-2000mW/ cm2.
As the improvement further to technique scheme, the uv power of described first ultra-violet curing device is 300- 2000mJ/cm2；A diameter of 60-200mm of described first roller platen；A diameter of 50-180mm of described second roller platen；Described Coating thickness on described substrate film for the uv-curable glue is 100～1500 μm；Described substrate film transfer rate be 5～ 100mm/s.Although the partial parameters in this preferred embodiment are identical with required parameter area when being fully cured, but it should reason Solution be their values in same scope be different.
As the improvement further to technique scheme, described nanostructured there is default deformation before be shaped as post Shape, its there is default deformation after be shaped as hat, mushroom-shaped, T-shaped or inverted trapezoidal.Hat, mushroom-shaped, T-shaped or inverted trapezoidal The advantage of structure is lyophobicity more preferably, and also has good lyophoby effect to the oils of low surface tension, organic solvent.
As the improvement further to technique scheme, methods described also includes：Step 7') to the thin substrates after impressing Film carries out strengthening the surface treatment of its lyophobicity.
As the improvement further to technique scheme, described surface treatment refers to the substrate film after impressing is carried out Fluorination treatment.
The present invention proposes ultraviolet nanometer impressing or ultraviolet nanometer imprints the method preparation super lyophoby table of secondary ultraviolet crimped again Face micro-structural, also can further enhance the super lyophoby performance of prepared substrate film material by fluorination process.Make in the present invention Uv-curable glue more pays close attention to the volume to volume ultraviolet nanometer imprinting apparatus preparation so as to fit the present invention of machinery and physical property Super lyophoby surfacing the combination property of reinforcing material, used in the present invention, uv-curable glue has curing rate soon, thoroughly The chemical properties such as photosensitiveness is good, toughness and the good advantage of mechanical property.And prior art is in the combination property of uv-curable glue used Not, such as hardening time is long, viscosity is unfavorable for greatly very much glue completely in micro-nano structure cavity for aspect concern.
With respect to prior art, beneficial effects of the present invention are：
The volume to volume ultraviolet nanometer imprinting apparatus features simple structure of the present invention, low cost of manufacture, can achieve simple, safely, soon Speed, low energy consumption, efficient, continuous, large area production super lyophoby thin-film material；
The volume to volume ultraviolet stamping mass of the present invention prepares the method for super lyophoby surface micro-structure without vacuum, high temperature In the environment of high pressure, can continuity, high efficiency, low cost preparation super lyophoby material；
The method that the volume to volume ultraviolet stamping mass of the present invention prepares super lyophoby surface micro-structure adopts uv-curable glue Coating is fully cured technique or the uv-curable glue coating secondary solidification of one-step solidification (semi-solid preparation) demoulding of the demoulding The technique of (being fully cured), solidification and knockout course are carried out using same device simultaneously, and solving ultra-violet curing glue can not be complete Entirely penetrate into the problem in super lyophoby surface micro-nano structure chamber, optimize volume to volume nano-imprint process；
The volume to volume ultraviolet stamping mass of the present invention prepares the method for super lyophoby surface micro-structure using modified ultraviolet Solidification glue substantially shortened as material to be imprinted, hardening time, improved super lyophoby material batch preparation efficiency；Meanwhile, modified The viscosity of uv-curable glue and mechanical performance are more suitable for mechanical stamping, can achieve the smaller micro- knot in nanoscale super lyophoby surface The duplication of structure, improves machinery and the physical property of gained super lyophoby material；
It is solid that the volume to volume ultraviolet stamping mass of the present invention prepares the ultraviolet adopting in the method for super lyophoby surface micro-structure Change glue coating, one-step solidification, the demoulding, the secondary crimped technique of secondary solidification, can continuously prepare with hat, mushroom-shaped, T batch Shape, the super lyophoby thin-film material of inversed trapezoid micro-structure.
Brief description
Fig. 1 is the structural representation of volume to volume ultraviolet nanometer imprinting apparatus in embodiment 1；
Fig. 2 is the structural representation of volume to volume ultraviolet nanometer imprinting apparatus in embodiment 2；
Fig. 3 is the structural representation of Auxiliary support roller in embodiment 1；
Fig. 4 is the structural representation of volume to volume ultraviolet nanometer imprinting apparatus；
Fig. 5 is the structural representation of tension control system；
Fig. 6 shows that columnar microstructure is changed into T-shaped micro-structural after secondary crimped；
Fig. 7 is the ultraviolet cured adhesive translucency comparison diagram of embodiment 5～9 before solidification；
Fig. 8 be embodiment 5～9 ultraviolet cured adhesive be cured as film after translucency comparison diagram；
Fig. 9 is gained film foldability comparison diagram after the ultraviolet light polymerization glue solidification of embodiment 5～9；
Figure 10 shows the ultraviolet cured adhesive micro-nano imprint molding effect of embodiment 9, and wherein B figure is the amplification of A figure Figure, a diameter of 20 microns of pillar, adjacent center-to-center is away from for 40 microns；
Figure 11 shows the Contact-angle measurement result of embodiment 5～9 ultraviolet cured adhesive gained film and water.
Specific embodiment
Nano impression can finely reappear layout, obtain the micro nano structure of hanging by the feet of proper alignment, solve random alignment The repeatable poor, unstable properties of micro nano structure generally existing, the problems such as be difficult to large-area applications.With nano impression not With, volume to volume preparation solves the problems, such as prepared by the large area that is difficult to that the batch preparation of current super lyophoby micro-structure surface exists, Improve preparation efficiency simultaneously, reduce preparation cost.The method that volume to volume ultraviolet nanometer imprints micro-structural, adopts with PUA class For Main Ingredients and Appearance and add the uv-curable glue that modifying agent obtains superior performance, realize the high-precision of super lyophoby surface treatment preparation Degree, high yield, low cost, it is integrally formed.With respect to existing nanometer embossing, this method has higher production effect Rate, lower preparation cost, and it is suitable for different micro-nano structure transfers, it is possible to achieve prepared by large area batch.
For better illustrating the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention It is described further.
As shown in figure 1, a kind of volume to volume ultraviolet nanometer imprinting apparatus that the present invention provides include：Transmitting device, painting arrange Put, the first rolling device and the first ultra-violet curing device.
Specifically, described transmitting device, including let off roll 1 and wind-up roll 15, for transferring substrate film 16；Let off roll 1 It is located at the two ends of volume to volume ultraviolet nanometer imprinting apparatus with wind-up roll 15 respectively, the convolution substrate film 16 of tubular is placed on and unreels On roller 1, and its open end is wound to wind-up roll 15, after impressing is opened, in the presence of Power Drive Unit, let off roll 1 With wind-up roll 15 with identical linear velocity towards rotating backward that substrate film is wound around, so that substrate film 16 is along the route of regulation Transmission.Described transmitting device also includes the Auxiliary support roller 2,7,8,12,13 being distributed on transmission route, these Auxiliary support rollers So that film is in tensioning state all the time.Wherein, Auxiliary support roller 2,12,13 is used for tensioning transferring substrate film, in order to Ensure tensioning, need Auxiliary support roller to produce support force it is therefore desirable to the transmission film at Auxiliary support roller two ends to substrate film Form an angle (cannot produce holding power if 180 °)；Auxiliary support roller 7,8 is to ensure that substrate film in coating glue After can horizontal stable enter first time rolling device, rise horizontal booster action, prevent in substrate film transmitting procedure vertically side Make glue uneven, in uneven thickness to rocking, therefore do not need to produce tension force to film.Auxiliary support roller 7 is also coordinated with scraper Frictioning.Under the conditions of meeting constraints above, the position of setting should make the substrate film of transmission long to Auxiliary support roller 2,7,8,12,13 Degree is as far as possible little.In the present embodiment, the structure of Auxiliary support roller 2,7,8,12,13 is identical, and size adjusts according to actual needs.With The structure of Auxiliary support roller to be described as a example Auxiliary support roller 2, as shown in figure 3, Auxiliary support roller 2 include thin for transferring substrate The intermediate supports portion 23 of film and be located at and fix the fixed part 24 of this Auxiliary support roller, described fixed part 24 is located at intermediate supports portion 23 Two ends, the two ends in described intermediate supports portion 23 are provided with rib 25 ringwise, are used for preventing substrate film in the horizontal direction Produce left and right skew, rib stretches out perpendicular to intermediate supports portion and its edge is provided with and prevents substrate film in vertical direction Produce the flange of skew.In the present embodiment, substrate film 16 is PET film.
Described apparatus for coating after described let off roll 1, for uv-curable glue is coated on described substrate film 16 On；In the present embodiment, described apparatus for coating includes upper glue roller 3, lower rubber roller 4 and scraper 6, and described lower rubber roller 4 is immersed in glue groove 5 In, the uv-curable glue in described glue groove 5 carries to described upper glue roller 3 through described lower rubber roller 4, is coated on described by this upper glue roller 3 On substrate film 16；Described scraper 6 after described upper glue roller 3, for removing unnecessary uv-curable glue.Scraping film is fixed Above corresponding section film, highly fine-tuning, conveniently prepare the film of different-thickness.Complete glue using double anilox roll gluing modes Liquid coats, then scraper blade coating can make glue thickness properly uniform, and structure is simple to meet this equipment glue coating precision again, be not required to Configuration automatic adhesive dispenser, simplifies device, reduces manufacturing cost.Double reticulate pattern gluings realize glue thickness with reference to spreading knife is fine-tuning Adjustable in 10-2000 micrometer range.Glue surface smoothness, in 2 micrometer ranges, coats precision typically but substantially meets needs. Described apparatus for coating it is also possible to use slot coated assembly, and slot coated assembly is the module made using precision optical machinery processing, By extrusion coated for liquid film on the substrate of movement, to produce the film that surface covers photosensitive material.Slot coated die head can be In the case that coating layer thickness only has 2 μm, the coating amount on whole width is controlled the tolerance variation scope ± 2.5% about Interior, coating precision is very high.
First rolling device, after described apparatus for coating, including the first roller platen 9 and the first platen support roller 10, Described first roller platen 9 surface has the pattern of nanostructured, and this pattern can be shallow line pattern or deep line pattern, Described first platen support roller 10 coordinates described first roller platen 9 by the imprint patterns of this nanostructured to described uv-curable glue On.In the present embodiment, described first roller platen 9 is the cylinder of hollow.It should be noted that described first roller platen 9 can With by its surface apply ointment or plaster desirable pattern masterplate be obtained, also can directly the first roller platen 9 surface making desirable pattern.? In the present embodiment, the template of desirable pattern of being applied ointment or plaster using the surface in the first roller platen 9, this masterplate is the anti-film of PDMS, and it adopts Deep reaction ion etching is obtained.Deep reaction ion etching (Deep Reactive Ion Etching, abbreviation DRIE) is a kind of micro- Electronics dry corrosion process, based on the silicon of high aspect ratio lithographic technique of fluorine base gas, using etching and passivation alternately Bosch technique, is performed etching by chemical action and physical action.Etch, with DRIE, the template obtaining silicon substrate first, then use PDMS overmolded obtains reverse, anti-for PDMS film is attached on impressing running roller and obtains final product nanoscale impression block.PDMS template is ratio For 10:1 silicon rubber and silicon rubber curing agent.Taking the preparation of T-shaped micro-structural mother matrix as a example, details are provided below for it：Super Under net environment, T-shaped micro-structural mother matrix is obtained on large-sized silicon wafers by DRIE.Silicon chip is carried out the surface treatment such as be fluorinated to drop Its surface energy low, is conducive to the PDMS demoulding below.In vavuum pump, the PDMS polymer of liquid is poured into silicon chip mother matrix table Face, and scratch PDMS glue and make it with master surfaces uniform contact and filling, then vacuumize, under suitable pressure condition, make mould Micro-structural on plate and PDMS are fully contacted and guarantee that PDMS glue is fully infiltrated in T-type structure.It is coated with the silicon chip of PDMS It is transferred to heater, a period of time naturally cools to room temperature again at a temperature of 100 DEG C about, so that PDMS is solidified completely, less Heart hand-stripping obtains the anti-film of PDMS.
First ultra-violet curing device 11, for solidifying the uv-curable glue of described first rolling device impressing.In this enforcement In example, the first ultra-violet curing device 11 is uviol lamp, and uviol lamp can be arranged as required in the first roller platen 9 or the first impressing Support roller 10 internal or external.Uviol lamp is paid the utmost attention to be arranged on the inside of the first roller platen 9, because ultraviolet lamp holder is from ultraviolet The solidification glue nearlyer radiation response of distance more preferably (from ultraviolet light source more away from local unit's area irradiation power lower, this away from From scope, we are scheduled on 1-5cm), more favorably accelerate glue curing speed and improve equipment speed of production.If being arranged in support roller Or outside roller, easily increase the distance of light source and glue.First ultra-violet curing device 11 is built in the advantage tool in the first roller platen 9 Body is：Can save space, reduce equipment volume, reduce film transmission range, reduce the offset deviation pair in film transmitting procedure The impact that impressing effect produces.Increase ultraviolet source irradiation region simultaneously and reduce light source to the distance of film, ultraviolet can be made solid Change glue more fully to solidify, accelerate equipment preparation super lyophoby material rate.Ultraviolet lamp source can also arbitrarily adjust, and realizes irradiating angle Control, to adapt to different ultra-violet curing glue.In the present embodiment, using extra small fuselage UV-LED lamp source as first The ultra-violet curing lamp source of ultra-violet curing device, irradiates area of bed and is only 260*30*95mm, be conducive to reducing the device space.Lamp source Irradiation power is up to 3000mW/cm2, power can shorten greatly the hardening time of uv-curable glue, accelerate equipment preparation speed.For reality Existing uviol lamp is arranged in the first roller platen 9 and is irradiated to ultra-violet curing glue it is desirable to this first roller platen 9 translucency is good, material Material intensity is enough, such as adopts quartz ampoule to make the first roller platen 9.
Under the cooperation of the first platen support roller 10, the first roller platen 9 and the uv-curable glue on substrate film closely connect Touch, then pass through to solidify under the irradiation of uviol lamp.Solidification herein can be for being fully cured, and alternatively semi-solid preparation (i.e. being capable of the demoulding But not yet completely crued state), by adjusting the coating of the power of uviol lamp, substrate film transmission speed, uv-curable glue The parameters such as thickness can achieve different solid states.
As shown in figure 4, in the present embodiment, volume to volume ultraviolet nanometer imprinting apparatus also include trestle table 26 and prop up with being fixed on Front panel 27 on pallet 26 and rear board 28, let off roll 1, wind-up roll 15, Auxiliary support roller, the first roller platen 9 and the first pressure The two ends of print support roller 10 are separately fixed on front panel 27 and rear board 28.
Further, described first roller platen be respectively arranged at two ends with T-shaped screw 29；The top of T-shaped screw 29 be located at Fixed seat 31 on the top of axle bed 30 of the first roller platen 9 and plate forward-mounted 27 or rear board 28 is threaded, under it Threadeded with the fixed seat 32 being arranged on axle bed 30 top in portion, in the present embodiment, T-shaped screw 29 is provided with two, respectively position In the two ends of the first roller platen 9, be can adjust between described first roller platen 9 and the first platen support roller 10 by T-shaped screw Distance, thus realize the regulation of pressure between the two.The adjustment on a large scale of pressure is completed by described T-shaped screw, described T-shaped screw Also the first roller platen 9 is played the role of fastening.Preferably, the fixed seat 32 being connected with T-shaped screw bottom and the axle of the first roller platen Seat 30 is integrally formed.
Described volume to volume ultraviolet nanometer imprinting apparatus are additionally provided with pressure sensor 33 and pressure control apparatus 34；Pressure sensing Device 33 is fixed on below the first roller platen 9, and it includes a flexible member (not shown) with free end, flexible member Free end can produce displacement under the control of pressure control apparatus 34；Described pressure sensor 32 is used for detecting described first impressing Pressure between roller 9 and the first platen support roller 10 is simultaneously fed back to pressure control apparatus 34, and pressure control apparatus 34 are to anti- Feed voltage power is compared with setting pressure, and whether produces displacement according to the free end of comparative result control pressure sensor 33 (realizing controlling by electric signal), (presses as shown in Figure 4 thus realizing the first roller platen 9 and whether producing movement in vertical direction Force snesor is arranged on below the first roller platen 9, and it is mobile that the generation displacement of sensor free end will push directly on the first roller platen 9), And then change the pressure between the first roller platen 9 and the first impressing support roller 10.Set pressure when feedback pressure is more than, pressure passes Move on sensor 33 free end, the first roller platen 9 moves, the pressure between the first roller platen 9 and the first platen support roller 10 reduces. Set pressure when feedback pressure is less than, pressure sensor 33 free end moves down, and the first roller platen 9 moves down, the first roller platen 9 and the Pressure between one platen support roller 10 increases.When feedback pressure recovers to set pressure, pressure sensor 33 free end resets.Pressure Power controller unit carries out the precise control that pressure is realized in pressure fine setting, and the pressure sensor in the present embodiment can pass for pressure Sensor.The flexible member attainable displacement very little of pressure sensor 33 controls it is impossible to realize pressure changeable on a large scale, therefore needs T-shaped screw is wanted first to determine the approximate range of pressure.
Further, the diameter of described first roller platen 9 is not less than 60mm.It is not less than the big roller platen of 60mm using diameter The coordination taking turns and passing through support roller increases the contact area of roller platen and substrate film, increases the micro-structural on impression block and glue Hydraulic pressure print or laminating time, uv-curable glue can be made to have the time well in micro-nano structure chamber.Preferably, described state the first pressure Print roller 9 is identical with the diameter of the first platen support roller 10, and described first roller platen 9 and the first platen support roller 10 adopt servo electricity Machine synchronously drives, and to ensure the synchronization of impression block and transmission film, prevents from destroying the micro-nano structure obtaining on film.
Further, as shown in figure 5, described volume to volume ultraviolet nanometer imprinting apparatus also include tension control system, described Tension control system includes tension controller 20, tension pick-up 21 and magnetic controller 22, and described tension pick-up detects institute State the actual tension of substrate film and using detected value as feedback signal back to described tension controller, the reality that will measure Value, compared with given tension value, produces control action by deviation.This tension controller feedback deviation simultaneously outputs control signals to Described magnetic controller, drives this magnetic controller to be applied to described let off roll through stabilized current supply, makes actual tension and give Tension force is equal.Tension control system controls lining by tension controller 21, tension pick-up 20 and magnetic controller 22 collective effect The Tensity size of bottom film transmission and transmission stability.Magnetic controller 22 includes magnetic powder cluth and magnetic powder brake, tension force Controller 21 adjusts the torque of magnetic powder cluth and magnetic powder brake.The tension force when tension pick-up 20 finds substrate film transmission During more than a preset value, magnetic controller 22 fine motion reduces winding rotating speed, and when finding that tension force is less than a preset value, magnetic controls Device 22 fine motion lifting winding rotating speed, thus control let off roll tension force to be a steady state value.By this tension control system it is ensured that serving as a contrast Bottom film is in the state of tensioning all the time it is ensured that not having between impression block and glue during micro-contact printing in moulding process Relative displacement is it is ensured that impressing effect, it is to avoid lead to the generation of waste product because of gauffer.Preferably, described tension pick-up located at Membrane tension measurement roller 35 on, membrane tension measure roller 35 be respectively provided on two sides with Auxiliary support roller 36,37, Auxiliary support roller 36th, 37 it be arranged in parallel, membrane tension measurement roller 35 is outwardly with respect to Auxiliary support roller 36,37, and Auxiliary support roller 37 is located at Before Auxiliary support roller 7.
Further, described volume to volume ultraviolet nanometer imprinting apparatus also include film surface processing meanss 14, for strengthening Impressing has the lyophobicity of the uv-curable glue of nanostructured.Specifically, described film surface processing meanss 14 are heating fumigating room, For fluorination treatment is carried out to the film after impressing.
Embodiment 2
As shown in Fig. 2 another kind of volume to volume ultraviolet nanometer imprinting apparatus that the present invention provides are in embodiment one or to implement On the basis of example two, further include the second rolling device and the second ultra-violet curing device.
Specifically, the second rolling device, after described first rolling device, including the second roller platen 17 and the second pressure Print support roller 18, described second roller platen 17 surface smooths, and described second platen support roller 18 coordinates described second roller platen 17 The uv-curable glue having nanostructured to impressing is extruded so that nanostructured occurs default deformation.In the present embodiment, institute Stating the second roller platen 17 is the cylinder of hollow.
Second ultra-violet curing device, in the present embodiment for uviol lamp 19, inside described second roller platen 17, is used for Solidify described uv-curable glue further.With the first ultra-violet curing device, the second ultra-violet curing device is also built in the second impressing In roller 17, equally can save space, reduce equipment volume, reduce film transmission range, reduce the displacement in film transmitting procedure The impact that deviation produces to impressing effect.Increase ultraviolet source irradiation region simultaneously and reduce light source to the distance of film, can make Uv-curable glue more fully solidifies, and accelerates equipment preparation super lyophoby material rate.Lamp source can also arbitrarily adjust, and realizes illumination angle The control of degree, to adapt to different ultra-violet curing glue.In the present embodiment, using extra small fuselage UV-LED lamp source as The ultra-violet curing lamp source of one ultra-violet curing device, irradiates area of bed and is only 260*30*95mm, be conducive to reducing the device space.Lamp Source irradiation power is up to 3000mW/cm2, power can shorten greatly the hardening time of uv-curable glue, accelerate equipment preparation speed.
Further, the two ends of described second roller platen are provided with T-shaped screw 35, are configured with for showing it by T-shaped screw The scale 36 of displacement, understands roller platen and support roller gap by observing reading on scale for the T-shaped head of screw, realizes between two rollers The rough control of pressure.The top of T-shaped screw with the top of axle bed positioned at the second roller platen 17 and plate forward-mounted or after Fixed seat on panel is threaded, is threadeded with the fixed seat being arranged on axle bed in its underpart, be can adjust by T-shaped screw The distance between described second roller platen 17 and the second platen support roller 18, thus realize the regulation of pressure between the two.At this In embodiment, T-shaped screw is provided with two, is located at the two ends of the second roller platen respectively.
Further, described second roller platen and the second platen support roller diameter identical (specifically, can be 90mm), described Second roller platen and the second platen support roller adopt servomotor synchronously to drive, to ensure the same of impression block and transmission film Step, prevents from destroying the micro-nano structure obtaining on film.
The setting of the second rolling device and the second ultra-violet curing device can achieve secondary crimped, through the first rolling device and After one ultra-violet curing device process, the pattern of the uv-curable glue film in semi-cured state can deform upon after secondary crimped, Thus the uv-curable glue film with given shape pattern can be prepared.
It should be noted that in the present embodiment, the transmission route of substrate film is different from embodiment 1, substrate film warp After Auxiliary support roller 12, then transmit to Auxiliary support roller 13 through the second roller platen, to carry out secondary coining manipulation.And embodiment In 1, substrate film is directly transferred to Auxiliary support roller 13 through after Auxiliary support roller 12.Meanwhile, through the first rolling device and After one ultra-violet curing device is processed, uv-curable glue is in semi-cured state.
Embodiment 3
Volume to volume ultraviolet stamping mass according to the present invention prepares an enforcement of the method for super lyophoby surface micro-structure Example, the method comprises the following steps：
Step S1：Volume to volume ultraviolet nanometer imprinting apparatus described in embodiment 1 are provided
Step S2：Extract out continuous from described let off roll 1 for substrate film and along fixed course transmission
Step S3：Using described apparatus for coating, uv-curable glue is coated on described substrate film 16
Wherein, described ultraviolet cured adhesive comprises the component of following weight/mass percentage composition：Aliphatic urethane acrylate： 20%～90%, bisphenol A epoxy acrylate：0～20%, reactive diluent：10%～50%, light trigger：1%～ 15%th, levelling defoamer：0～5%.
Further, described ultraviolet cured adhesive comprises the component of following weight/mass percentage composition：Aliphatic polyurethane third Olefin(e) acid ester：78%～85%, Ethoxylated bisphenol A (10EO) dimethylacrylate (BPA (EO) 10DMA)：10～15%, three Propylene glycol diacrylate：4～6%, 2- hydroxy-2-methyl -1- phenyl -1- acetone：2～5%, wherein, Ethoxylated bisphenol A (10EO) dimethylacrylate and tripropylene glycol diacrylate are reactive diluent, 2- hydroxy-2-methyl -1- phenyl -1- Acetone is light trigger.The ultraviolet cured adhesive that this embodiment is obtained has curing rate soon (hardening time is not more than 7s), Translucency is good, toughness more preferably, the advantage of prepared based superhydrophobic thin films lyophobicity more preferably (contact angle is more than 140 °).Wherein, ethoxy Base bisphenol-A (10EO) dimethylacrylate is also called (10) Ethoxylated bisphenol A dimethylacrylate, and its No. CAS is 41637-38-1, it is commercially available to obtain, such as Miwon Specialty Chemical Co., Ltd company MIRAMER M2101 type product.
Further, described ultraviolet cured adhesive comprises the component of following weight/mass percentage composition：Aliphatic polyurethane third Olefin(e) acid ester：80%th, Ethoxylated bisphenol A (10EO) dimethylacrylate (BPA (EO) 10DMA)：12%th, tripropylene glycol dipropyl Olefin(e) acid ester：4.8%th, 2- hydroxy-2-methyl -1- phenyl -1- acetone：3.2%.
Further, described aliphatic urethane acrylate is bifunctionality aliphatic urethane acrylate oligomer With at least one in 4 degree of functionality aliphatic urethane acrylate oligomer.Described aliphatic urethane acrylate glutinous Spend for 3000CPS-20000CPS.The viscosity of aliphatic urethane acrylate should be not less than 1000CPS, now can increase mixing Solidification adhesiveness afterwards is so as to can achieve even application on substrate film, when viscosity is in the range of some tens of pm to millimeter During 3000CPS-20000CPS, it is not only easy to apply, and is easy to the follow-up demoulding.
Further, described aliphatic urethane acrylate is that bifunctionality aliphatic urethane acrylate is oligomeric Thing.The performance of the ultraviolet cured adhesive being obtained using bifunctionality aliphatic urethane acrylate oligomer is more preferably.Described double Degree of functionality aliphatic urethane acrylate oligomer is preferably EBECRYL8807, UA-232P, MIRAMER SC4240, JAZO At least one in JZ802, JAZO JZ302, JAZO JZ304, JAZO JZ401, JAZO JZ404.These materials all can be from It is commercially available on market.
Described 4 degree of functionality aliphatic urethane acrylate oligomer are preferably JAZO JZ306.
Further, described reactive diluent is Ethoxylated bisphenol A (10EO) dimethylacrylate (BPA (EO) 10DMA), tripropylene glycol diacrylate, isobornyl methacrylate (IBOMA), ethoxylated neopentylglycol diacrylate At least one in ester (PO2-NPGDA), pentaerythritol triacrylate (PETA), monomer JZND.
Further, described light trigger be 2,4,6- trimethylbenzoy-dipheny phosphorous oxide, 1- hydroxyl-ring At least one in base-phenyl ketone, benzophenone, reactive amines, 2- hydroxy-2-methyl -1- phenyl -1- acetone.
Further, described levelling defoamer is at least one in BYK-066N, BYK-052, BYK-410.
Further, the hardening time of described ultraviolet cured adhesive is not more than 10 seconds.Preferably, described ultraviolet cured adhesive Hardening time be not more than 6 seconds.
In technique scheme, bifunctionality aliphatic urethane acrylate oligomer and 4 degree of functionality aliphatic polies Urethane acrylate oligomer have excellent pliability, elasticity, wearability and curing rate fast the features such as；Bisphenol-A epoxy Acrylate has that high glaze, hardness is good, chemical resistance, quick solidifying, low-cost advantage；Suitable reactive diluent can improve The mechanical properties such as the toughness before and after ultra-violet curing adhesive curing；Add sufficient light trigger, solidification glue can be made under ultraviolet irradiation Rapid solidification；Add levelling defoamer, the generation of bubble in the extruding of volume to volume roller and ultraviolet irradiation solidification process, suppression can be reduced The generation of foam, improves pattern integrity degree.Under the effect of cooperating of this several material, the ultraviolet cured adhesive tool of the present invention There is hardening time short and good translucency.
Uv-curable glue photocuring detailed process is as follows：Light trigger absorbs ultraviolet radiation energy and is activated, its point Sub- outer-shell electron jumps, and generates activated centre within the extremely short time, then the unsaturated group in activated centre and resin Group's effect, causes the double bond in light-cured resin and reactive diluent molecule to disconnect, continuous polymerization reaction occurs, by low-molecular-weight Material is transformed into high molecular weight product, thus realize molecule being cross-linked with each other film forming.
AB → AB'(light trigger absorbs luminous energy finally becomes excitation state)
AB' → A'+B (formation free radical)
Reactive radical species clash into the double bond in photocureable coating and react formation growing chain：
A'+C=C → A-C-C-
The preparation method of above-described ultraviolet cured adhesive, comprises the following steps：In room temperature no ultraviolet light environment Under, by each component mixing of described ultraviolet cured adhesive, dispersed after, obtain final product described ultraviolet cured adhesive.
By selecting suitable component and proportioning, the ultraviolet cured adhesive of the present invention has the advantages that curing rate is fast, more suitable Conjunction is applied to ultraviolet nanometer imprint process, is simultaneously adapted to prepare super lyophoby film, super lyophoby film prepared therefrom has well Lyophobicity, the contact angle of film and water is more than 130 °, and by the optimization further to each component and proportioning, prepared purple Outer optic-solidified adhesive also can have the advantages that the chemical properties such as the good, toughness of translucency and mechanical property are good.
Step S4：Using described first rolling device, the substrate film being coated with uv-curable glue is imprinted, make institute State in the imprint patterns extremely described uv-curable glue of the nanostructured on the first roller platen 9；
The uv-curable glue being had the pattern of nanostructured using described first ultra-violet curing device to impressing is cured to It is fully cured, and the uv-curable glue after being subsequently fully cured departs from from described first roller platen 9
Realize completely crued requirement, the first ultra-violet curing device in order to meet uv-curable glue after the first rolling device Uv power, the diameter of the first roller platen, the coating thickness of uv-curable glue on substrate film, substrate film transmission speed Rate can be adjusted according to the characteristic of uv-curable glue.For example, indoor in experiment, record our uv-curable glues of use and existed It is not more than under the ultraviolet environments of 18mJ/cm2, when glue thickness is not more than 1.5mm, it is fully cured the time less than 5S.According to These data, the volume to volume nano impression roller diameter 160mm of our designs, control substrate film transfer rate in 50mm/s Can ensure that glue ultraviolet is fully cured the time.Generally, in the first ultra-violet curing device of volume to volume ultraviolet nanometer imprinting apparatus Uv power, the first roller platen diameter fixing under conditions of, can be by adjusting uv-curable glue on substrate film Coating thickness or substrate film transfer rate are actually needed to meet.
Preferably, the uv power of described first ultra-violet curing device is 300-2000mJ/cm2；Described first impressing A diameter of 60-200mm of roller；Coating thickness on described substrate film for the described uv-curable glue is 100～1500 μm；Described Substrate film transfer rate is 5～100mm/s.
Step S5：Substrate film after impressing is wound by wind-up roll 15
Step S6：Film after impressing is carried out strengthening the surface treatment of its lyophobicity.
Wherein, described surface treatment refers to carry out fluorination treatment to the substrate film after impressing.Fluorination treatment can reduce table Face energy, strengthens lyophobicity.Fluorination treatment is applying fluorine mixed gas (fluorine mixed gas bag on pending plastic part surface Include fluoro-gas (as steam fluorocarbons), air etc., wherein the content of fluoro-gas is from 1%-70%).Carry out fluorine When change, a kind of highly polar surface characteristic can be produced, and basic material will not be corroded.
Further, by heating fluorine mixed gas in advance, then fluorine mixed gas are imported in closed chamber to come in fact Now carry out fluorination treatment to the film after impressing.Preferably, the temperature of heating is 40-100 DEG C.When temperature is higher than 100 DEG C, Lyophoby better performances, the time of needs is shorter, but so that film is turned to be yellow, when temperature is less than 40 DEG C, then when needing longer Between.
Test shows, compared to conventional process, even if up to several weeks film resting period after processing, surface tension is also only There is inappreciable reduction.Another fluorine can produce required surface change because having the reactivity of height, and without going through Supply energy carrys out activating reaction process.Therefore, it can very easily carry out this process merely with closed chamber.
The method that the volume to volume ultraviolet stamping mass of the present invention prepares super lyophoby surface micro-structure adopts uv-curable glue Coating is fully cured the demoulding and is surface-treated the technique being surface-treated again again, and solidification and knockout course utilize same device simultaneously Carry out, solve the problems, such as that ultra-violet curing glue can not penetrate in super lyophoby surface micro-nano structure chamber completely, optimize volume right Volume nano-imprint process.
Embodiment 4
Volume to volume ultraviolet stamping mass according to the present invention prepares an enforcement of the method for super lyophoby surface micro-structure Example, the method comprises the following steps：
Step S1'：Volume to volume ultraviolet nanometer imprinting apparatus in embodiment 2 are provided
Step S2'：Extract out continuous from described let off roll 1 for substrate film and along fixed course transmission
Step S3'：Using described apparatus for coating, uv-curable glue is coated on described substrate film 16
Wherein, described ultraviolet cured adhesive comprises the component of following weight/mass percentage composition：Aliphatic urethane acrylate： 20%～90%, bisphenol A epoxy acrylate：0～20%, reactive diluent：10%～50%, light trigger：1%～ 15%th, levelling defoamer：0～5%.
Further, described ultraviolet cured adhesive comprises the component of following weight/mass percentage composition：Aliphatic polyurethane third Olefin(e) acid ester：78%～85%, Ethoxylated bisphenol A (10EO) dimethylacrylate (BPA (EO) 10DMA)：10～15%, three Propylene glycol diacrylate：4～6%, 2- hydroxy-2-methyl -1- phenyl -1- acetone：2～5%, wherein, Ethoxylated bisphenol A (10EO) dimethylacrylate and tripropylene glycol diacrylate are reactive diluent, 2- hydroxy-2-methyl -1- phenyl -1- Acetone is light trigger.The ultraviolet cured adhesive that this embodiment is obtained has curing rate soon (hardening time is not more than 7s), Translucency is good, toughness more preferably, the advantage of prepared based superhydrophobic thin films lyophobicity more preferably (contact angle is more than 140 °).Wherein, ethoxy Base bisphenol-A (10EO) dimethylacrylate is also called (10) Ethoxylated bisphenol A dimethylacrylate, and its No. CAS is 41637-38-1, it is commercially available to obtain, such as Miwon Specialty Chemical Co., Ltd company MIRAMER M2101 type product.
Further, described ultraviolet cured adhesive comprises the component of following weight/mass percentage composition：Aliphatic polyurethane third Olefin(e) acid ester：80%th, Ethoxylated bisphenol A (10EO) dimethylacrylate (BPA (EO) 10DMA)：12%th, tripropylene glycol dipropyl Olefin(e) acid ester：4.8%th, 2- hydroxy-2-methyl -1- phenyl -1- acetone：3.2%.
Further, described aliphatic urethane acrylate is bifunctionality aliphatic urethane acrylate oligomer With at least one in 4 degree of functionality aliphatic urethane acrylate oligomer.Described aliphatic urethane acrylate glutinous Spend for 3000CPS-20000CPS.The viscosity of aliphatic urethane acrylate should be not less than 1000CPS, now can increase mixing Solidification adhesiveness afterwards is so as to can achieve even application on substrate film, when viscosity is in the range of some tens of pm to millimeter During 3000CPS-20000CPS, it is not only easy to apply, and is easy to the follow-up demoulding.
Further, described aliphatic urethane acrylate is that bifunctionality aliphatic urethane acrylate is oligomeric Thing.The performance of the ultraviolet cured adhesive being obtained using bifunctionality aliphatic urethane acrylate oligomer is more preferably.Described double Degree of functionality aliphatic urethane acrylate oligomer is preferably EBECRYL8807, UA-232P, MIRAMER SC4240, JAZO At least one in JZ802, JAZO JZ302, JAZO JZ304, JAZO JZ401, JAZO JZ404.These materials all can be from It is commercially available on market.
Described 4 degree of functionality aliphatic urethane acrylate oligomer are preferably JAZO JZ306.
Further, described reactive diluent is Ethoxylated bisphenol A (10EO) dimethylacrylate (BPA (EO) 10DMA), tripropylene glycol diacrylate, isobornyl methacrylate (IBOMA), ethoxylated neopentylglycol diacrylate At least one in ester (PO2-NPGDA), pentaerythritol triacrylate (PETA), monomer JZND.
Further, described light trigger be 2,4,6- trimethylbenzoy-dipheny phosphorous oxide, 1- hydroxyl-ring At least one in base-phenyl ketone, benzophenone, reactive amines, 2- hydroxy-2-methyl -1- phenyl -1- acetone.
Further, described levelling defoamer is at least one in BYK-066N, BYK-052, BYK-410.
Further, the hardening time of described ultraviolet cured adhesive is not more than 10 seconds.Preferably, described ultraviolet cured adhesive Hardening time be not more than 6 seconds.
In technique scheme, bifunctionality aliphatic urethane acrylate oligomer and 4 degree of functionality aliphatic polies Urethane acrylate oligomer have excellent pliability, elasticity, wearability and curing rate fast the features such as；Bisphenol-A epoxy Acrylate has that high glaze, hardness is good, chemical resistance, quick solidifying, low-cost advantage；Suitable reactive diluent can improve The mechanical properties such as the toughness before and after ultra-violet curing adhesive curing；Add sufficient light trigger, solidification glue can be made under ultraviolet irradiation Rapid solidification；Add levelling defoamer, the generation of bubble in the extruding of volume to volume roller and ultraviolet irradiation solidification process, suppression can be reduced The generation of foam, improves pattern integrity degree.Under the effect of cooperating of this several material, the ultraviolet cured adhesive tool of the present invention There is hardening time short and good translucency.
The preparation method of above-described ultraviolet cured adhesive, comprises the following steps：In room temperature no ultraviolet light environment Under, by each component mixing of described ultraviolet cured adhesive, dispersed after, obtain final product described ultraviolet cured adhesive.
By selecting suitable component and proportioning, the ultraviolet cured adhesive that the present invention uses has the advantages that curing rate is fast, It is more suitably applied to ultraviolet nanometer imprint process, be simultaneously adapted to prepare super lyophoby film, super lyophoby film prepared therefrom has Good lyophobicity, film is more than 130 ° with the contact angle of water, and by the optimization further to each component and proportioning, is obtained Ultraviolet cured adhesive also can have the advantages that the chemical properties such as the good, toughness of translucency and mechanical property are good.What is more important, The ultraviolet cured adhesive of the present invention, under semi-cured state, can achieve the good demoulding, and semi-cured state herein can be regarded as Hardening time is ultraviolet cured adhesive state in which during be fully cured the time 1/2～3/4.
Step S4'：Using described first rolling device, the substrate film being coated with uv-curable glue is imprinted, make institute State in the imprint patterns extremely described uv-curable glue of the nanostructured on the first roller platen 9；
The uv-curable glue being had the pattern of nanostructured using described first ultra-violet curing device to impressing is carried out once admittedly Change, subsequently the uv-curable glue in semi-cured state departs from from described first roller platen 9
Wherein, refer to be in being capable of the demoulding but the purple in the state of being not yet fully cured for the uv-curable glue of semi-cured state Outer solidification glue, be usually fully cured the time 1/2～3/4 when ultraviolet cured adhesive state in which, be not fully cured with Beneficial to later-stage secondary impressing.
The distance between two roller platens is controlled to realize the control to glue force of impression and depth of indentation for the template.In order to meet ultraviolet Solidification glue realizes the requirement of semi-solid preparation, the uv power of the first ultra-violet curing device, the first impressing after the first rolling device Coating thickness on the diameter of roller, substrate film, substrate film transfer rate can be adjusted according to the characteristic of uv-curable glue. Generally, the fixing bar of the coating thickness on the uv power of the first ultra-violet curing device, the diameter of the first roller platen, film Under part, control substrate film transfer rate to can achieve time control under ultraviolet environments for the glue, realize to glue hardening time Control.For example, indoor in experiment, the uv-curable glue having recorded our uses is in no more than 18mJ/cm2Ultraviolet environments Under, when glue thickness is not more than 1.5mm, it is fully cured the time less than 5S.According to these data, the volume to volume of our designs Nano impression roller diameter 160mm, and accelerate substrate film transfer rate and realize the ultraviolet light time to foreshorten to 3 seconds about, make Glue is partially cured, and now the solidification glue after the first rolling device is in semi-solid.The hardness of polymer or rigidity are just Imprinted column figure can be kept also not to be destroyed in the demoulding.It is then transmit to secondary crimped module, still in ultraviolet It is irradiated under luminous environment, now secondary volume to volume running roller does not have any pattern, but pass through volume to volume running roller extrusion film Columnar microstructure is made to deform upon, the reason because of ultraviolet light direction, the solidification glue state of cure away from substrate is lower also more Easily there is compressional deformation in extruding, and the distance between two compression rollers during the secondary crimped of precise control, may be implemented in the micro- knot of column On structure, extruding is had the T-shaped micro-structural of " cap ".The lyophoby of super lyophoby surfacing prepared by improving in microstructure Property.
Preferably, the uv power of described first ultra-violet curing device is 300-2000mJ/cm2；Described first impressing A diameter of 60-200mm of roller；A diameter of 50-180mm of described second roller platen；Described uv-curable glue is in described thin substrates Coating thickness on film is 100～1500 μm；Described substrate film transfer rate is 5～100mm/s.
It should be noted that semi-solid preparation be fully cured depending on required uv agent amount.For example, in same condition Under, if being fully cured required dosage is 1000mJ, then we pass through the parameter such as governing speed, range of exposures so that The uv agent amount that on first solidification equipment, colloid is irradiated to is less than 1000mJ, is such as 700-800mJ, then be just non-complete All solidstate, the first solidification equipment is identical with the parameter of the second solidification equipment, then be irradiated on the second solidification equipment is again 700-800mJ, adds up more than 1000mJ twice it is possible to realize being fully cured.
Step S5'：Using described second rolling device to impressing have nanostructured uv-curable glue extruded so that There is default deformation in nanostructured；
Secondary solidification is carried out to the uv-curable glue after deformation using described second ultra-violet curing device, is subsequently fully cured Uv-curable glue afterwards departs from from described second roller platen 17
Step S6'：Substrate film after impressing is wound by wind-up roll 15
Step S7'：Film after impressing is carried out strengthening the surface treatment of its lyophobicity.
Wherein, described surface treatment refers to carry out fluorination treatment to the film after impressing.Fluorination treatment can reduce surface energy, Strengthen lyophobicity.Fluorination treatment be on pending plastic part surface apply fluorine mixed gas (fluorine mixed gas include containing Fluorine gas (as steam fluorocarbons), air etc., wherein the content of fluoro-gas is from 1%-70%).It is fluorinated When, a kind of highly polar surface characteristic can be produced, and basic material will not be corroded.
Further, by heating fluorine mixed gas in advance, then fluorine mixed gas are imported in closed chamber to come in fact Now carry out fluorination treatment to the film after impressing.Preferably, the temperature of heating is 40-100 DEG C.When temperature is higher than 100 DEG C, Lyophoby better performances, the time of needs is shorter, but so that film is turned to be yellow, when temperature is less than 40 DEG C, then when needing longer Between.
Test shows, compared to conventional process, even if up to several weeks film resting period after processing, surface tension is also only There is inappreciable reduction.Another fluorine can produce required surface change because having the reactivity of height, and without going through Supply energy carrys out activating reaction process.Therefore, it can very easily carry out this process merely with closed chamber.
The technique that the present invention is surface-treated using uv-curable glue coating, one-step solidification, the demoulding, secondary solidification again.First profit With impression block (as column type), semi-solid preparation uv-curable glue film is obtained by a crimped, now film is not yet completely solid Change, the micro-structural on film is consistent with the micro-structural of impression block (such as when the micro-structural of impression block is for column type, on film Micro-structural be column structure).Then carry out secondary crimped under ultraviolet light environments, can be made thereon by volume to volume extrusion film Micro-structural deform upon, thus the micro-structural obtaining given shape is (as T-shaped micro- in obtain after being deformed upon by columnar microstructure Structure).In the present embodiment, because of ultraviolet light direction the reason, when the solidification glue state of cure away from substrate is lower also more When easily there is compressional deformation in extruding, the distance between two compression rollers during the secondary crimped of precise control, may be implemented in column simultaneously In micro-structural, extruding is had the T-shaped micro-structural (as shown in Figure 6) of " cap ".Improve volume to volume ultraviolet nanometer impressing work Skill.
Therefore, for the transfer of nanoscale T-shaped super lyophoby micro-structural, it is secondary again that we pass through once impressing column type micro-structural The mode that impressing obtains T-shaped micro-structural is realized.We extrude ultra-violet curing using the roller platen volume to volume posting the anti-film of PDMS Glue, accelerates film transfer rate and realizes the ultraviolet light time to foreshorten to 3 seconds about, make glue partially cured, now solidify Glue is in semi-solid, and the hardness of polymer or rigidity can just keep imprinted column figure also not broken in the demoulding Bad.It is then transmit to secondary crimped module, is still irradiated under ultraviolet light environments, now secondary volume to volume running roller does not have Any pattern, but make columnar microstructure deform upon by volume to volume running roller extrusion film, former because of ultraviolet light direction Cause, the solidification glue state of cure away from substrate lower is also more easy in extruding compressional deformation, and the secondary crimped of precise control When two compression rollers between distance, may be implemented on columnar microstructure the T-shaped micro-structural that extruding is had " cap ".In microcosmic knot The lyophobicity of super lyophoby surfacing prepared by improving on structure.
Embodiment 5～9
Embodiment 5～9 is five embodiments of the ultraviolet cured adhesive of the present invention, sets forth every group of uv-curable glue In each component weight percent concentration.
Wherein, SC4240 is 2 official's aliphatic urethane acrylates, and EBECRYL8807 is 2 official's aliphatic polyurethane propylene Acid esters, UA-232P is 2 official's aliphatic urethane acrylates, and M2101 reactive diluent is Ethoxylated bisphenol A (10EO) two Methacrylate (BPA (EO) 10DMA), M220 reactive diluent is tripropylene glycol diacrylate, and 1173 light triggers are 2- hydroxy-2-methyl -1- phenyl -1- acetone.
Test for preparing the performance of the ultraviolet cured adhesive of super lyophoby thin-film material in embodiment 5～9, tool Body is as follows：
1st, hardening time test
Take the ultraviolet light polymerization glue described in a small amount of above-described embodiment 5～9 with dropper respectively, drop coating is in 4 inches of glass On substrate or silicon wafer substrate, using film applicator by glue drawout, glue THICKNESS CONTROL, in 200-600 micron, will scribble glue Substrate put in the EVG610 litho machine of EVG GROUP company of the U.S. and carry out uv-exposure (365nm length ultraviolet light, power 18mJ/cm2), will be set to the time for exposure 3 seconds, and take out substrate after exposure and observe glue solidification situation, if not being fully cured again gradually Increase by 1 second, until glue is fully cured, measure glue hardening time.Wherein the whether completely crued criterion of glue so that Touching positive and negative two surfaces of ultra-violet curing film with hardboard or plastics and not producing the visible adhesion coating of any naked eyes is to be fully cured.Finally Record each embodiment hardening time as shown in table 1 below.
Table 1 present invention is used for preparing the hardening time test result of the ultraviolet cured adhesive of super lyophoby thin-film material
Group It is fully cured the time
Embodiment 5 5 seconds
Embodiment 6 10 seconds
Embodiment 7 8 seconds
Embodiment 8 6 seconds
Embodiment 9 6 seconds
As can be seen from the above results, the ultraviolet light polymerization adhesive curing for preparing super lyophoby thin-film material of the present invention Time, its curing rate was substantially better than some ultraviolet photoresists of the prior art within ten seconds.
2nd, translucency test before and after solidifying
Before solidification, translucency method of testing is：A small amount of ultraviolet curing transfer adhesive liquid is put in 100ml plastic beaker, In bright place, detect by an unaided eye glue color and transparency.The ultraviolet cured adhesive translucency of embodiment 5～9 before solidification As shown in table 2, before solidification, the ultraviolet cured adhesive translucency comparison diagram of embodiment 5～9 is as shown in Figure 7 for contrast test result：
Translucency contrast test result before table 2 ultraviolet light polymerization adhesive curing of the present invention
Group Translucency Explanation
Embodiment 5 Typically Glue is in faint yellow
Embodiment 6 Good Glue is in colorless and transparent
Embodiment 7 Good Glue is in colorless and transparent
Embodiment 8 Good Glue is in colorless and transparent
Embodiment 9 Good Glue is in colorless and transparent
After solidification, translucency method of testing is：After solidification, film is placed on on the hard fabrication piece of word, through light Film after solidification observes civilian word articulation, and word more clear film translucency is better.The ultraviolet of embodiment 5～9 after solidification As shown in table 3, after solidification, the ultraviolet cured adhesive of embodiment 5～9 is cured as film to optic-solidified adhesive translucency contrast test result Translucency comparison diagram afterwards is as shown in Figure 8：
Translucency contrast test result after table 3 ultraviolet light polymerization adhesive curing of the present invention
Translucency Explanation
Embodiment 5 Typically Film is in colorless and transparent
Embodiment 6 Good Film is in colorless and transparent
Embodiment 7 Good Film is in colorless and transparent
Embodiment 8 Good Film is in colorless and transparent
Embodiment 9 Good Film is in colorless and transparent
3rd, the toughness after solidifying and foldability test
Toughness after solidification/foldability method of testing is：Will be big for thickness after embodiment 5～9 ultraviolet light polymerization adhesive curing Cause identical film repeatedly to be folded, pin film one end with tweezers, other end tweezers grip and fold makes it build up 3 Layer, observes the complexity folding and the situation that fractures.Gained film toughness after the ultraviolet light polymerization glue solidification of embodiment 5～9 Contrast test result is as shown in table 4, gained film foldability comparison diagram after the ultraviolet light polymerization glue solidification of embodiment 5～9 As shown in Figure 9.
Gained film toughness contrast test result after the solidification of table 4 ultraviolet light polymerization glue of the present invention
4th, the hydrophobicity test result of gained ultraviolet light polymerization film after solidifying
Thin-film hydrophobic method of testing is：Examine under a microscope each embodiment ultraviolet cured adhesive micro-nano imprint first Ratio of briquetting and pattern percentage of head rice situation, confirm that shaping well uses contact angle measurement to measure film micro-nano graph area and water afterwards Contact angle.Shaping well finger pattern forming rate more than 95% and under the microscope no visible broken situation, observes as shown in Figure 10 A Result is that effect is good.Then using cylindricality micro-nano stamping stencil (20 microns of pillar diameter, two 40 microns of adjacent pillar spacing, Contact-angle measurement result such as table 5 and Figure 11 of impressing embodiment 5～9 ultraviolet cured adhesive gained film and water as shown in Figure 10 B) Shown：
Table 5 ultraviolet cured adhesive gained film and the Contact-angle measurement result of water
Group Contact angle average with water
Embodiment 5 131.26°
Embodiment 6 137.67°
Embodiment 7 131.26°
Embodiment 8 147.10°
Embodiment 9 142.42°
Comprehensive above each performance test understands, for prepare super lyophoby its uv-curable glue of ultraviolet cured adhesive chemically Energy, mechanical property are all more excellent, and the combination property of wherein embodiment 8 and embodiment 9 is more excellent.
To sum up, the present invention obtains super lyophoby micro-structural using micro-contact-printing, and micro-contact printing uses soft template (such as PDMS template) on relief pattern press mold come the surface of stock by face contact formed self-assembled monolayer pattern.? Uv power is not less than 20mJ/cm2Ultraviolet environments under, ultra-violet curing glue occur polymerisation gradually become solid-like State, and in this process the function of column type, mushroom-head or T-shaped anti-film and micro-nano structure are retained.Ultra-violet curing glue exists It is fully cured into rapidly solid film from liquid state under ultraviolet light, and replicates and retain the structure of anti-film, obtain final product through the demoulding To the film with super lyophoby micro-nano structure.
Last should be noted that above example is only in order to illustrate technical scheme rather than to present invention guarantor The restriction of shield scope, although being explained in detail to the present invention with reference to preferred embodiment, those of ordinary skill in the art should Understand, technical scheme can be modified or equivalent, without deviating from the essence of technical solution of the present invention And scope.

Claims (31)

1. a kind of volume to volume ultraviolet nanometer imprinting apparatus it is characterised in that：Described volume to volume ultraviolet nanometer imprinting apparatus include：
Transmitting device, including let off roll and wind-up roll, for by the transmission route transferring substrate film setting；
Apparatus for coating, for being coated on described substrate film by uv-curable glue；
First rolling device, including the first roller platen and the first platen support roller, described first impressing roller surface has nano junction The pattern of structure, described first platen support roller coordinates described first roller platen by the imprint patterns of this nanostructured to being coated on State in the uv-curable glue on substrate film；And
First ultra-violet curing device, for solidifying the uv-curable glue of described first rolling device impressing.
2. volume to volume ultraviolet nanometer imprinting apparatus according to claim 1 it is characterised in that：Described first ultra-violet curing dress It is arranged in inside described first roller platen.
3. volume to volume ultraviolet nanometer imprinting apparatus according to claim 1 it is characterised in that：Described apparatus for coating includes Rubber roll, lower rubber roller, described lower rubber roller is immersed in glue groove, and the uv-curable glue in described glue groove carries on described through described lower rubber roller Rubber roll, is coated on described substrate film by this upper glue roller.
4. volume to volume ultraviolet nanometer imprinting apparatus according to claim 3 it is characterised in that：Described apparatus for coating also includes Scraper, described scraper after described upper glue roller, for removing unnecessary uv-curable glue.
5. volume to volume ultraviolet nanometer imprinting apparatus according to claim 1 it is characterised in that：Described volume to volume ultraviolet nanometer Imprinting apparatus also include tension control system, and described tension control system includes tension controller, tension pick-up and magnetic control Device processed, the actual tension of the described tension pick-up described substrate film of detection is simultaneously extremely described as feedback signal back using detected value Tension controller, this tension controller feeds back the deviation between actual tension value and given tension value and outputs control signals to institute State magnetic controller, drive this magnetic controller to be applied to described let off roll through stabilized current supply.
6. volume to volume ultraviolet nanometer imprinting apparatus according to claim 1 it is characterised in that：Described transmitting device also includes It is distributed in the Auxiliary support roller on described transmission route, described Auxiliary support roller includes the intermediate supports for transferring substrate film Portion and the fixed part for fixing this Auxiliary support roller, described fixed position is in intermediate supports portion two ends, described intermediate supports portion Two ends be provided with rib ringwise, rib stretches out perpendicular to intermediate supports portion and its edge is provided with and prevents substrate film Produce the flange of skew in vertical direction.
7. volume to volume ultraviolet nanometer imprinting apparatus according to claim 1 it is characterised in that：The two of described first roller platen End is respectively fixed with T-shaped screw, and T-shaped screw can adjust the distance between the first roller platen and the first platen support roller；
Described volume to volume ultraviolet nanometer imprinting apparatus are additionally provided with pressure sensor and pressure control apparatus, and pressure sensor includes one There is the flexible member of free end, the free end of flexible member can produce displacement under the control of described pressure control apparatus；Institute State pressure sensor and for the pressure that detects between described first roller platen and the first platen support roller and be fed back to described Pressure control apparatus, this pressure control apparatus is compared and according to comparative result controls with setting pressure to feedback pressure Whether flexible member free end produces displacement to promote described first roller platen or the first platen support roller to produce in vertical direction Raw movement, thus control the pressure between described first roller platen and the first platen support roller.
8. volume to volume ultraviolet nanometer imprinting apparatus according to claim 1 it is characterised in that：Described first roller platen straight Footpath is not less than 60mm.
9. volume to volume ultraviolet nanometer imprinting apparatus according to claim 1 it is characterised in that：Described first roller platen and One platen support roller adopts servomotor synchronously to drive.
10. the volume to volume ultraviolet nanometer imprinting apparatus according to any one of claim 1 it is characterised in that：Described volume pair Volume ultraviolet nanometer imprinting apparatus also include film surface processing meanss, imprint, for strengthening, the uv-curable glue having nanostructured Lyophobicity.
11. volume to volume ultraviolet nanometer imprinting apparatus according to claim 10 it is characterised in that：Described film surface is processed Device is heating fumigating room, for carrying out fluorination treatment to the substrate film after impressing.
12. volume to volume ultraviolet nanometer imprinting apparatus according to any one of claim 1～11 it is characterised in that：Described Volume to volume ultraviolet nanometer imprinting apparatus also include：
Second rolling device, after described first rolling device, including the second roller platen and the second platen support roller, described Second impressing roller surface smooths, and described second platen support roller coordinates described second roller platen to have the ultraviolet of nanostructured to impressing Solidification glue is extruded so that nanostructured occurs default deformation；
Second ultra-violet curing device, located at described second roller platen inside or outside, for solidifying described ultra-violet curing further Glue.
13. volume to volume ultraviolet nanometer imprinting apparatus according to claim 12 it is characterised in that：Described second ultra-violet curing Device is inside described second roller platen.
14. volume to volume ultraviolet nanometer imprinting apparatus according to claim 12 it is characterised in that：Described second roller platen Two ends are provided with T-shaped screw, are configured with the scale for showing its displacement by T-shaped screw.
15. volume to volume ultraviolet nanometer imprinting apparatus according to claim 12 it is characterised in that：Described second roller platen and Second platen support roller adopts servomotor synchronously to drive.
16. a kind of volume to volume ultraviolet stamping mass prepare super lyophoby surface micro-structure method it is characterised in that：Including following Step：
1) the volume to volume ultraviolet nanometer imprinting apparatus according to any one of claim 1～11 are provided；
2) extract out continuous from described let off roll for substrate film and along fixed course transmission；
3) using described apparatus for coating, uv-curable glue is coated on described substrate film；
4) using described first rolling device, the substrate film being coated with uv-curable glue is imprinted, make described first impressing The imprint patterns of the nanostructured on roller are to described uv-curable glue；
Using described first ultra-violet curing device, impressing is had the pattern of nanostructured uv-curable glue carry out being cured to it complete All solidstate, the uv-curable glue after being subsequently fully cured departs from from described first roller platen；
5) substrate film after impressing is wound by described wind-up roll.
17. methods according to claim 16 it is characterised in that：Described uv-curable glue comprises following weight/mass percentage composition Component：Aliphatic urethane acrylate：20%～90%, bisphenol A epoxy acrylate：0～20%, reactive diluent： 10%～50%, light trigger：1%～15%, levelling defoamer：0～5%.
18. methods according to claim 16 are it is characterised in that described uv-curable glue comprises following weight/mass percentage composition Component：Aliphatic urethane acrylate：78%～85%, Ethoxylated bisphenol A (10EO) dimethylacrylate：10% ～15%, tripropylene glycol diacrylate：4%～6%, 2- hydroxy-2-methyl -1- phenyl -1- acetone：2%～5%, wherein, Ethoxylated bisphenol A (10EO) dimethylacrylate and tripropylene glycol diacrylate are reactive diluent, 2- hydroxyl -2- first Base -1- phenyl -1- acetone is light trigger.
19. methods according to claim 17 or 18 are it is characterised in that described aliphatic urethane acrylate is double official In energy degree aliphatic urethane acrylate oligomer and 4 degree of functionality aliphatic urethane acrylate oligomer at least one Kind.
20. methods according to claim 16 are it is characterised in that the uv power of described first ultra-violet curing device is 300-2000mJ/cm2；A diameter of 60-200mm of described first roller platen；Described uv-curable glue is on described substrate film Coating thickness be 100～1500 μm；Described substrate film transfer rate is 5～100mm/s.
21. methods according to claim 16 it is characterised in that：Methods described also includes：Step 6) to the lining after impressing Bottom film carries out strengthening the surface treatment of its lyophobicity.
22. methods according to claim 21 it is characterised in that：Described surface treatment refers to the substrate film after impressing Carry out fluorination treatment.
A kind of 23. volume to volume ultraviolet stamping mass prepare super lyophoby surface micro-structure methods it is characterised in that：Including following Step：
Volume to volume ultraviolet nanometer imprinting apparatus according to any one of claim 12～15 1') are provided；
2') extract out continuous from described let off roll for substrate film and along fixed course transmission；
3') using described apparatus for coating, uv-curable glue is coated on described substrate film；
4') using described first rolling device, the substrate film being coated with uv-curable glue is imprinted, make described first pressure The imprint patterns of the nanostructured on print roller are to described uv-curable glue；
The uv-curable glue having the pattern of nanostructured using described first ultra-violet curing device to impressing carries out one-step solidification, with Uv-curable glue in semi-cured state departs from from described first roller platen afterwards；
5') extruded so that nanostructured is sent out using the uv-curable glue that described second rolling device has nanostructured to impressing Raw default deformation；
Secondary solidification is carried out to the uv-curable glue after deformation using described second ultra-violet curing device, after being subsequently fully cured Uv-curable glue departs from from described second roller platen；
6') substrate film after impressing is wound by wind-up roll.
24. methods according to claim 23 it is characterised in that：Described uv-curable glue comprises following weight/mass percentage composition Component：Aliphatic urethane acrylate：20%～90%, bisphenol A epoxy acrylate：0～20%, reactive diluent： 10%～50%, light trigger：1%～15%, levelling defoamer：0～5%.
25. methods according to claim 23 are it is characterised in that described uv-curable glue comprises following weight/mass percentage composition Component：Aliphatic urethane acrylate：78%～85%, Ethoxylated bisphenol A (10EO) dimethylacrylate：10% ～15%, tripropylene glycol diacrylate：4%～6%, 2- hydroxy-2-methyl -1- phenyl -1- acetone：2%～5%, wherein, Ethoxylated bisphenol A (10EO) dimethylacrylate and tripropylene glycol diacrylate are reactive diluent, 2- hydroxyl -2- first Base -1- phenyl -1- acetone is light trigger.
26. methods according to claim 24 or 25 are it is characterised in that described aliphatic urethane acrylate is double official In energy degree aliphatic urethane acrylate oligomer and 4 degree of functionality aliphatic urethane acrylate oligomer at least one Kind.
27. methods according to claim 23 it is characterised in that：The uv power of described first ultra-violet curing device is 300-2000mJ/cm2；A diameter of 60-200mm of described first roller platen；A diameter of 50-180mm of described second roller platen； Coating thickness on described substrate film for the described uv-curable glue is 100～1500 μm；Described substrate film transfer rate is 5 ～100mm/s.
28. methods according to claim 23 it is characterised in that：There is the shape before default deformation in described nanostructured For cylindricality, its there is default deformation after be shaped as hat, mushroom-shaped, T-shaped or inverted trapezoidal.
29. methods according to claim 23 it is characterised in that：Methods described also includes：Step 7') to the lining after impressing Bottom film carries out strengthening the surface treatment of its lyophobicity.
30. methods according to claim 29 it is characterised in that：Described surface treatment refers to the substrate film after impressing Carry out fluorination treatment.
The super lyophoby material that 31. methods according to any one of claim 16～30 are obtained.
CN201610811891.8A 2016-09-08 2016-09-08 Roll-to-roll ultraviolet nano-imprinting device and method for preparing super-hydrophobic surface micro-structure by using roll-to-roll ultraviolet nano-imprinting device Pending CN106444275A (en)

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