TW202017987A - Anti-ultraviolet biodegradable transparent film based on bionic structure and method fabricating the same - Google Patents

Abstract

The invention relates to an anti-ultraviolet bio-degradable transparent film made by using a bionic structure and a method for manufacturing the same, which is first to mix styrene, sodium styrene mineral and double deionized water, and fill with nitrogen in a condensing reflux device and add an initiator to react. After centrifugal rotation, the supernatant is taken out to obtain a polystyrene nanosphere suspension. The silk is taken out, in which the sericin is removed with an aqueous solution of sodium carbonate and dried to obtain a dried silk fibroin protein. The silk fibroin protein is completely dissolved by heating with an aqueous solution of lithium bromide, and the silk fibroin solution is obtained by dialysis, centrifugal rotation and removal of impurities. The polystyrene nanosphere suspension is deposited on a substrate surface with nano-scale polystyrene opal array of molds using a Langmuir-Blodgett deposition technique. The silk fibroin protein is cast into the nano-scale polystyrene opal array of molds, so that the silk fibroin completely penetrates into the gap of the nano-scale polystyrene and then dried and solidified at room temperature to form a cured sheet. Then the cured sheet is immersed in a toluene solvent until the polystyrene nanospheres thereon are completely removed to obtain an inverse opal structure film.

Description

Using biomimetic structure to make UV-resistant biodegradable transparent film and its preparation method

The invention relates to a bio-degradable transparent film made by using a bionic structure and a method for manufacturing the same, in particular to a reverse opal structure film made of styrene nanospheres and modified silk fibroin protein for supplying UV-resistant Technology of biodegradable optical products.

In 2011, Diao et al. discovered the effects of color mixing and polarization of two butterfly colors, Papilio ulysses and Papilio blumei, through observation by a scanning electron microscope. When Papilio ulysses butterfly is irradiated with UV-Vis light, it will produce two reflection peaks at 550nm and 350nm respectively. One of these two reflection peaks comes from the concave surface of the wing, and the other comes from the protruding back ridge. But the butterfly's eyes have a repetitive gene, which allows them to recognize the range of visible light to ultraviolet, and distinguish the visual color and spatial distribution, as a signal for communication and mating. Inspired by these butterfly scales, we plan to use a specific photon energy band structure to design a structure that can reduce the incidence of ultraviolet rays and apply it to the design of contact lenses to resist ultraviolet rays.

In many research fields, biocompatible materials have been widely used in food, biopharmaceuticals, clinical treatment, medical materials and environmental protection. Among them, silk fibroin (SF) is widely used in various research fields. For example, sericin is used to make maintenance products, silk protein is used as a drug carrier, and artificial skin and cornea synthesized with silk fibroin film are all based on It is the raw material. In addition, as a carrier for culturing corneal cells, it was found that silk fibroin, in addition to having good optical permeability and biocompatibility, can also diffuse metabolites well, and is suitable as a good carrier for corneal epithelial regeneration culture. . The extracted silk fibroin can be divided into two types in structure, namely Silk I and Silk II. Silk I is a random coil and α-helix structure; Silk II is a stack parallel and β-fold structure. Also due to the α-helical structure, the dried silk fibroin film will dissolve in water. To use silk fibroin to make contact lens materials, the first thing to overcome is the need to change the α-helix structure into a β-fold structure through cross-linking or hydrogen bonding, and then modify the silk fibroin to be insoluble in water. material.

The invention develops a kind of anti-ultraviolet function that does not require the addition of ultraviolet absorbers and combines with the silk fibroin protein, which is a biocompatible material, by imitating the appearance and structure of insects, and mimicking the appearance and structure of insects. Transparent film. The silk fiber has good hygroscopicity, good health care function for the human body, and can be biodegraded by itself after being discarded, combined with the ultraviolet reflection function of the multilayer nano-hole array to solve the above problems. A transparent film with anti-ultraviolet function and biodegradability is produced.

The first object of the present invention is to provide a method for manufacturing a UV-resistant biodegradable transparent film with a bionic structure. The technical means include the following steps: (a) Preparation of polystyrene nanospheres: (a1) Nanopolystyrene microspheres required for polymerization by emulsion-free polymerization method, that is, first styrene, styrene mineral acid Sodium and secondary ionized water are fully stirred and mixed, and the reaction is carried out by filling a nitrogen in an environment above room temperature with a condensing and refluxing device, and reacting after adding an initiator; (a3) After centrifugal rotation through a centrifuge, take the The supernatant to obtain the required particle size A polystyrene nanosphere suspension of polystyrene nanospheres; (b) silk fibroin protein extraction: (b1) take silkworms and heat them with aqueous sodium carbonate solution to remove sericin in silkworms; b2) Store the silk in an oven and dry to obtain the dried silk fibroin protein; (b3) Mix the silk fibroin protein with lithium bromide aqueous solution, heat and stir to make the silk fibroin protein completely dissolved; (b4) after completely dissolved The silk fibroin protein is put into a dialysis bag and injected with pure water for dialysis; (b5) The dialyzed silk fibroin protein is centrifuged in a centrifuge to remove impurities to obtain an aqueous solution of silk fibroin; and (c) Made of silkworm silk fibroin protein to make anti-opal structure film: using blue muer deposition technology to make polystyrene nano ball array, using pure water as the carrier for spreading polystyrene nano ball in the selection of secondary phase, through volatile When high ethanol is added to the polystyrene nanosphere suspension, the polystyrene nanospheres will diffuse on the water surface due to the concentration gradient. When ethanol volatilizes rapidly from the water surface, it will increase the solvent on the water surface (gas/liquid interface). Convection, so that the polystyrene nanospheres are transferred to the water surface (gas/liquid interface) and assembled into a single-layer ordered hexagonal close-packed pattern; using a blue Mouth deposition device, the polystyrene nanospheres are placed on a glass Different layers of nano-scale polystyrene opal arrays were deposited on the surface of the substrate; then the silk fibroin modified by acrylamide was cast into the nano-scale polystyrene opal array, so that the silk fibroin completely penetrated into the nano-array The gap of the grade polystyrene is dried and cured at room temperature to form a cured piece; finally, the cured piece is immersed in a predetermined volume of toluene solvent for a predetermined time, until the polystyrene nano on the cured piece After the ball is completely removed, a reverse opal structure film can be obtained.

The second object of the present invention is to provide a biodegradable transparent film made by using the bionic structure produced by the above-mentioned manufacturing method, which includes a reverse opal structure film with ultraviolet resistance and biodegradability.

The third object of the present invention is to provide an article applied with a bio-degradable transparent film made of bionic structure, which is a spectacle lens or a contact lens, including a multi-layer inverse opal structure film, which has the function of anti-UV and Environmental protection with biodegradability.

(a) Preparation of polystyrene nanospheres

(a1)‧‧‧ Nano polystyrene microspheres required for polymerization by emulsion-free polymerization

(a2) ‧‧‧Condensate reflux device filled with nitrogen and added initiator to react

(a3) ‧‧‧ Centrifugal spin to take supernatant to obtain polystyrene nanosphere suspension

(b)‧‧‧Extract silk fibroin protein

(b1)‧‧‧Remove silk sericin

(b2) ‧‧‧ Preparation of silk fibroin protein

(b3)‧‧‧Dissolve silk fibroin protein

(b4)‧‧‧dialysis silk fibroin protein

(b5)‧‧‧Preparation of silk fibroin protein solution

(c)‧‧‧‧Inverse opal structure film made of silk fibroin protein

(c1)‧‧‧Preparation of nano-scale polystyrene opal array mold core

(c2)‧‧‧Molded inverse opal structure film

(c3)‧‧‧Remove nano-scale polystyrene opal array mold core

Figure 1 is a schematic diagram of silk fibroin protein extraction of the present invention; Figure 2 (a) is Silk I of the present invention Silk I is an α-helix structure; (b) Silk II is a β-sheet structure; (c) is a silk fibroin Schematic diagram of the structure after the addition of acrylamide; Figure 3 is a schematic diagram of the present invention using modified silk fibroin to make an inverse opal array structure; Figure 4 is a particle size and distribution of polymerized PS nanospheres analyzed by Zetasizer in the present invention; Figure 5 (a) is the π-A curve diagram of the liquid phase of the polystyrene nanosphere array of the present invention; (b) is the solid-liquid phase; (c) is the solid phase; FIG. 6(a) is the present invention using AFM to observe the monolayer 3D perspective view of the surface morphology of the polystyrene nano opal array; (b) is a 2D top view; (c) is a section line; FIG. 7 (a) is the single-layer, double-layer and triple-layer polystyrene nano-particles of the present invention Schematic diagram of the ball-deposited opal array; (b) is the actual sample photo; (c) is the surface morphology of the opal array in the single layer observed by SEM; (d) the surface morphology of the opal array in the three-layer arrangement area is observed by SEM; 8(a) is a cross-sectional morphology of (i) single-layer, (ii) double-layer, and (iii) three-layer polystyrene opal arrays observed by SEM of the present invention; (b) modified silk fibroin The cross-sectional morphology of the inverse opal structure; FIG. 9(a) is the surface morphology of the inverse opal structure of the modified silk fibroin observed by SEM; (b) is the surface morphology observed by AFM; Fig. 10 (a) is the transmission spectrum of the silk fibroin film of the present invention before being modified with acrylamide; (b) is the transmission spectrum after modification; and FIG. 11 (a) is the pure silk fibroin film of the present invention ; (B) Single-layer inverse opal film made of modified silk fibroin, (c) Three-layer inverse opal film made of modified silk fibroin, (d) Six-layer inverse opal made of modified silk fibroin The transmission spectrum of the film.

In order to allow your reviewing committee to further understand the overall technical features of the present invention and the technical means to achieve the purpose of the invention, the specific embodiments and drawings are used to explain in detail as follows: Please refer to Figures 1~2 and 5 for cooperation. The first embodiment of the invention is a method for manufacturing a UV-resistant biodegradable transparent film with a bionic structure. The specific embodiment includes the following steps: (a) preparing a polystyrene nanosphere suspension, including: (a1) Nano-polystyrene microspheres required for polymerization by emulsion-free polymerization method, that is, styrene (St), styrene sodium ore (NaSS) and secondary ionized water are fully stirred and mixed; (a2) and through a condensation The reflux device is filled with nitrogen in an environment above room temperature to react, and the reaction is started after adding the initiator; (a3) Then it is centrifuged and rotated by a centrifuge, and the supernatant is taken to obtain the desired particle size including A polystyrene nanosphere suspension of uniform size polystyrene nanospheres; (b) extraction of silk fibroin protein, which includes: (b1) removal of silk sericin, that is, taking a predetermined weight of silkworm silkworm ( Bombyx mori silk), and heated with sodium carbonate Na ₂ CO ₃ aqueous solution to remove the sericin in the silkworm silkworm; (b2) prepare silkworm silk fibroin protein, that is, subsequently store the silkworm silkworm silk above room temperature Dry in the oven to obtain the dried silk fibroin protein; (b3) Dissolve the silk fibroin protein, then mix with lithium bromide LiBr aqueous solution, and heat and stir to completely dissolve the silk fibroin protein; (b4) Dialysis silk fibroin Protein, that is, the completely dissolved silk fibroin protein is put into a dialysis bag, and the outside of the dialysis belt is filled with pure water for dialysis; (b5) A silk fibroin protein aqueous solution is prepared, that is, the dialyzed silk fibroin is subsequently prepared. The protein is rotated in a centrifuge to remove impurities to obtain an aqueous solution of silk fibroin; and (c) the modified silk fibroin protein is used to make an inverse opal structure film: (c1) preparing nano-grade polystyrene opal array mold core, That is, a polystyrene nanosphere array is made by a Langmuir-Blodgett (LB) deposition technique; pure water is used as a carrier for spreading polystyrene nanospheres in the selection of the secondary phase; through high-volatility ethanol After the polystyrene PS nanosphere suspension is added, the polystyrene PS nanospheres will diffuse on the water surface due to the concentration gradient; when ethanol volatilizes rapidly from the water surface, it will increase the convection of the solvent on the water surface (gas/liquid interface) , So that the polystyrene PS nanospheres are transferred to the gas/liquid interface; due to the hydrophobic nature of the surface of the polystyrene PS nanospheres, they will self-assemble on the gas/liquid interface into a single layered ordered hexagonal close Stacking patterns; and using an LB deposition device to deposit polystyrene nanospheres on a glass substrate surface with different layers of nano-grade polystyrene opal array mold cores; (c2) molding inverse opal structure films, namely Subsequently, the silk fibroin modified by acrylamide was cast into the nano-scale polystyrene opal array, so that the silk fibroin completely penetrated into the nano-scale polystyrene opal array mold core After the gap is dried and cured at room temperature to form a cured piece; (c3) remove the nano-scale polystyrene opal array mold core, that is, the cured piece is finally immersed in a predetermined volume of toluene solvent for a predetermined time, Until the polystyrene nanospheres on the cured sheet are completely removed, a reverse opal structure film can be obtained.

In a preferred embodiment of the present invention, in step (a1), styrene (St) is 5 to 15 ml, styrene sodium ore (NaSS) is 20 to 30 mg, and secondary ionized water is 70 to 110 ml; step (a2) ), the temperature of the condensing reflux device is 60~80ºC, the starting agent is 70~100mg potassium persulfate (KPS), and the reaction time is 18~30 hours.

In a preferred embodiment of the present invention, in step (a3), the rotation speed and time of the centrifuge are 5000~7000rpm and 10~30 minutes, respectively.

In a preferred embodiment of the present invention, in step (b1), the Bombyx mori silk is 1~3g, the molar concentration of the sodium carbonate Na ₂ CO ₃ aqueous solution is 0.01~0.03M, and the sodium carbonate Na _{2 The} heating temperature in the CO ₃ aqueous solution is 80~100ºC and the heating time is 15~45 minutes; in step (b2), the drying temperature and time are 50~70ºC and 8~16 hours, respectively.

In a preferred embodiment of the present invention, in step (b3), the lithium bromide LiBr aqueous solution is 10 to 30 ml, the molar concentration is 9.0 to 10.0 M, and the heating and stirring temperature and time are respectively 50 to 70ºC and 3 to 5 hours.

Among them, in a preferred embodiment of the present invention, in step (b4), the silk fibroin protein is dialyzed with pure water for 65-80 hours.

In a preferred embodiment of the present invention, in step (b4), the silk fibroin protein is dialyzed against pure water for 72 hours, and the pure water is changed every 24 hours.

In step (b5), the speed of centrifugal rotation of the dialyzed silk fibroin is 8000-10000 rpm, and the time of centrifugal rotation is 10-30 minutes.

In an embodiment that achieves the second object of the present invention, the biodegradable transparent film made by the bionic structure made by the above-mentioned manufacturing method includes a reverse opal structure film with ultraviolet resistance and biodegradability.

Please refer to the examples shown in Figures 7 to 9 to achieve the third object of the invention, which is a biodegradable transparent film made by the above-mentioned method with a biomimetic structure that is resistant to ultraviolet rays. A decomposable article, which is a spectacle lens or a contact lens, including a multi-layer inverse opal structure film.

The experimental content of the present invention. In the present invention, it is expected that the blocked ultraviolet wavelength range is UV-A between 320 nm and 400 nm, and the particle size of the polystyrene nanospheres required for synthesis can be calculated by the following formulas (1) and (2).

Among them, n _{sf in} formula (1) is the refractive index of modified silk fibroin (=1.574), n _air is the refractive index of air (=1.000), and n _neff is the effective refractive index of inverse opal. From formula (2), it can be seen that if the inverse opal structure wants to block the UV-A band of ultraviolet rays, the relationship between its aperture and the reflection wavelength. D _{inverse opal} is the size of the inverse opal pores and the particle size of the polystyrene nanospheres we need to prepare. λ _peak is the wavelength of the reflected light corresponding to D _{inverse opal} , θ is the angle between the incident light and the normal, n _neff is the effective refractive index of the inverse opal structure. It is known from formulas (1) and (2) that if the UV-A is to be blocked from normal incidence, that is, when θ=0º, the pore size of inverse opal should be between 166 and 208 nm.

The modification and structure discussion of silk fibroin protein of the present invention. Silk fibroin is composed of amino acids as a whole, which contains Glycine, Alanine and Serine, and is arranged into more regular segments according to the sequence structure. As shown in Figure 2 and can be divided into two categories in terms of type structure, namely Silk I and Silk II. Figure 2(a) shows the irregular curl and α-helical structure of Silk I; Figure 2(b) shows the parallel and β-fold structure of Silk II. Also, because the side chain segments of the silk fibroin peptide chain are neatly arranged and connected by hydrogen bonds, there is van der Waals force between the layers, which makes the silk fibroin stretch-resistant and more resistant to acids, alkalis, salts, enzymes and heat. Strong resistance. However, since the extracted silk fibroin has a majority of α-helical structure, even the dried and formed film will dissolve in water. Therefore, we add 1% Acrylamide (AM) to the silk fibroin. As shown in Fig. 2(c), the α-helix structure is converted into β-sheet structure through hydrogen bonding and cross-linking. Make the modified silk fibroin insoluble in water.

The invention uses modified silk fibroin protein to make inverse opal structure film. In the experiment of the present invention, a polystyrene nanosphere array was fabricated by the Langmuir-Blodgett (LB) deposition method, and pure water was used as a carrier for spreading polystyrene nanospheres in the selection of the secondary phase. For the dispersion solvent in the liquid phase, select ethanol. Mainly because ethanol has a lower boiling point, it helps to improve the agglomeration of nanoparticles during the rapid volatilization process. After adding PS nanosphere suspension through ethanol with high volatility (volume ratio of ethanol to PS nanosphere suspension = 1:1), PS nanospheres will diffuse on the water surface due to the concentration gradient. When ethanol evaporates rapidly from the water surface, it will increase the convection of the solvent on the water surface (gas/liquid interface), so that the PS nanospheres are transferred to the gas/liquid interface. Due to the hydrophobic nature of the surface of PS nanospheres, they will self-assemble on the gas/liquid interface into a single layer of ordered hexagonal close-packed patterns.

Using an LB deposition device, polystyrene nanospheres are respectively deposited on the surface of the glass substrate with different layers of nano-scale polystyrene opal arrays to obtain a nano-scale polystyrene opal array mold core. Subsequently, the modified silk fibroin of acrylamide is poured into the nano-scale polystyrene opal array mold core to make it completely penetrate into its gaps, and then dried and cured at room temperature to form a cured tablet. After curing, finally immerse the cured piece in toluene solvent for several minutes until the polystyrene nanospheres are completely removed, and the inverse opal structure film can be obtained. The overall process of deposition is shown in Figure 3.

Experimental analysis of the present invention. The particle size and distribution of aggregated nano-microspheres were analyzed by laser nanometer particle size and interface potential measuring instrument (Zetasizer, 3000HS). Field Emission Scanning Electron Microscope (FE-SEM; JSM-7800F, JEOL) and Atomic Force Microscope (AFM; DI 3100, Digital Instruments) were used to observe the morphology of opal arrays and inverse opal pores . Measured by ultraviolet visible spectrometer (VARIAN 50 Conc) and ellipsometer (Model 2010/M) The optical transmittance and the refractive index of visible light are used to discuss the optical properties of the modified silk fibroin.

Experimental results of the present invention. The particle size distribution of nanospheres: Figure 4 is the analysis of the average particle size (Z-Average) of polystyrene nanospheres polymerized by soap-free emulsion polymerization with dynamic light scattering particle size analyzer. The diameter is about 182 nm, and the dispersion coefficient (Polydispersity Index, PdI) is about 0.007, indicating that the particle size distribution of the polymerized PS nanospheres is quite uniform.

Π-A constant temperature curve of polystyrene nanosphere deposition. The prepared PS nanosphere suspension was slowly dropped into the liquid phase of the secondary phase (deionized water) of the LB device with a micro pipette, and then the PS nanospheres were arranged at the gas/liquid interface. By pushing the baffle, the area of the gas/liquid interface is continuously reduced, so that the force between the PS nanospheres changes, which in turn affects their surface tension, so that the single-layer PS nanospheres produce a gaseous phase when arranged (Gas phase), liquid phase (Liquid phase), solid phase (Solid phase) arrangement, as shown in Figure 5. It can be found from Fig. 5 that there are three curves with different slopes in the π-A isothermal curve diagram: Fig. 5(a) is the liquid phase, and the surface tension of the PS nanosphere is about 30 minutes after dropping into the gas/liquid interface. Between 0.4m~1N/m. In the liquid phase area, the polystyrene nanospheres are not squeezed excessively due to the reduction of the gas/liquid interface area, so the surface tension is relatively small. At this time, most of the polystyrene nanospheres have formed an orderly arrangement. With the further squeezing of the baffle, Figure 5(b) is the solid-liquid phase (Solid-Liquid phase) area, and its surface tension is between 1~8mN/m. In this area, the slope rises sharply, which is the transition period from the liquid phase to the solid phase. As the gas/liquid interface decreases, the balls gradually move closer together, and the surface tension rises rapidly under extrusion. Figure 5(c) shows the solid phase region. The surface tension starts from 8.5mN/m, and the arrangement between PS nanospheres is the most compact, and the compressibility is like a solid. The arrangement between PS nanospheres is tight and the most typical single-layer film morphology. Even if the area of the gas/liquid interface shrinks, the pressure will not rise again. The reason why the surface tension does not rise or fall, as long as the surface of the polystyrene nanosphere is not hydrophobic It will be submerged in water, so even if the gas/liquid boundary area continues to decrease, PS nanospheres will only accumulate on both sides of the baffle, and there will be no multi-layer overlap.

Observation of opal and inverse opal structures. Fig. 6 is the surface structure of the tight array of polystyrene nanospheres observed by AFM. Both the perspective view (a) and the top view (b) of FIG. 6 can prove that the array is very close in arrangement and free of defects. After the AFM probe scan, the cross-sectional line in FIG. 6(c) shows that the diameter of the polystyrene nanosphere is 180 nm, which is consistent with the results measured by the Zetasizer analysis with a dynamic light scattering particle size analyzer. 7(a) is a schematic diagram of the structure of an opal deposited with different layers of polystyrene nanosphere arrays. For comparison, we made samples on the same piece of hydrophilic glass by LB dip drawing, as shown in Figure 7(b). Through the LB device, the glass is dipped repeatedly, and single-layer, double-layer and three-layer ordered polystyrene nanosphere arrays can be quickly produced. However, due to the multi-layer arrangement of the opal structure, defects are often generated when the layers are stacked. 7(c) and 7(d) are the surface morphology of single-layer and three-layer opal structures observed by SEM, respectively. It shows that after multilayer stacking, the surface has more defects than the single layer arrangement, and it is obvious that the perfect multilayer opal structure is not easy to obtain. Fig. 8 is a longitudinal section of observing the opal structure deposited by PS nanospheres and the inverse opal array made by modified silk fibroin in (i) single layer, (ii) double layer and (iii) three layers, respectively. Photos (Figure 8 (a), (b) respectively). It can be clearly identified from Fig. 8 that the different number of layers does not affect the number of layers and structure due to the existence of internal defects. The reversed opal structure morphology produced by the modified silk fibroin basically corresponds to the opal structure deposited by PS nanospheres, and the reverse opal structure will not be severely distorted or deformed due to defects in the opal array. Fig. 9 (a) and (b) are the surface morphology of the modified opal structure of modified silk fibroin observed by SEM and AFM, respectively, and the two show an ordered arrangement of holes. This means that after the modified silk fibroin is perfused into the opal array, it does fill the gaps of the PS opal array, so that after removing the opal structure, it can present an ordered array of holes. In Figure 9(b) AFM The shape of the hole in the image cannot be the same as the structure of the round hole taken by the SEM, which is mainly limited by the shape of the AFM probe.

Transmission spectrum analysis of silk fibroin before and after modification with acrylamide. Fig. 10 shows the optical transmission curves of the films made by silk fibroin before and without modification with acrylamide (as shown in Figs. 10(a) and (b), respectively). The optical transmittance of the two in the visible light range is about 90~91%, showing that both have good optical transparency. But the two have no significant effect on the anti-ultraviolet function of the UV-A (320~400nm) section.

Analysis of optical properties of modified opal structure with modified silk fibroin. Fig. 11 is a transmission spectrum of an inverse opal structure made with modified silk fibroin. Figure 11(a) shows that the film of pure silk fibroin modified with acrylamide still has 85% penetration in the ultraviolet (UV-A) region. After the modified silk fibroin is used to make single-layer and three-layer inverse opal structures, there will be obvious anti-ultraviolet function in the UV-A section, and their values drop to 70% and 65%, respectively (see Figure 11(b), respectively). , (C)). As the number of inverse opal layers increases to 6, the UV-A penetration rate of ultraviolet light has been reduced to 50% (see Figure 11(d)). From the above, it is shown that as the number of anti-opal layers increases, its anti-ultraviolet capability will also increase, but its optical transmittance will tend to decline in the visible light region. The main reason is that as the number of PS nanospheres increases, more defects will accumulate in the opal structure. After overmolding, too many defects remain in the inverse opal structure, resulting in a decrease in the optical transmittance of visible light. It is theoretically feasible to make a UV-resistant film with a multi-layer inverse opal structure, but in fact it is not easy to make a perfect multi-layer inverse opal structure. Nevertheless, through appropriate theoretical derivation, this technology can still be applied to the manufacture of anti-blue light filter membranes to reduce the damage of blue light to eyes in handheld mobile devices. In addition, the technology provided by the present invention can also be used to make a lens that can filter yellow light to increase the visual black and white contrast to improve the effectiveness of athlete training.

The biological material (silk fibroin protein) used in the present invention can reduce environmental pollution in addition to high human compatibility. Through the bionic structure, there is no need to add an ultraviolet absorber to produce a transparent film with an anti-ultraviolet structure to reduce the penetration of ultraviolet rays and can decompose after use. It can be applied to the production of filter films with different functions (such as anti-blue light and anti-yellowing films). Through the LB deposition dipping device, single-layer, double-layer and multi-layer opal and inverse opal arrays can be produced. The technology of the present invention can be applied to biomedical materials, such as carrier scaffolds for cell growth.

The above is only a feasible embodiment of the present invention and is not intended to limit the patent scope of the present invention. Any equivalent implementation of other changes based on the content, features and spirit described in the following claims should be Included in the patent scope of the present invention. The structural features of the invention specifically defined in the claim are not found in similar items, and are practical and progressive. They have met the requirements of the invention patent. You have filed an application in accordance with the law, and I would like to ask the Jun Bureau to approve the patent in accordance with the law to maintain this. The applicant's legal rights and interests.

(a) Preparation of polystyrene nanospheres

(a1)‧‧‧ Nano polystyrene microspheres required for polymerization by emulsion-free polymerization

(a2) ‧‧‧Condensate reflux device filled with nitrogen and added initiator to react

(a3) ‧‧‧ Centrifugal spin to take supernatant to obtain polystyrene nanosphere suspension

(b)‧‧‧Extract silk fibroin protein

(b1)‧‧‧Remove silk sericin

(b2) ‧‧‧ Preparation of silk fibroin protein

(b3)‧‧‧Dissolve silk fibroin protein

(b4)‧‧‧dialysis silk fibroin protein

(b5)‧‧‧Preparation of silk fibroin protein solution

(c)‧‧‧‧Inverse opal structure film made of silk fibroin protein

(c1)‧‧‧Preparation of nano-scale polystyrene opal array mold core

(c2)‧‧‧Molded inverse opal structure film

(c3)‧‧‧Remove nano-scale polystyrene opal array mold core

Claims (10)

A method for making a UV-resistant biodegradable transparent film with a bionic structure, which includes the following steps: (a) Preparation of polystyrene nanospheres, including the following steps: (a1) Nanoparticles required for polymerization by a milkless polymerization method Rice polystyrene microspheres, that is, styrene, sodium styrene mineral and secondary ionized water are fully stirred and mixed; (a2) and reacted by a condensing reflux device filled with nitrogen in an environment above room temperature, And add the initiator reaction; (a3) Then centrifuge and spin through a centrifuge, take the supernatant, you can get the required amount of polystyrene nanospheres with a uniform particle size and a predetermined amount of polybenzene Ethylene nanosphere suspension; (b) extracting silk fibroin protein, which includes the following steps: (b1) removing silk sericin, that is, taking silkworm silkworm, and using a predetermined molar sodium carbonate aqueous solution in a predetermined Heating for a predetermined time under the condition of temperature to remove sericin in silkworm silkworm; (b2) preparing silkworm silk fibroin protein, that is, subsequently storing silkworm silkworm silk in an environment that is higher than room temperature and dried, it can be obtained Dried silk fibroin protein; (b3) Dissolve silk fibroin protein, then mix with lithium bromide aqueous solution, and heat and stir, so that silk fibroin protein is completely dissolved; (b4) Dialysis silk fibroin protein, that is, the completely dissolved silk silk Put the silk fibroin into a dialysis bag and dialyze the outside of the dialysis belt with pure water; (b5) Preparation of silk fibroin protein aqueous solution, that is, the dialyzed silk fibroin protein is then centrifuged in a centrifuge to remove impurities to obtain silk fibroin protein aqueous solution; and (c) silk fibroin protein is used to make inverse opal Structural film: (c1) Preparation of nano-scale polystyrene opal array mold core, that is, a polystyrene nanosphere array is produced by a blue mulch deposition technique, that is, pure water is used as a spreading polybenzene in the selection of the secondary phase The carrier of vinyl nanospheres, add ethanol to the suspension of polystyrene nanospheres, so that the polystyrene nanospheres diffuse on the water surface and self-assemble into a single layer of ordered hexagonal close-packed pattern, so that the polystyrene nanometer The ball deposits at least one layer of nano-scale polystyrene opal array mold core on the surface of a glass substrate; (c2) Molding inverse opal structure film, that is, casting silk fibroin protein solution in nano-scale polystyrene opal array mold core , So that the silk fibroin protein fully penetrates into the gaps of the nano-grade polystyrene opal array mold kernels, and then dried and solidified at room temperature to form a cured piece; (c3) remove the nano-grade polystyrene opal array mold kernels, The cured piece is immersed in toluene solvent until the polystyrene nanospheres on the cured piece are completely removed, and an inverse opal structure film can be obtained. The method according to claim 1, wherein in step (a1), styrene is 5 to 15 ml, styrene sodium mineral is 20 to 30 mg, and secondary ionized water is 70 to 110 ml; in step (a2), the The temperature of the condensing reflux device is 60~80ºC, the starting agent is 70~100mg potassium persulfate (KPS), and the reaction time is 18~30 hours. The method according to claim 1, wherein in step (a3), the rotation speed and time of the centrifuge are 5000~7000rpm and 10~30 minutes, respectively. The manufacturing method according to claim 1, wherein in step (b1), the silkworm silkworm is 1~3g, The molar concentration of the sodium carbonate aqueous solution is 0.01~0.03M, and the heating temperature in the sodium carbonate aqueous solution is 80~100ºC and the heating time is 15~45 minutes; in step (b2), the drying temperature and time are 50~ 70ºC and 8~16 hours. The method according to claim 1, wherein in step (b3), the volume of the lithium bromide aqueous solution is 10 to 30 ml, the molar concentration is 9.0 to 10.0 M, and the heating and stirring temperature and time are 50 to 70ºC and 3 to 5, respectively. hour. The method according to claim 1, wherein, in step (b4), the silk fibroin protein is dialyzed with pure water for 65-80 hours, and the pure water is changed every at least 15 hours. The method according to claim 1, wherein, in step (b5), the speed of the centrifugal rotation of the dialyzed silk fibroin is 8000 to 10000 rpm, and the time of the centrifugal rotation is 10 to 30 minutes. A biodegradable transparent film made by using a bionic structure made by the manufacturing method as described in claim 1, which includes at least one inverse opal structure film. An article using the bionic structure as described in claim 8 to produce an ultraviolet-resistant biodegradable transparent film, the article is a spectacle lens, a contact lens, or a filter element. An article using the bionic structure as described in claim 9 to make a biodegradable transparent film with ultraviolet resistance, the article is a filter element, by adjusting the size of the hole of the inverse opal structure to filter out light of different wavelengths, for example Filter out blue, yellow or infrared light.

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