Long-wave ultraviolet absorbing photosensitive materials and their applications

Abstract

The present invention discloses a long-wavelength ultraviolet (UV) absorbing photosensitive material and its applications. The photosensitive material has the following structure: #imgabs0#, wherein R1 comprises a linear or branched alkyl group with a carbon number of 1-20, a substituted alkyl group, a substituted aryl group, a substituted heterocyclic aryl group, an ethylene glycol chain with a carbon number of 1-20, or an N-substituted linear or branched alkyl group. The oxygen-containing groups in the novel photosensitive material system capable of long-wavelength absorption and hydrophilic-hydrophobic conversion can significantly red-shift the material's absorption. The light source is inexpensive and readily available, and large-scale fabrication is possible. It can also be applied to flexible substrates, offering greater application prospects. The fine-structured circuits fabricated using the present method exhibit excellent electrical conductivity.

Description

Technical Field

[0001] The present invention relates to a photosensitive material, in particular to a long-wave ultraviolet absorbing photosensitive material and a preparation method thereof, as well as an application of the photosensitive material in preparing hydrophilic and hydrophobic patterns, belonging to the technical field of circuit printing. Background Art

[0002] The maximum resolution of conventional printed electronics processes often depends on the droplet size and the surface energy and tension of the droplet on the substrate. To minimize feature size, ink diffusion on the surface must be limited. While dewetting can improve pattern resolution to some extent, on substrates with low surface energy, unstable lines can form bumps, which locally widen the printed pattern and reduce feature continuity.

[0003] In addition to surface energy modification, pre-patterning of surfaces with different wettability or surface topography in different areas of the substrate can also help reduce the spread of the ink solution. Wettability gradients can enable self-aligned printing of ink droplets, and are a method that relies on wettability differences to prepare ultrafine gaps (Noh YY, Zhao N, Caironi M, et al. Downscaling of self-aligned, all-printed polymer thin-film transistors [J]. Nature Nanotechnology, 2007, 2 (12): 784-789.). Currently, there are two main methods for inducing wettability gradients on substrate surfaces:

[0004] One method is to gradually apply a self-assembled monolayer, polymer brush, polymer film or coating to a substrate (Bliznyuk O, Seddon JRT, Veligura V, et al. Directional Liquid Spreading over Chemically Defined Radial Wettability Gradients[J]. Acs Applied Materials&Interfaces, 2012, 4(8): 4141-4148.), such as microcontact printing (Schlisske S, Raths S, Ruiz-Preciado LA, et al. Surface energy patterning for ink-independent process optimization of inkjet-printed electronics[J]. Flexible and Printed Electronics, 2021, 6(1).), which has the advantages of convenience, speed, and a wide range of materials.

[0005] The other type mainly modifies the polymer surface by irradiation, chemical etching, corona discharge or radio frequency plasma discharge (Caelen I, Gao H, Sigrist H. Protein density gradients on surfaces [J]. Langmuir, 2002, 18 (7): 2463-2467.).

[0006] The inventors of this case discovered in their work that, using the acrylate-NBE photosensitive material developed by Rossegger (Rossegger E, Nees D, Turisser S, et al. Photo-switching of surface wettability on micropatterned photopolymers forfast transport of water droplets over a long-distance [J]. Polymer Chemistry, 2020, 11 (18): 3125-3135.), after visible light curing, a mask can be used to expose a designated area by 254nm ultraviolet light to create a wettability gradient, thereby providing a printing process for a fine structure conductive circuit that spontaneously patterns the ink using surface energy differences. The contact exposure used in the above technology can only be at the micron resolution level, and the scattering of the scattered light source will inevitably have a certain impact on the exposure accuracy. Summary of the Invention

[0007] The main purpose of the present invention is to provide a long-wave ultraviolet absorbing photosensitive material and a preparation method thereof, as well as an application thereof in preparing hydrophilic and hydrophobic patterns, so as to overcome the deficiencies in the prior art.

[0008] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include:

[0009] An embodiment of the present invention provides a long-wave ultraviolet absorbing photosensitive material having a structure as shown in Formula I:

[0010]

[0011] Among them, R1 includes any one of a straight chain or branched chain alkyl group containing 1 to 20 carbon atoms, a substituted alkyl group, a substituted aryl group, a substituted heterocyclic aryl group, an ethylene glycol chain containing 1 to 20 carbon atoms, an N-substituted straight chain or branched chain alkyl group, and the like.

[0012] The present invention also provides a method for preparing a long-wave ultraviolet absorbing photosensitive material, which comprises:

[0013] allowing a first mixed reaction system comprising 5-hydroxy-2-nitrobenzyl alcohol, a compound containing an R1 group, a first catalyst, and a first solvent to undergo a first reaction to produce an intermediate product;

[0014] A second mixed reaction system comprising the intermediate product, acryloyl chloride, a second catalyst, and a second solvent is subjected to a second reaction to prepare a long-wave ultraviolet absorbing photosensitive material having a structure as shown in Formula I.

[0015] Among them, R1 of the compound containing the R1 group includes any one of a straight chain or branched chain alkyl group with a carbon number of 1-20, a substituted alkyl group, a substituted aryl group, a substituted heterocyclic aryl group, an ethylene glycol chain with a carbon number of 1-20, an N-substituted straight chain or branched chain alkyl group, etc.

[0016] The embodiment of the present invention also provides a long-wave ultraviolet absorbing photosensitive material prepared by the above preparation method.

[0017] An embodiment of the present invention further provides a method for preparing a hydrophilic-hydrophobic patterned substrate, which comprises:

[0018] Providing a mixed solution comprising the long-wave ultraviolet absorbing photosensitive material, a multifunctional thiol, a fluorinated ester monomer, and a photoreactive resin;

[0019] The mixed solution is applied to a substrate, and the formed initial film is cured under visible light irradiation conditions, and then contact-exposed under ultraviolet light, so that the initial film in the exposed area is transformed and induced to produce a hydrophilic-hydrophobic pattern substrate with a wettability gradient.

[0020] The embodiment of the present invention also provides a hydrophilic-hydrophobic patterned substrate prepared by the above preparation method.

[0021] An embodiment of the present invention further provides a method for preparing a fine conductive circuit, which includes:

[0022] The conductive ink is uniformly deposited on the surface of the hydrophilic-hydrophobic patterned substrate, the ink is self-aligned and transferred, and finally dried and sintered to form a fine conductive circuit.

[0023] Correspondingly, an embodiment of the present invention also provides a fine conductive circuit manufactured by the aforementioned manufacturing method.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1) The present invention provides a novel photosensitive material system capable of long-wavelength absorption and hydrophilic-hydrophobic conversion. The oxygen-containing groups in the system can significantly red-shift the absorption of the material. The light source is inexpensive and readily available, which is conducive to industrial application. It can be prepared on a large scale and can be extended to flexible substrates, showing great application prospects.

[0026] 2) The present invention breaks through the resolution limit of existing conventional printing processes, and the preparation process is simple and can be achieved only by scraping. The fine structure circuit prepared by the method of the present invention has excellent conductivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0028] Figure 1 This is a schematic diagram comparing exposures using a 254nm diffuse light source and a 365nm parallel light source;

[0029] Figure 2a 、 Figure 2b are respectively BNO-[CH2] prepared in Example 1 of the present invention n -ONB compounds, P-BNO-[CH2] n -NMR spectrum of ONB-P photosensitive material (n=3);

[0030] Figure 3a 、 Figure 3b They are respectively the NMR spectra of the BNO-PEG-ONB compound and the P-BNO-PEG-ONB-P photosensitive material (m=1) prepared in Example 2 of the present invention;

[0031] Figure 4a 、 Figure 4b They are respectively the NMR spectra of the BNO-PEG-ONB compound and the P-BNO-PEG-ONB-P photosensitive material (m=2) prepared in Example 3 of the present invention;

[0032] Figure 5a 、 Figure 5b They are respectively the NMR spectra of the BNO-PEG-ONB compound and the P-BNO-PEG-ONB-P photosensitive material (m=3) prepared in Example 4 of the present invention;

[0033] Figure 6 is BNO-[CH2-CH2-O] with different m values ​​in a typical embodiment of the present invention m -ONB(m=1,2), and BNO-[CH2] with different n values n -UV absorption pattern of ONB (n=3) compound;

[0034] Figure 7 Schematic diagram of the difference in contact angles of the hydrophilic and hydrophobic patterned substrate in Example 1 of the present invention;

[0035] Figure 8 1 is a graph showing the conductivity test results of the fine conductive circuit prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0036] Given the limitations of contact exposure methods used in the prior art, which only achieve micron-level resolution and the inevitable impact of scattered light sources on exposure accuracy, the inventors of this case, after extensive research and extensive practice, were able to propose the technical solution of the present invention. To improve exposure accuracy and produce higher-resolution conductive circuits, a parallel light source is undoubtedly a better choice. Because parallel light sources in the UV-C band are expensive and difficult to obtain, the inventors of this case developed a photosensitive material system that can induce conversion under long-wavelength UV-A ultraviolet light.

[0037] The technical solution, its implementation process and principles are further explained below.

[0038] One aspect of an embodiment of the present invention provides a long-wave ultraviolet absorbing photosensitive material having a structure as shown in Formula I:

[0039]

[0040] Among them, as a preferred embodiment, R1 can be selected from any one of a linear or branched alkyl group, a substituted alkyl group, a substituted aryl group, a substituted heterocyclic aryl group, etc. having a carbon number of 1-20, but is not limited thereto.

[0041] As another preferred embodiment, R1 may also be an ethylene glycol chain having a carbon number of 1-20.

[0042] As another preferred embodiment, R1 can also be selected from any one of N-substituted straight-chain or branched alkyl groups, but is not limited thereto.

[0043] In some preferred embodiments, R1 in the photosensitive material has any of the following structures: etc., but not limited to.

[0044] Wherein, n is an integer greater than or equal to 1, preferably 1 to 20; m is an integer greater than or equal to 1, preferably 1 to 9; x is an integer greater than or equal to 1, preferably 1 to 4; R2 includes, but is not limited to, a straight-chain or branched alkyl group with a carbon number of 1-6, a substituted alkyl group, a substituted aryl group, a substituted heterocyclic aryl group, and the like.

[0045] Specifically, in some more specific embodiments, the long-wave ultraviolet absorbing photosensitive material may have any of the following structures:

[0046]

[0047] Wherein, n is an integer greater than or equal to 1, preferably 1 to 3; m is an integer greater than or equal to 1, preferably 1 to 3; R2 includes a straight chain or branched alkyl group with a carbon number of 1-6, a substituted alkyl group, a substituted aryl group, a substituted heterocyclic aryl group, etc., preferably an alkane with a carbon number of 1-3, but not limited thereto.

[0048] For example, Taking (P-BNO-PEG-ONB-P) as an example, the mechanism of this case is:

[0049] Compared with the previously used material NBE, whose main absorption peak is located at 260nm, the absorption spectrum of the new molecule BNO-PEG-ONB shows that the main absorption peak of the material is concentrated at 310nm.

[0050] A=εbc

[0051] Where:

[0052] A——Absorbance

[0053] ε——molar absorption coefficient, L / mol·cm;

[0054] b——liquid layer thickness, em;

[0055] c——Concentration of substance, mol / L.

[0056] The present invention provides a series of photosensitive materials with long-wavelength ultraviolet absorption properties. Through molecular modification, this series of materials achieves a red-shift in the material's absorption spectrum, resulting in strong absorption in common ultraviolet bands, such as 365nm. Currently, the molar absorption coefficient of these materials can reach ε = 125 L / mol·em at 365nm. Therefore, this series of materials can adapt to currently common collimated ultraviolet light sources, inducing a wettability gradient in the substrate and enabling spontaneous patterning of metallic conductive inks.

[0057] Another aspect of the embodiments of the present invention further provides a method for preparing a long-wave ultraviolet absorbing photosensitive material, which comprises:

[0058] allowing a first mixed reaction system comprising 5-hydroxy-2-nitrobenzyl alcohol, a compound containing an R1 group, a first catalyst, and a first solvent to undergo a first reaction to produce an intermediate product;

[0059] allowing a second mixed reaction system comprising the intermediate product, acryloyl chloride, a second catalyst, and a second solvent to undergo a second reaction to prepare a long-wave ultraviolet absorbing photosensitive material having a structure as shown in Formula I;

[0060] The type of the R1 group of the compound containing the R1 group is as described above and will not be repeated here.

[0061] In a specific embodiment, the first solvent may include at least any one of N,N-dimethylformamide (DMF), tetrahydrofuran (THF), etc., but is not limited thereto.

[0062] Further, the second solvent may include tetrahydrofuran (THF), but is not limited thereto.

[0063] Furthermore, the first catalyst includes K2CO3, but is not limited thereto.

[0064] Furthermore, the second catalyst includes Et3N, but is not limited thereto.

[0065] In a specific embodiment, the molar ratio of the 5-hydroxy-2-nitrobenzyl alcohol, the compound containing an R1 group and the first catalyst is 6:1:9 to 2:1:3.

[0066] In a specific embodiment, the molar ratio of the intermediate product, acryloyl chloride and the second catalyst is 1:4:5 to 1:8:10.

[0067] In a specific embodiment, the temperature of the first reaction is 60° C. to 80° C., and the time is 24 h to 48 h.

[0068] In a specific embodiment, the temperature of the second reaction is room temperature, and the time is 24 hours to 48 hours.

[0069] In a specific embodiment, taking the photosensitive material (P-BNO-PEG-ONB-P) as an example, the preparation method thereof specifically includes:

[0070] allowing a first mixed reaction system comprising 5-hydroxy-2-nitrobenzyl alcohol, a TsO-PEG-OTS compound having a PEG segment structure, a first catalyst, and a first solvent to undergo a first reaction to prepare a BNO-PEG-ONB compound;

[0071] allowing a second mixed reaction system comprising a BNO-PEG-ONB compound, acryloyl chloride, a second catalyst, and a second solvent to undergo a second reaction to prepare a long-wave ultraviolet absorbing photosensitive material;

[0072] The TsO-PEG-OTS compound having a PEG segment structure has a structure as described in Formula II:

[0073]

[0074] The BNO-PEG-ONB compound has a structure as described in Formula III:

[0075]

[0076] Here, m is an integer greater than or equal to 1, and preferably 1-9.

[0077] The preparation mechanism of P-BNO-PEG-ONB-P in this application is:

[0078] In previous work, the o-NBE material used by the inventors of this case exhibited a characteristic absorption wavelength at 254 nm. In the technical solution of the present invention, the inventors devised a synthetic route using 5-hydroxy-2-nitrobenzyl alcohol and TsO-PEG-OTS with varying PEG chain lengths to synthesize BNO-PEG-ONB, which was then reacted with acryloyl chloride to form P-BNO-PEG-ONB-P, as shown in the reaction formula below. The oxygen-containing groups in P-BNO-PEG-ONB-P significantly red-shift the material's absorption wavelength.

[0079]

[0080] In a specific embodiment, Taking photosensitive materials as an example, the preparation reaction formula is as follows:

[0081]

[0082] Here, m is an integer greater than or equal to 1, preferably 1-9, and particularly preferably 1-3.

[0083] In a specific embodiment, Taking photosensitive materials as an example, the preparation reaction formula is as follows:

[0084]

[0085] In a specific embodiment, Taking photosensitive materials as an example, the preparation reaction formula is as follows:

[0086]

[0087] R2 includes straight-chain or branched alkyl groups, substituted alkyl groups, substituted aryl groups, substituted heterocyclic aryl groups, etc. having a carbon number of 1-6, and is preferably an alkane having a carbon number of 1-3.

[0088] The molar ratios of the raw materials used in the above preparations are all within the ranges defined above.

[0089] Another aspect of the embodiments of the present invention further provides a long-wave ultraviolet absorbing photosensitive material prepared by the above-mentioned preparation method.

[0090] Furthermore, based on this material, the inventors of this case developed a photosensitive material formulation system comprising a long-wave ultraviolet absorbing photosensitive material, a multifunctional thiol, a fluorinated ester monomer, and a photoreactive resin, which can be cured into a hydrophobic film under visible light and then photolyzed and converted into a hydrophilic film under ultraviolet light.

[0091] Another aspect of an embodiment of the present invention further provides a method for preparing a hydrophilic-hydrophobic patterned substrate, comprising:

[0092] Providing a mixed solution comprising the aforementioned long-wave ultraviolet absorbing photosensitive material, a multifunctional thiol, a fluorinated ester monomer, and a photoreactive resin;

[0093] The mixed solution is applied to a substrate, and the formed initial film is cured under visible light irradiation conditions, and then contact-exposed under ultraviolet light, so that the initial film in the exposed area is transformed and induced to produce a hydrophilic-hydrophobic pattern substrate with a wettability gradient.

[0094] Furthermore, the visible light irradiation condition is white light irradiation with a wavelength of more than 400 nm for 10 to 30 minutes, and the contact angle of the hydrophobic film obtained after curing with water is more than 100°.

[0095] Furthermore, the contact exposure conditions of the ultraviolet light include exposure at a wavelength of 260 to 365 nm for 15 to 50 minutes, and the contact angle between the hydrophilic film obtained by photolysis and conversion under ultraviolet light and water is below 10°.

[0096] Furthermore, the preparation method includes: applying the mixed solution on a substrate by spin coating.

[0097] In a specific embodiment, the present invention also provides a specific method for preparing a hydrophilic and hydrophobic pattern using the above-mentioned material:

[0098] The photosensitive material (P-BNOv[CH2] n -ONB-P (n=3)), multifunctional thiol (such as PETMP), fluorinated ester monomer (such as FD700 resin) and photosensitizer (such as BAPO) are prepared into a solution and spin-coated on a substrate. The initial film is cured under white light >400nm; then, a chrome-plated mask is used for ultraviolet light exposure to induce a hydrophilic-hydrophobic pattern with a wettability gradient.

[0099] Another aspect of the embodiments of the present invention further provides a hydrophilic-hydrophobic patterned substrate prepared by the aforementioned preparation method.

[0100] Specifically, another aspect of the embodiments of the present invention further provides a method for preparing a fine conductive circuit, which includes:

[0101] The conductive ink is evenly deposited onto the surface of the aforementioned hydrophilic and hydrophobic patterned substrate, the ink is self-aligned and transferred, and finally dried and sintered to form a fine conductive circuit.

[0102] In a specific embodiment, the sintering temperature is 120° C. to 300° C., and the sintering time is 20 to 30 minutes.

[0103] In a specific embodiment, the conductive ink may include Ag nanoparticle conductive ink, but is not limited thereto.

[0104] In a specific embodiment, the preparation method includes: uniformly depositing the conductive ink onto the surface of the hydrophilic-hydrophobic patterned substrate through a doctor blade coating process.

[0105] Furthermore, the present invention aims to obtain a method for obtaining a fine structure with a high contrast wettability difference based on contact exposure, and provide a method for preparing fine conductive circuits by self-assembly of Ag nanoparticle ink using a hydrophilic-hydrophobic patterned substrate assisted scraping process.

[0106] Fine conductive circuit printing: This invention utilizes a scraping process and adjusts parameters to uniformly deposit conductive ink onto a pre-structured substrate. The ink is self-aligned and transferred, and finally dried and sintered to obtain a fine conductive circuit with a conductive pattern.

[0107] Correspondingly, another aspect of an embodiment of the present invention further provides a fine conductive circuit, which is prepared by the above-mentioned preparation method, that is, a fine conductive circuit prepared by a scraping process on a hydrophilic and hydrophobic patterned substrate.

[0108] Furthermore, the width of the fine conductive circuit is 1 μm.

[0109] The present invention will be more fully understood through the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it should be understood that the disclosed embodiments are merely exemplary of the present invention, which can be embodied in various forms. Therefore, the specific functional details disclosed herein should not be construed as limiting, but rather as a basis for the claims and as a representative basis for teaching those skilled in the art to employ the present invention in various ways in virtually any appropriately detailed embodiment.

[0110] Example 1

[0111] In this embodiment, P-BNO-[CH2] n The preparation process of the -ONB-P (n=3) photosensitive material is as follows:

[0112]

[0113] 5-Hydroxy-2-nitrobenzyl alcohol, Br-[CH2] n -Br(n=3), K2CO3, THF mixture, 5-hydroxy-2-nitrobenzyl alcohol, Br-[CH2] n -Br (n = 3) and K2CO3 in a molar ratio of 6:1:9, and reacted at 65 ° C for 48 h to obtain BNO-[CH2] n -ONB compound (n=3);

[0114] BNO-[CH2] n -ONB compound, acryloyl chloride, Et3N, THF mixture, BNO-[CH2] n -ONB compound, acryloyl chloride, and Et3N were reacted at a molar ratio of 1:4:5 at room temperature for 24 h to obtain P-BNO-[CH2] n -ONB-P (n=3) photosensitive material.

[0115] The BNO-[CH2] n -ONB (n = 3) compound NMR spectrum is as follows Figure 2a As shown in the UV absorption diagram Figure 6 As shown; P-BNO-[CH2] n -ONB-P (n = 3) NMR spectrum is as follows Figure 2b shown.

[0116] The photosensitive material P-BNO-[CH2] prepared in this example n-ONB-P (n=3), PETMP, FD700 resin, and photosensitizer BAPO were mixed to form a photosensitive material solution, which was spin-coated on a substrate at room temperature. The initial film was cured under white light >400nm, and a hydrophobic film was obtained after curing. Then, a chrome-plated quartz mask was used to expose the film under ultraviolet light to induce a hydrophilic-hydrophobic pattern substrate with a wettability gradient. The difference in contact angle before and after UV irradiation was compared. Figure 7 Then, conductive ink Ag nanoparticles were scraped onto the pre-hydrophobic patterned substrate, dried, and sintered at 300°C for 30 minutes to produce a fine conductive circuit corresponding to the mask design pattern. The conductivity test results are shown in Figure 8 shown.

[0117] Example 2

[0118] The preparation process of the P-BNO-PEG-ONB-P (m=1) photosensitive material in this embodiment is as follows:

[0119]

[0120] 5-hydroxy-2-nitrobenzyl alcohol, TsO-PEG-OTS (m=1), K2CO3, and THF were mixed in a molar ratio of 2:1:3, and reacted at 65°C for 24 hours to prepare a BNO-PEG-ONB compound (m=1);

[0121] The BNO-PEG-ONB compound (m=1), acryloyl chloride, Et3N, and THF were mixed, with the molar ratio of compound II-1, acryloyl chloride, and Et3N being 1:8:10, and reacted at room temperature for 36 hours to obtain the P-BNO-PEG-ONB-P photosensitive material (m=1).

[0122] The NMR spectrum of the BNO-PEG-ONB compound (m=1) obtained in this example is shown in FIG. Figure 3a As shown in the UV absorption diagram Figure 6 As shown; the NMR spectrum of P-BNO-PEG-ONB-P photosensitive material (m=1) is as shown Figure 3b shown.

[0123] Example 3

[0124] 5-hydroxy-2-nitrobenzyl alcohol, TsO-PEG-OTS (m=2), K2CO3, and DMF were mixed in a molar ratio of 6:1:9 and reacted at 80°C for 40 h to prepare a BNO-PEG-ONB compound (m=2);

[0125] The BNO-PEG-ONB compound (m=2), acryloyl chloride, Et3N, and THF were mixed, with the molar ratio of compound II-1, acryloyl chloride, and Et3N being 1:8:10, and reacted at room temperature for 34 hours to obtain the P-BNO-PEG-ONB-P photosensitive material (m=2).

[0126] The NMR spectrum of the BNO-PEG-ONB compound (m=2) obtained in this example is shown in FIG. Figure 4a As shown in the UV absorption diagram Figure 6 As shown; the NMR spectrum of P-BNO-PEG-ONB-P photosensitive material (m=2) is as shown Figure 4b shown.

[0127] Example 4

[0128] 5-hydroxy-2-nitrobenzyl alcohol, TsO-PEG-OTS (m=3), K2CO3, and DMF were mixed in a molar ratio of 2:1:3, and reacted at 60°C for 48 hours to prepare a BNO-PEG-ONB compound (m=3);

[0129] The BNO-PEG-ONB compound (m=3), acryloyl chloride, Et3N, and THF were mixed, with the molar ratio of compound II-1, acryloyl chloride, and Et3N being 1:4:5, and reacted at room temperature for 48 hours to obtain the P-BNO-PEG-ONB-P photosensitive material (m=3).

[0130] The NMR spectrum of the BNO-PEG-ONB compound (m=3) obtained in this example is shown in FIG. Figure 5a As shown; the NMR spectrum of P-BNO-PEG-ONB-P photosensitive material (m=3) is as shown Figure 5b shown.

[0131] Example 5

[0132] The preparation process of another photosensitive material in this embodiment is as follows:

[0133]

[0134] Mix 5-hydroxy-2-nitrobenzyl alcohol, compound 5-1, K2CO3, and DMF. The molar ratio of 5-hydroxy-2-nitrobenzyl alcohol, compound 5-1, and K2CO3 is 6:1:9. React at 80°C for 24h to obtain the intermediate product. 5-2;

[0135] Compound 5-2, acryloyl chloride, Et3N, and THF were mixed in a molar ratio of 1:4:5, and reacted at room temperature for 24 hours to obtain the final product, a photosensitive material (compound 5-3).

[0136] The intermediate product obtained in this example The UV absorption diagram of Figure 6 shown.

[0137] Comparative Example 1

[0138] The difference between this comparative example and Example 1 is that a compound without a PEG segment structure, such as an acrylate-NBE material system, is used.

[0139] Compared to Comparative Example 1, the present invention primarily modifies existing materials to red-shift their absorption, enabling long-wave conversion. Parallel long-wavelength light sources are more affordable and readily available, and collimated light sources help improve the resolution of hydrophilic and hydrophobic patterns and subsequent fine circuits. Existing material systems, however, convert at 254nm and use conventional diffuse light sources. Due to the inevitable gap between the mask and the substrate, although small, it still affects exposure. The diffuse light source can overexpose edges, resulting in reduced pattern accuracy.

[0140] In addition, the inventors of this application also used other raw materials and process conditions listed in this specification, and prepared a series of long-wavelength ultraviolet-absorbing photosensitive materials in the manner described in Examples 1-7. Testing revealed that these long-wavelength ultraviolet-absorbing photosensitive materials also exhibited the excellent properties described in this specification.

[0141] In summary, the present invention provides a new photosensitive material system capable of long-wavelength absorption and hydrophilic-hydrophobic conversion. The oxygen-containing groups therein can cause a significant red shift in the absorption of the material. The light source is inexpensive and readily available, can be prepared on a large area, and can be extended to flexible substrates, showing greater application prospects. The fine structure circuits prepared by the method of the present invention have excellent conductivity.

[0142] Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions, and / or additions may be made and that substantial equivalents may be substituted for elements of the described embodiments without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present invention without departing from the scope of the invention. Therefore, it is not intended that the present invention be limited to the specific embodiments disclosed for carrying out the invention, but rather that the invention will encompass all embodiments falling within the scope of the appended claims.

Claims

1. A method for preparing a fine conductive circuit, characterized in that: include: Conductive ink is uniformly deposited onto a hydrophilic and hydrophobic patterned substrate surface, the ink is self-aligned and transferred, and finally dried and sintered to form a fine conductive circuit; The method for preparing the hydrophilic-hydrophobic patterned substrate comprises: (1) providing a mixed solution comprising a long-wave ultraviolet absorbing photosensitive material, a multifunctional thiol, a fluorinated ester monomer, and a photoreactive resin; (2) applying the mixed solution to a substrate, curing the formed initial film under visible light irradiation conditions, and then contact-exposing the initial film under ultraviolet light, so that the initial film in the exposed area is transformed and induced to produce a hydrophilic and hydrophobic pattern substrate with a wettability gradient; The visible light irradiation condition includes irradiation with white light of a wavelength of 400 nm or more for 10 to 30 minutes, and the contact angle between the hydrophobic film obtained after curing and water is greater than 100°; the contact exposure condition of the ultraviolet light includes exposure at a wavelength of 260 to 365 nm for 15 to 50 minutes, and the contact angle between the hydrophilic film obtained by photolysis and conversion under ultraviolet light and water is less than 10°; The long-wave ultraviolet absorbing photosensitive material has any one of the following molecular structural formulas: ； Wherein, n is 1 to 3; m is 1 to 3; and R2 is an alkane having a carbon number of 1 to 3.

2. The preparation method according to claim 1, wherein: In step (2), the mixed solution is applied to the substrate by spin coating.

3. The preparation method according to claim 1, wherein: The conductive ink is Ag nanoparticle conductive ink.

4. The preparation method according to claim 1, characterized in that include: The conductive ink is uniformly deposited on the surface of the hydrophilic-hydrophobic patterned substrate through a doctor blade coating process.

5. A fine conductive circuit, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 4, and the width of the fine conductive circuit is 1 μm.

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