CN112835268B - Bio-based water-soluble negative photoresist and application thereof in femtosecond laser direct writing processing method - Google Patents
Bio-based water-soluble negative photoresist and application thereof in femtosecond laser direct writing processing method Download PDFInfo
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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
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70383—Direct write, i.e. pattern is written directly without the use of a mask by one or multiple beams
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a bio-based water-soluble negative photoresist and application thereof in a femtosecond laser direct writing processing method, wherein the negative photoresist comprises a modified biological material, a water-based photoinitiator, a cross-linking agent and an auxiliary agent; the minimum processing resolution of the bio-based water-soluble negative photoresist under the exposure of 515nm wavelength laser is 200nm; the negative photoresist has the advantages of safety, no toxicity and high printing precision; the three-dimensional space scaffold obtained by using the negative photoresist by adopting a femtosecond laser direct writing processing method has the advantages of uniform quality, good biocompatibility and easy degradation, and improves the application of biological materials in biological tissue engineering.
Description
Technical Field
The invention relates to the technical field of photoresist preparation and application, in particular to a bio-based water-soluble negative photoresist and application thereof in a femtosecond laser direct writing processing method.
Background
With the development of science and technology, the application of the laser direct writing technology is more and more extensive, and the application of the laser direct writing technology in the biological tissue process has huge potential due to the advantage of high precision. In biological tissue engineering, a three-dimensional scaffold with good biocompatibility is used as a support to provide a space for cell growth and proliferation; after the three-dimensional space scaffold is degraded, cells proliferate at the lesion site in the organism to form new tissues and organs. In the process, the three-dimensional space scaffold has a key function, and plays a role in carrying cells and providing a cell growth space.
The laser direct writing technology can obtain a three-dimensional space support with high precision, and in the laser direct writing technology, photoresist is used as an important material and has an irreplaceable effect. The photoresist used for the laser direct writing technology in the prior art is not suitable for being applied in biological tissue engineering because the raw materials have certain toxicity, poor biocompatibility and difficult degradation.
Although the common biomaterials such as gelatin, hyaluronic acid, chondroitin sulfate, chitosan and the like are applied to biological tissue engineering, the biomaterials mainly comprise naked amino, hydroxyl and the like, in the prior art, the biomaterials are placed in a mould by using the mould to perform condensation polymerization reaction to generate gel, the finishing cannot be achieved, and the biomaterials cannot be used as a photoresist because the hydroxyl, the amino and the like cannot perform multiphoton absorption and multiphoton polymerization reaction, so that the application of the biomaterials in the biological tissue engineering is limited.
At present, the biological-based photoresist is also researched or patented, but many biological materials and polymerizable monomers are physically mixed and then are subjected to photoetching crosslinking, and the mode easily causes the quality of the obtained three-dimensional space scaffold to be uneven; and due to physical mixing, the biocompatibility and degradability of the three-dimensional scaffold formed after crosslinking are difficult to control, so that the three-dimensional scaffold is limited in use.
In an application document with the application number of CN 2019106481563 and the subject name of 'a femtosecond laser internal photopolymerization direct writing processing method of methacrylic acid gelatin hydrogel', a material proportion of a methacrylic acid gelatin hydrogel photosensitive solution for 780nm femtosecond laser photopolymerization direct writing processing is disclosed, wherein the methacrylic acid gelatin hydrogel photosensitive solution comprises freeze-dried GelMA hydrogel particles, a VA-086 photoinitiator, a rose bengal photosensitizer and a 1 multiplied by PBS buffer solution; and discloses a minimum processing resolution of 253nm at a wavelength of 780 nm; in some examples of the photoresist in the application, freeze-dried methacrylate gelatin is used, but the photoresist in the application has higher initiation activity and small absorption wavelength, and according to the Relay formula, the resolution R is better when the wavelength lambda is smaller under the condition of determining other parameters, so that the resolution of the three-dimensional space scaffold in the application has the potential of being reduced. Therefore, it is important to provide a photoresist that can be applied to a short wavelength and a high process resolution.
Disclosure of Invention
In the bio-based water-soluble negative photoresist, a modified biological material is used as a main raw material, and a photoinitiator, a cross-linking agent and an auxiliary agent which are matched with the main raw material are added, so that the modified biological material is subjected to multi-photon absorption and multi-photon polymerization reaction, and the minimum processing precision of 200nm under the wavelength of 515nm laser is realized; the negative photoresist has the advantages of safety, no toxicity and high printing precision; the three-dimensional space scaffold obtained by using the negative photoresist by adopting a femtosecond laser direct writing processing method has the advantages of uniform quality, good biocompatibility and easy degradation, and improves the application of biological materials in biological tissue engineering.
The technical scheme of the invention is as follows:
a bio-based water-soluble negative photoresist comprises a modified biological material, a water-based photoinitiator, a cross-linking agent and an auxiliary agent; the minimum processing resolution of the bio-based water-soluble negative photoresist under the exposure of 515nm wavelength laser is 200nm.
Preferably, the bio-based water-soluble negative photoresist comprises the following raw materials in percentage by weight: 5-30% of modified biological material, 0.1-5% of water-based photoinitiator, 0-20% of cross-linking agent, 0.01-5% of auxiliary agent and the balance of deionized water.
Preferably, the modification method of the modified biomaterial comprises the following steps:
mixing the biological material with PBS buffer solution according to the weight volume ratio of 1:4-10, then adding a modifier into the mixture, wherein the weight volume ratio of the biological material to the modifier is 3; then controlling the temperature at 60 ℃, reacting for 8h under the condition of stirring speed of 500r/min, stopping the reaction, then using ethanol for precipitation, filtering and collecting the precipitate; dissolving the precipitate in deionized water at room temperature, dialyzing for 8 days, changing water for 3 times per day, and freeze-drying the dialysate in the dialysis bag to obtain modified biomaterial.
Preferably, the modifier is one of methacrylic anhydride or acrylic anhydride; in the application, methacrylic anhydride or acrylic anhydride is selected to interact with amino or hydroxyl in a biological material, so that an acrylic group with high free radical polymerization reactivity is grafted on the biological material, the biological material is changed into a modified biological material with multiphoton absorption and multiphoton polymerization performances, and the application of the biological material in biological tissue engineering is improved.
Preferably, the biological material is one or more of hyaluronic acid, gelatin, chondroitin sulfate and chitosan; the biological material is modified by a modifier to obtain methacrylated hyaluronic acid, methacrylated gelatin, methacrylated chondroitin sulfate, methacrylated chitosan, acrylated hyaluronic acid, acrylated gelatin, acrylated chondroitin sulfate and acrylated chitosan.
Preferably, the aqueous photoinitiator is one or more of LAP (phenyl-2, 4, 6-trimethylbenzoyllithium phosphite), irgacure2959, irgacure 184D, irgacure 907, irgacure 819DW, irgacure369, irgacure 1173, lucirin TPO-L, quantacure BTC, quantacure BPQ, quantacure QTX and Quantacure ABP.
Preferably, the cross-linking agent is a raw material containing two or more acrylate or acrylamide functional groups.
Preferably, the cross-linking agent is one or more of bifunctional acrylamide, polyfunctional acrylamide, bifunctional acrylate and polyfunctional acrylate.
Preferably, the bifunctional acrylamide is N, N-methylene bisacrylamide or polyethylene glycol bisacrylamide; the difunctional acrylate is ethoxylated bisphenol A diacrylate, ethoxy propoxy dimethacrylate, polyethylene glycol diacrylate or dipropylene glycol diacrylate; the multifunctional group acrylamide is N- [ tri (3-acrylamide propyl methyl ether) methyl ] acrylamide; multifunctional acrylates such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like.
The auxiliary agent is one or more of a photosensitizing agent, a viscosity regulator, an antibacterial agent, a polymerization inhibitor and an adhesion promoter.
Wherein, the photosensitizing agent has the following functions: the initiator is used in cooperation with the initiator, so that the initiation activity of the photoresist is improved, the initiation of reaction resin in the photoresist solution is facilitated, and the photoetching power is reduced; the viscosity regulator has the functions of: the viscosity of the photoresist is low, so that the coating thickness of the photoresist solution in the photoetching process is too thin, the immersion laser direct writing or the high three-dimensional structure processing is difficult to perform, and the viscosity of the photoresist solution can be improved by adding the tackifier in the formula, so that the coating thickness and the processability are ensured; the antibacterial agent has the functions of: the three-dimensional structure printed by the photoresist is a bio-based material, and the breeding of microorganisms is easily caused after the photoresist is placed for a long time. A small amount of antibacterial agent is added into the formula, so that the antibacterial performance of a target product can be improved; the adhesion promoter has the following functions: the resin after the photoresist solution is cured has poor binding capacity with a base material due to the characteristics of the material, and is easy to fall off in the developing and later processes, and the adhesive force of the photoresist resin can be obviously improved by adding the adhesion promoter in the formula.
The preparation method of the negative photoresist comprises the following steps: dissolving the modified biological material in water, stirring at 40 ℃ and 500r/min for 15min, then adding the cross-linking agent, stirring for 10min, continuing to add the water-based photoinitiator and the auxiliary agent, and stirring until the mixture is uniform and transparent; filtering the negative photoresist by using a 0.22 μm hydrophilic needle filter, and performing ultrasonic treatment for 30 min.
The application of a bio-based water-soluble negative photoresist in a femtosecond laser direct writing processing method comprises the following steps:
(1) Carrying out ultrasonic treatment on the prepared photoresist for 10min, and then dropwise adding 100 mu L of the photoresist to the center of a pretreated glass sheet;
(2) Selecting 515nm femtosecond laser, and adjusting the position of an objective lens to focus the femtosecond laser on the contact surface of the photoresist and the glass sheet; then realizing selective solidification through the relative displacement of the laser focus in the photoresist, and processing a three-dimensional structure at the scanning speed of 100 mu m/s and the laser power range of 5-30 mW;
(3) After exposure, the glass sheet is placed in a mixed solvent of propylene glycol monomethyl ether acetate and water in a volume ratio of 9.
When the photoresist is used in the femtosecond laser direct writing processing method, after the exposure of the laser wavelength of 515nm, the initiator in the photoresist generates free radicals to initiate polymerization and curing reactions among acrylate groups and between the acrylate groups and the cross-linking agent in the modified biological material to form cross-linked cured products, and the cross-linked cured products are insoluble in the mixed solvent, so that a three-dimensional space scaffold is formed on the glass sheet after the development through the step (3).
The principle of photoresist printing is that an initiator is excited to directly transfer electrons to a monomer or generate electron transfer to initiate polymerization. The monomers contain unsaturated double bonds or epoxy active groups and can carry out polymerization reactions such as free radicals or cations and the like so as to achieve the purpose of curing and forming. And common biobased materials do not have active groups capable of free radical or cationic polymerization, and cannot be directly printed by photoetching. Lithographic printing is generally achieved by doping polymerizable monomers or functionalizing biobased materials.
Negative photoresist: the photosensitive mixed liquid consists of photosensitive resin, photoinitiator, photosensitizer, solvent and other components. After illumination, the photoinitiator in the exposure area generates free radicals or cations to initiate the photosensitive resin to generate chemical reaction, the negative photoresist is the photoresist which generates the photocrosslinking curing reaction in the exposure area to form insoluble substances, and then the unexposed soluble part is dissolved by proper solvent treatment to obtain the photoetching image.
Compared with the prior art, the invention has the beneficial effects that:
1. in the preparation process of the negative photoresist, the modified biological material is adopted as a raw material, and the monomer of the modified material is fully utilized to react with functional groups such as amino, hydroxyl and the like on a molecular chain of the biological material, so that the obtained modified material has biocompatibility and degradability of the biological material and polymerizability of the modified material, the negative photoresist prepared by the modified biological material can be suitable for producing a high-precision three-dimensional space scaffold, and the obtained three-dimensional space scaffold can meet the requirements of biological tissue engineering and expand the application range of the biological material.
2. By using the negative photoresist provided by the invention, the minimum processing resolution is 200nm under the exposure of 515nm wavelength laser; in addition, the negative photoresist is a uniform material when in use, and the uniformity of the quality of the printed three-dimensional space support can be ensured on the premise of determining the wavelength of the photoetching machine.
3. The biological material is derived from renewable resources such as natural biological materials and the like, can be degraded, participates in chemical circulation in biological tissues after being degraded, and promotes the growth of the biological tissues.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
Figure 1 is an SEM photograph of the minimum line width of a negative photoresist of example 2.
Fig. 2 is an SEM picture of three-dimensional scaffold a obtained in example 6.
FIG. 3 shows the mechanism of photopolymerization for the photoresist containing methacrylated hyaluronic acid and methacrylated gelatin in example 1.
Fig. 4 is an SEM picture of the three-dimensional space scaffold obtained in the comparative example.
In the figure, 1-methacrylated hyaluronic acid and 2-methacrylated gelatin.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
Example 1 preparation of modified biomaterial
(1) Methacrylated gelatin: weighing 10g of gelatin, placing the gelatin into 100ml of PBS buffer solution at 60 ℃, then slowly adding 10ml of methacrylic anhydride, oscillating, magnetically stirring and uniformly mixing; then reacting for 8h at 60 ℃ and 500r/min, terminating the reaction, precipitating by using ethanol, filtering and collecting the precipitate; dissolving the precipitate in deionized water at room temperature, dialyzing at room temperature for 8 days, changing water for 3 times per day, and freeze drying dialysate in dialysis bag to obtain modified biological material
(2) Methacrylated hyaluronic acid: the difference from (1) is that the biological material is hyaluronic acid (10g), PBS buffer solution (60 ml) and methacrylic anhydride (30 ml).
(3) Methacrylated chondroitin sulfate: the difference from (1) is that the biomaterial is chondroitin sulfate 10g, PBS buffer 70ml, and methacrylic anhydride 15ml.
(4) Methacrylated chitosan: the difference from (1) is that the biomaterial is chitosan (10g), PBS buffer solution (50 ml) and methacrylic anhydride (3.5 ml).
(5) Acrylated chitosan: the difference from (4) is that the modifier is acrylic anhydride.
(6) Acrylated hyaluronic acid: the difference from (2) is that the modifier is acrylic anhydride.
(7) Acrylated gelatin: the difference from (1) is that the modifier is acrylic anhydride.
(8) Acrylated chondroitin sulfate: the difference from (3) is that the modifier is acrylic anhydride.
The modified biomaterial prepared in example 1 was applied in the following example.
EXAMPLE 2 preparation of a Bio-based methacrylate negative photoresist
Weighing 10g of deionized water in a brown reagent bottle, adding magnetons, and stirring at 40 ℃ and 500 r/min; sequentially adding 0.9g of methacrylated gelatin and 0.1g of methacrylated hyaluronic acid under the condition of stirring, continuously stirring for 15min, adding 0.2g of N, N-methylene bisacrylamide, stirring for 10min, adding a photoinitiator Irgacure2959 and a phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite mixture (the mass ratio of the photoinitiator Irgacure2959 to the phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite is 1); and filtering the negative photoresist by using a 0.22-micron hydrophilic needle filter, then carrying out homogenization and defoaming by ultrasonic treatment for 30min, and sealing for later use.
Example 3 preparation of a biobased acrylate negative photoresist
Weighing 10g of deionized water in a brown reagent bottle, adding magnetons, and stirring at 40 ℃ and 500 r/min; sequentially adding 3g of acrylated chitosan under the condition of stirring, continuously stirring for 15min, adding a mixture of 0.3g of photoinitiator Irgacure2959 and phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite (the mass ratio of the photoinitiator Irgacure2959 to the phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite is 3; and filtering the negative photoresist by using a 0.22-micron hydrophilic needle filter, then carrying out homogenization and defoaming by ultrasonic treatment for 30min, and sealing for later use.
EXAMPLE 4 preparation of negative Photoresist
Weighing 10g of deionized water in a brown reagent bottle, adding magnetons, and stirring at 40 ℃ and 500 r/min; sequentially adding 1g of prepared methacrylated chitosan and 0.5g of methacrylated chondroitin sulfate under the stirring condition, continuously stirring for 15min, adding 1g of N, N-methylene bisacrylamide, stirring for 10min, adding 0.5g of photoinitiator Irgacure2959, and stirring until the mixture is uniform and transparent to obtain the negative photoresist; and filtering the negative photoresist by using a 0.22-micron hydrophilic needle filter, then carrying out homogenization and defoaming by ultrasonic treatment for 30min, and sealing for later use.
EXAMPLE 5 preparation of negative Photoresist
The difference from example 2 is that 1.2g of acrylated chondroitin sulfate and 0.4g of methacrylated gelatin are used as modified biomaterials.
Photoetching test:
the negative photoresist prepared by the method is subjected to photoetching test, and specifically comprises the following steps: carrying out ultrasonic treatment on the negative photoresist for 10min, coating 100 mu L of the negative photoresist on a treated glass sheet, carrying out exposure direct writing test by using 515nm wavelength laser, carrying out scanning speed of 100 mu m/s and laser power range of 5-30mW, developing in a mixed solvent of propylene glycol monomethyl ether acetate and water (ratio is 9: 20mW.
In the photoetching test process, the glass sheet is processed by the following steps: performing acetone ultrasonic treatment for 10min, performing isopropanol ultrasonic treatment for 10min, performing deionized water ultrasonic treatment for 10min, drying by compressed nitrogen, and performing final surface cleaning treatment by PLASMA (PLASMA gas).
The formula of the photoresist needs to be matched with the photoetching wavelength (515 nm) to realize high-precision processing, so that the composition of the negative photoresist is reasonably configured, and the multiphoton absorption and the multiphoton polymerization reaction under the exposure wavelength are ensured.
Example 6 application of negative photoresist prepared in example 2 in femtosecond laser direct writing processing method
(1) Treating a base material: selecting a 5 x 5cm glass sheet as a sample substrate, respectively carrying out ultrasonic treatment on the glass sheet for 10min by using acetone, isopropanol and deionized water in sequence before processing, drying the glass sheet by using compressed nitrogen, and then carrying out surface treatment on the glass sheet by using PLASMA (PLASMA enhanced chemical vapor deposition);
(2) Fixing a base material: fixing the glass sheet treated in the step (1) on a three-dimensional displacement platform by using glue;
(3) Preparing a photoresist: carrying out ultrasonic treatment on the negative photoresist prepared in the embodiment 2 for 10min, and then dropwise adding 100 mu L of the negative photoresist to the central position of a glass sheet;
(4) Preparing photoetching: selecting 515nm femtosecond laser, and adjusting the position of an objective lens to focus the femtosecond laser on the contact surface of the photoresist and the glass sheet;
(5) And (3) photoetching process: realizing selective solidification through the relative displacement of a laser focus in the photoresist, wherein the scanning speed is 100 mu m/s, the laser power is 20mW, and the three-dimensional structure processing is carried out;
(6) And (3) developing: and after exposure, developing in a mixed solvent of propylene glycol monomethyl ether acetate and water with the volume ratio of 9.
The negative photoresists prepared in examples 3 to 5 were applied by the same method as in example 6, and three-dimensional scaffolds were prepared, which were named three-dimensional scaffold b, three-dimensional scaffold c, and three-dimensional scaffold d in this order.
Observing the appearances of the three-dimensional space bracket a, the three-dimensional space bracket b, the three-dimensional space bracket c and the three-dimensional space bracket d, wherein the three-dimensional space bracket a, the three-dimensional space bracket b, the three-dimensional space bracket c and the three-dimensional space bracket d are all in a complete hemisphere shape, and the hemisphere is complete and accords with the target setting of the bracket at the beginning of printing; in addition, the surface of the hemisphere is smooth and has no burrs, which shows that the three-dimensional space scaffold produced by using the negative photoresist has good strength and hardness and can be applied to biological tissue engineering.
Comparative example 1
The difference from example 2 is that the modified biomaterial ratio was changed and the addition amount was 3%.
Weighing 10g of deionized water in a brown reagent bottle, adding magnetons, and stirring at 40 ℃ and the rotating speed of 500 r/min; sequentially adding 0.3g of methacrylic acid esterified gelatin under the stirring condition, continuously stirring for 15min, adding 0.1g of photoinitiator Irgacure2959, and stirring until the mixture is uniform and transparent to obtain the negative photoresist; and filtering the negative photoresist by using a 0.22-micron hydrophilic needle filter, then carrying out homogenization and defoaming by ultrasonic treatment for 30min, and sealing for later use.
The obtained hemisphere has incomplete three-dimensional shape, concave top, rough surface and poor photoetching printing effect.
Although the present invention has been described in detail by referring to the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (2)
1. A bio-based water-soluble negative photoresist is characterized by comprising the following raw materials in percentage by weight: 5-30% of modified biological material, 0.1-5% of water-based photoinitiator, 0-20% of cross-linking agent, 0.01-5% of auxiliary agent and the balance of deionized water; the minimum processing resolution of the bio-based water-soluble negative photoresist under the exposure of 515nm wavelength laser is 200nm;
the modifier is one of methacrylic anhydride or acrylic anhydride;
the aqueous photoinitiator is one or more of LAP (phenyl-2, 4, 6-trimethyl benzoyl lithium phosphite), irgacure2959, irgacure 184D, irgacure 907, irgacure 819DW, irgacure369, irgacure 1173, lucirin TPO-L, quantacure BTC, quantacure BPQ, quantacure QTX and Quantacure ABP;
the cross-linking agent is one or more of bifunctional acrylamide, polyfunctional acrylamide, bifunctional acrylate and polyfunctional acrylate;
the auxiliary agent is one or more of a photosensitizing agent, a viscosity regulator, an antibacterial agent, a polymerization inhibitor and an adhesion force increasing agent; the modification method of the modified biomaterial comprises the following steps:
mixing the biological material with the PBS buffer solution uniformly according to the weight volume ratio of 1; then controlling the temperature at 60 ℃, reacting for 8 hours under the condition of stirring speed of 500r/min, stopping the reaction, then using ethanol for precipitation, filtering and collecting the precipitate; dissolving the precipitate in deionized water at room temperature, dialyzing for 8 days, changing water for 3 times per day, and freeze-drying dialysate in dialysis bag to obtain modified biological material; the biological material is one or more of hyaluronic acid, gelatin, chondroitin sulfate and chitosan; the application of the bio-based water-soluble negative photoresist in the femtosecond laser direct writing processing method comprises the following steps:
(1) Carrying out ultrasonic treatment on the prepared photoresist for 10min, and then dropwise adding 100 mu L of the photoresist to the center of a pretreated glass sheet;
(2) Selecting 515nm femtosecond laser, and adjusting the position of an objective lens to focus the femtosecond laser on the contact surface of the photoresist and the glass sheet; then realizing selective solidification through the relative displacement of the laser focus in the photoresist, and carrying out three-dimensional structure processing at the scanning speed of 100 mu m/s and the laser power range of 5-30 mW;
(3) After exposure, the glass sheet is placed in a mixed solvent of propylene glycol monomethyl ether acetate and water in a volume ratio of 9.
2. The bio-based water-soluble negative photoresist of claim 1, wherein the negative photoresist is prepared by a process comprising: dissolving the modified biological material in water, stirring at 40 ℃ and 500r/min for 15min, then adding the cross-linking agent, stirring for 10min, continuing adding the water-based photoinitiator and the auxiliary agent, and stirring until the mixture is uniform and transparent; filtering the negative photoresist by using a 0.22 μm hydrophilic needle filter, and performing ultrasonic treatment for 30 min.
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