A photosensitive resin composition, a method for preparing the same, a metal circuit, a method for preparing the same, and an application thereof
By electroless deposition of conductive metal patterns on an insulating substrate using photosensitive resin compositions, the problems of environmental pollution and high equipment costs associated with traditional methods are solved. This method achieves high-precision and stable preparation of conductive metal patterns, making it suitable for large-scale production of flexible electronic devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SOUTHERN UNIVERSITY OF SCIENCE AND TECHNOLOGY
- Filing Date
- 2026-03-11
- Publication Date
- 2026-06-23
AI Technical Summary
Existing technologies struggle to efficiently and cost-effectively fabricate high-quality conductive metal patterns on insulating substrates, especially on complex three-dimensional structures. Furthermore, traditional methods suffer from environmental pollution, expensive equipment, and low precision.
A photosensitive resin composition comprising functional monomers, acrylate monomers, crosslinking agents, photoinitiators, and light absorbers is used to form a metal conductive pattern on the substrate surface via an electroless deposition method. Metal deposition is achieved by utilizing quaternary ammonium cations to catalyze active anions, and rapid self-crosslinking and adaptability to various substrates are achieved by combining ultraviolet curable groups.
It achieves high-precision and stable fabrication of conductive metal patterns on insulating substrates, applicable to a variety of substrates, and solves the problems of environmental pollution and high equipment cost of traditional methods, making it suitable for large-scale production of flexible electronic devices.
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Figure CN122255346A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electronic device materials technology, and in particular to a photosensitive resin composition and its preparation method, a metal circuit and its preparation method and application. Background Technology
[0002] Flexible electronic devices, with their unique properties of bendability, stretchability, lightweight and portability, have been deeply integrated into numerous fields such as information display, energy conversion and storage, medical diagnosis and actuation, robotics, and wearable devices, becoming a vital force driving the electronics industry towards intelligence and portability. As the core functional unit of flexible electronic devices, conductive metal patterns play crucial roles in signal transmission and energy supply. The advancement of their fabrication technology directly determines the device's performance ceiling, production cost, and the feasibility of large-scale mass production. Therefore, developing efficient, low-cost fabrication methods that can adapt to complex three-dimensional structures has always been a core issue that urgently needs to be addressed in the field of flexible electronics.
[0003] Currently, various metal conductive pattern fabrication technologies have been developed in the industry, such as photolithography and electroplating. These technologies differ significantly in principle and application scenarios, and also reveal many limitations that cannot be ignored. Common problems include complex processes, high costs, and difficulty in achieving complex three-dimensional structures. Their specific limitations are as follows: Photolithography is a classic process in traditional microelectronics manufacturing systems. It achieves the transfer of fine patterns through multiple steps of mask preparation, exposure and development, and chemical etching. While it can achieve high resolution, the process is cumbersome and complex, requiring strict environmental control and precision equipment at each step. Furthermore, it generates a large amount of waste liquid containing chemical reagents, resulting in significant waste of raw materials and posing a potential threat to the environment. Screen printing transfers metallic ink to the substrate surface through mask mesh. It is relatively simple to operate and is used in some scenarios where high precision is not required. However, this method also relies on customized masks, and the adhesion between the formed metal layer and the substrate is weak. During long-term bending and stretching, problems such as detachment and breakage can easily occur, seriously affecting the lifespan and reliability of the device. Laser direct writing requires no mask and can directly induce metal deposition or etching to form patterns on the substrate surface using a laser beam. It offers flexibility for small-batch, personalized conductive pattern fabrication. However, its core equipment is expensive, processing efficiency is low, and the fabrication time for a single pattern is long. Furthermore, it suffers from poor uniformity and controllability of the metal coating thickness, making it difficult to meet the efficiency and quality requirements of large-scale industrial production. Traditional electroplating relies on an external power source to provide an electric field, using a conductive substrate as the cathode to achieve the reduction deposition of metal ions. While this method can obtain thicker metal layers, it requires a conductive substrate and cannot directly fabricate patterns on insulating substrates such as plastics and ceramics, greatly limiting its application on non-conductive substrates. The rise of 3D printing technology has made rapid prototyping of complex three-dimensional structures possible, demonstrating unique advantages in personalized customization and complex device manufacturing. However, directly printing metal materials faces challenges such as high equipment costs, limited material selection, and the difficulty in balancing printing accuracy and mechanical properties, hindering its widespread application in the large-scale production of flexible electronic devices.Electrodeposition technology, as a metal deposition method that does not require an external power source, can grow metal coatings on non-conductive surfaces through autocatalytic reactions, opening up a new path for the preparation of conductive patterns on insulating substrates. However, traditional electrodeposition methods rely on complex pretreatment processes for chemical plating, requiring the grafting of catalytically active polymer layers onto the substrate surface. These grafted polymers are usually prepared through time-consuming in-situ polymerization processes, which are difficult to match with the high efficiency of rapid manufacturing processes such as 3D printing. At the same time, the nanoparticle inks developed for electrodeposition generally suffer from poor stability. They usually need to be prepared and used immediately, and long-term storage can easily lead to particle agglomeration and loss of activity. Furthermore, the coffee ring effect is prone to occur during the deposition and drying process, resulting in defects such as uneven morphology and edge protrusions in the metal deposition layer, which seriously affects the flatness and conductivity of the conductive pattern.
[0004] Therefore, there is an urgent need to develop a stable and printable functional material system that can efficiently deposit high-quality metallic conductive patterns on the surfaces of various substrates, including insulating substrates, while taking into account the low cost and environmental friendliness of the fabrication process, in order to meet the urgent needs of the flexible electronics industry to rapidly develop towards high performance, low cost, and large-scale applications. Summary of the Invention
[0005] This invention aims to at least solve one of the technical problems existing in the prior art. To this end, this invention proposes a photosensitive resin composition that can effectively improve the plating properties of the photosensitive resin composition, ultimately enhancing the accuracy of the subsequent metal conductive pattern size and the stability of conductivity.
[0006] The present invention also provides a method for preparing the above-mentioned photosensitive resin composition.
[0007] The present invention also provides a metal circuit prepared by means of the above-mentioned photosensitive resin composition.
[0008] The present invention also provides a method for manufacturing the above-mentioned metal circuit.
[0009] The present invention also provides applications of the above-described photosensitive resin composition and / or metal circuits.
[0010] According to an embodiment of a first aspect of the present invention, a photosensitive resin composition is provided, wherein the raw materials for preparing the photosensitive resin composition include: Functional monomers, acrylate monomers, crosslinking agents, photoinitiators, and light absorbers; The functional monomer is an ionic compound composed of a quaternary ammonium cation and a fluorosulfonyl imide anion; the quaternary ammonium cation includes a UV-curable group.
[0011] The photosensitive resin composition according to embodiments of the present invention has at least the following beneficial effects: (1) In the functional monomers used in this invention, the quaternary ammonium cations can adsorb anions with catalytic activation properties; therefore, after the photosensitive resin composition is cured, the adsorbed catalytically active ions can catalyze the electroless deposition of subsequent metal conductive patterns; that is to say, the use of the functional monomers improves the dimensional accuracy and conductivity stability of the subsequent metal conductive patterns to a certain extent.
[0012] (2) The functional monomers used in this invention contain UV curable groups. Combined with the acrylate monomers, crosslinking agents and initiators, the self-crosslinking of the photosensitive resin composition and grafting to the substrate surface in the subsequent metal circuit can be completed at room temperature in one step (only ≈10 seconds), without the need for time-consuming in-situ polymerization. In addition, the functional monomers used in this invention are miscible with a variety of organic solvents, which broadens the application scenarios of the photosensitive resin composition.
[0013] (3) Compared with traditional metal nanoparticle inks, the photosensitive resin composition provided by the present invention has each component dissolved and dispersed in a homogeneous molecular or ionic state, avoiding the inherent problems of aggregation, sedimentation and deactivation of nanoparticle inks. Therefore, the photosensitive resin composition provided by the present invention can be stably stored for more than 12 months in a conventional laboratory environment (room temperature, protected from light) without precipitation, viscosity change or UV-Vis absorption attenuation, thus solving the stability problem of existing electrodeposition inks; thereby enabling large-scale, repetitive production.
[0014] (4) In the photosensitive resin composition provided by the present invention, the synergistic effect between the raw materials ensures that it has good 3D printing adaptability, curing strength and precision control capability, and the resulting photosensitive resin layer has excellent mechanical properties; in addition, it can be adapted to various printing technologies such as soft photolithography, inkjet printing, and screen printing, and has a wide range of applications.
[0015] According to some embodiments of the present invention, the UV-curable group includes at least one of acryloyloxy and acrylamide.
[0016] According to some embodiments of the present invention, the acrylate monomers include at least one selected from butyl acrylate (CAS: 141-32-2), methyl acrylate (CAS: 292638-85-8), ethyl acrylate (CAS: 140-88-5), benzyl acrylate (CAS: 2495-35-4), isooctyl acrylate (CAS: 103-11-7), hexyl acrylate (CAS: 2499-95-8), isobornyl acrylate (CAS: 5888-33-5), tert-butyl acrylate (CAS: 1663-39-4), epoxy acrylate (CAS: 71281-65-7), butyl methacrylate (CAS: 97-88-1), and benzyl methacrylate (CAS: 2495-37-6).
[0017] According to some embodiments of the present invention, the acrylate monomers include butyl acrylate and isobornyl acrylate. The mass ratio of butyl acrylate to isobornyl acrylate is 0.8 to 1.2:1; for example, it can be 1:1.
[0018] According to some embodiments of the present invention, the crosslinking agent includes a multifunctional acrylate crosslinking agent.
[0019] According to some embodiments of the present invention, the crosslinking agent is selected from at least one of polyethylene glycol diacrylate (CAS: 26570-48-9), 1,6-hexanediol dimethacrylate (CAS: 6606-59-3), triallyl isocyanurate (CAS: 1025-15-6), ethoxylated trimethylolpropane triacrylate (CAS: 28961-43-5), and pentaerythritol tetraacrylate (CAS: 4986-89-4). These substances have different functionalities and molecular chain lengths, which can regulate the crosslinking density and network structure, thereby optimizing the final properties of the photosensitive resin composition.
[0020] According to some embodiments of the present invention, when the crosslinking agent is selected from polyethylene glycol diacrylate, the number average molecular weight (Mn) of the crosslinking agent is 500 to 800; for example, it can be 500, 600, 700, 800; or a range of values composed of any two of the above points.
[0021] According to some embodiments of the present invention, the photoinitiator is selected from at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (CAS: 75980-60-8), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (CAS: 162881-26-7), 2-hydroxy-2-methyl-1-phenyl-1-propanone (CAS: 7473-98-5), and 1-hydroxycyclohexylphenyl ketone (CAS: 947-19-3).
[0022] According to some embodiments of the present invention, the light absorber is selected from at least one of Sudan Orange G (CAS: 842-07-9), Sudan I (CAS: 842-07-9), quercetin (CAS: 117-39-5), and mushey yellow (CAS: 605-69-6).
[0023] According to some embodiments of the present invention, the photosensitive resin composition comprises, by weight, the following: The functional monomer is 10 to 30 parts; for example, it can be 10 parts, 15 parts, 20 parts, 25 parts, or 30 parts; or a range of values composed of any two of the above point values.
[0024] 70 to 90 parts of acrylate monomers; for example, specifically 70 parts, 75 parts, 80 parts, 85 parts, or 90 parts; or a range of values consisting of any two of the above points.
[0025] Crosslinking agent 0.1 to 1 part; for example, it can be 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1 part; or a range of values composed of any two of the above points.
[0026] The photoinitiator is 0.5 to 2 parts; for example, it can be 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 2 parts; or a range of values consisting of any two of the above points.
[0027] The light absorber is 0.02 to 0.5 parts. For example, it can be 0.02 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.3 parts, 0.4 parts, or 0.5 parts; or a range of values consisting of any two of the above points.
[0028] According to an embodiment of a second aspect of the present invention, a method for preparing the photosensitive resin composition described in the first aspect of the present invention is provided, the preparation method comprising the following steps: S1. The functional monomer and the acrylate monomer are mixed and then mixed with the crosslinking agent; S2. Mix the mixture obtained in step S1 with the photoinitiator and the light absorber.
[0029] Since the preparation method adopts all the technical solutions of the photosensitive resin composition of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments.
[0030] According to some embodiments of the present invention, in step S1, the method for synthesizing the functional monomer includes a mixed reaction of a first raw material and a second raw material; The first raw material includes a quaternary ammonium cation; the second raw material includes a fluorosulfonamide anion.
[0031] According to some embodiments of the present invention, the first raw material includes at least one of acryloyloxyethyltrimethylammonium chloride (80 wt.% aqueous solution, CAS: 44992-01-0) or (3-acrylamidopropyl)trimethylammonium chloride (75% aqueous solution, CAS: 45021-77-0).
[0032] The first monomer available on the market exists in solution form and is not miscible with other acrylate monomers. Therefore, by mixing and reacting it with the second monomer to obtain the functional monomer, the hydrophilic first raw material is modified, and its lipophilicity is improved. This not only overcomes the problem that the first raw material is not miscible with other monomers, but also obtains a stable photosensitive resin composition.
[0033] According to some embodiments of the present invention, the second raw material comprises lithium bis(trifluoromethanesulfonyl)imide (CAS: 90076-65-6).
[0034] According to some embodiments of the present invention, the weight ratio of the first monomer and the second monomer is 1~3:1.5~4. For example, it can be 1:0.5, 1:1, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:3, 1:4; or a range of values consisting of any two of the above points.
[0035] According to some embodiments of the present invention, the method for synthesizing the functional monomer is as follows: an aqueous solution of the first raw material and water are mixed, then mixed with the second raw material, stirred, and allowed to stand for separation; the lower oil phase is collected, washed with water, and dried to obtain the final product. The aqueous solution of the first raw material has a mass concentration of 75-80%. For example, it can be 75%, 77%, 80%; or a range of values consisting of any two of the above points.
[0036] The mass ratio of the aqueous solution of the first raw material to water is 1~1.5:10~13. For example, it can be 1:13, 1.2:13, 1.5:13; or a range of values consisting of any two of the above points.
[0037] The stirring time is 24h to 48h. For example, it can be 36h.
[0038] The water washing is performed 5 times.
[0039] The drying conditions were vacuum drying at 60°C for 12 hours.
[0040] The washing and drying conditions described herein are merely illustrative and not strictly limited. In actual production, they can be adjusted according to the reaction volume and available experimental conditions.
[0041] According to an embodiment of a third aspect of the present invention, a metal circuit is provided, the metal circuit comprising a substrate, an activation layer and a metal conductive pattern superimposed thereon; the activation layer comprises a photosensitive resin layer and catalytically active ions adsorbed thereon; the raw material for preparing the photosensitive resin layer comprises the photosensitive resin composition described in the first aspect of the present invention.
[0042] Since the metal circuit employs all the technical solutions of the photosensitive resin composition described in the above embodiments, it possesses at least all the beneficial effects brought about by the technical solutions of the above embodiments. Furthermore, the metal conductive pattern exhibits excellent conductivity; specifically, the conductivity of the metal conductive pattern is 2.7~6.4×10⁻⁶. 6 S m -1 For example, it could be 3×106 S m -1 4×10 6 S m -1 5×10 6 S m -1 6×10 6 S m -1 ; or the range of values formed by any two of the above point values.
[0043] According to some embodiments of the present invention, the minimum linewidth of the metallic conductive pattern is 10 μm. That is, metallic conductive patterns with a linewidth ≥ 10 μm can be prepared.
[0044] According to an embodiment of a fourth aspect of the present invention, a method for fabricating a metal circuit as described in an embodiment of a third aspect of the present invention is provided, the method comprising the following steps: D1. Using the photosensitive resin composition as raw material, print the photosensitive resin layer on the surface of the substrate; D2. Immerse the component obtained in step D1 in a catalytic activation solution to obtain the activation layer; D3. No conductive metal pattern is electrodeposited on the surface of the activated layer.
[0045] Since the fabrication method employs all the technical solutions of the metal circuits described in the above embodiments, it possesses at least all the beneficial effects brought about by the technical solutions of the above embodiments. Furthermore, In the aforementioned manufacturing method, the photosensitive resin layer capable of being plated with metal is first precisely patterned using photopolymerization molding technology, so that functional monomers with metal ion adsorption capacity are positioned in the photosensitive resin layer. Then, step D2 is performed, in which the positive and negative ions in the functional monomers selectively adsorb catalytically active metal ions to form patterned catalytically active centers. Finally, in an electroless deposition solution, the catalytic centers guide the metal ions to be reduced and deposited only in the patterned area (activation layer area), thereby directly transforming the pattern of the activation layer into a high-performance metal conductive pattern.
[0046] Furthermore, considering the special components of the photosensitive resin composition, the manufacturing method provided by this invention can achieve room temperature, high precision, rapid, and large-scale preparation of various metal conductive patterns such as copper, nickel, gold, and silver on two-dimensional planes or complex three-dimensional structural surfaces. The prepared metal conductive patterns have precise linewidths and stable conductivity.
[0047] According to some embodiments of the present invention, in step D1, the printing method includes at least one of 3D printing, soft photolithography, inkjet printing, or screen printing. Furthermore, the printing process also incorporates a photocuring step.
[0048] When the selected printing method is 3D printing, the wavelength of the light source used for photopolymerization is 385nm or 405nm; the duration of photopolymerization is 5~10min.
[0049] According to some embodiments of the present invention, step S1 further includes cleaning after printing. This removes excess photosensitive resin composition. If the printing method is 3D printing, the cleaning occurs between the printing and photocuring processes.
[0050] According to some embodiments of the present invention, in step D1, the substrate includes at least one of a rigid substrate or a flexible substrate. The rigid substrate includes at least one of glass, ceramic, resin, and silicon wafer; the flexible substrate includes at least one of polydimethylsiloxane, polyimide, polyethylene terephthalate, polyurethane, and nonwoven fabric.
[0051] Furthermore, the substrate can be commercially available or obtained directly by 3D printing.
[0052] According to some embodiments of the present invention, step D1 further includes pre-treating the substrate before printing. The pre-treatment method includes ultrasonication. The solvent used in the ultrasound includes at least one of anhydrous ethanol and acetone. This removes oil, dust, and other impurities from the substrate surface. If necessary, the substrate can be rinsed with water and dried after ultrasound. The duration of the ultrasound is 5 to 20 minutes. For example, it can be 5 minutes, 10 minutes, 15 minutes, or 20 minutes; or a range of values consisting of any two of the above points.
[0053] According to some embodiments of the present invention, in step D2, the catalytic activation solution includes PdCl4. 2- .
[0054] According to some embodiments of the present invention, in step D2, the solute of the catalytic activation solution includes at least one of (NH4)2PdCl4 or Na2PdCl4.
[0055] According to some embodiments of the present invention, in step D2, the concentration of the catalytic activation solution is 1~3 g / L. For example, it can be 1 g / L, 1.5 g / L, 2 g / L, 2.5 g / L, 3 g / L; or a range of values consisting of any two of the above points.
[0056] According to some embodiments of the present invention, in step D2, the soaking time is 5 to 30 minutes. For example, it can be 5 minutes, 10 minutes, 15 minutes, 20 minutes, or 30 minutes; or a range of values composed of any two of the above points.
[0057] According to some embodiments of the present invention, step D2 further includes rinsing and drying after soaking.
[0058] According to some embodiments of the present invention, in step D3, the target metal ions in the plating solution used for electrodeposition include at least one of copper ions, nickel ions, silver ions, gold ions, or their complexed ions. Therefore, the material of the conductive metal pattern can be a single metal, an alloy of multiple metals, or a stack of multiple metals or alloys.
[0059] According to some embodiments of the present invention, the plating solution includes: a metal source, a reducing agent, and a complexing agent. Wherein, The metal source includes at least one of copper sulfate, nickel sulfate, silver nitrate, and chloroauric acid.
[0060] The concentration of the metal source is 25~30 g / L. For example, it can be 25 g / L, 28 g / L, 30 g / L; or a range of values consisting of any two of the above points.
[0061] The reducing agent includes at least one of formaldehyde and sodium hypophosphite (CAS: 7681-53-0).
[0062] The concentration of the reducing agent is 8~15 g / L. For example, it can be 8 g / L, 10 g / L, 12 g / L, 15 g / L; or a range of values consisting of any two of the above points.
[0063] The complexing agent includes at least one of disodium EDTA and sodium citrate.
[0064] The concentration of the complexing agent is 18~22 g / L. For example, it can be 18 g / L, 20 g / L, 22 g / L; or a range of values consisting of any two of the above points.
[0065] According to some embodiments of the present invention, in step S4, the pH of the electroplating solution used for electrodeposition is 5 to 12. For example, it can be 5, 6, 7, 10, 11, or 12; or a range of values consisting of any two of the above points.
[0066] According to some embodiments of the present invention, in step S4, the electroplating solution used for electrodeposition has the following composition: Copper sulfate 25g / L, formaldehyde 8mL / L, disodium EDTA 20g / L, pH=12.
[0067] According to some embodiments of the present invention, in step S4, the electroplating solution used for electrodeposition has the following composition: Nickel sulfate 30 g / L, sodium hypophosphite 15 g / L, sodium citrate 20 g / L, pH=5.
[0068] According to some embodiments of the present invention, in step D3, the temperature for electrodeposition is 25~70°C. For example, it can specifically be 25°C, 30°C, 40°C, 50°C, 60°C, or 70°C; or a range of values consisting of any two of the above points.
[0069] According to some embodiments of the present invention, in step D3, the electrodeposition time is 5 to 60 minutes. Specifically, it can be 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, or 60 minutes; or a range of values consisting of any two of the above points. By adjusting this duration, the thickness of the conductive metal pattern can be precisely controlled.
[0070] According to some embodiments of the present invention, the manufacturing method further includes post-processing after step D3. The post-processing includes sequential cleaning, drying, and passivation.
[0071] The cleaning process removes the plating solution adhering to the surface of the resulting component.
[0072] The drying temperature is 60~120℃. For example, it can be 70℃, 80℃ or 100℃.
[0073] The passivation treatment method includes immersing the resulting component in a passivation solution for 1-5 minutes. This forms an ultra-thin passivation layer on the surface of the conductive metal pattern, thereby improving its oxidation and corrosion resistance.
[0074] According to some embodiments of the present invention, the passivation solution comprises: Benzotriazole (CAS: 95-14-7) 0.8~1.2 g / L; Anhydrous ethanol 50~80mL / L; for example, it can be 50mL / L, 60mL / L, 70mL / L, 80mL / L; or a range of values consisting of any two of the above points.
[0075] Acetic acid-sodium acetate buffer solution 12~17mL / L; for example, it can be 15mL / L.
[0076] According to some embodiments of the present invention, the pH of the passivation solution is 5 to 6. For example, it can be 5.5.
[0077] The concentration of the acetate-sodium acetate buffer solution is 0.8~1.2 mol / L.
[0078] According to an embodiment of the fifth aspect of the present invention, the photosensitive resin composition described in the first aspect of the present invention, or the application of the metal circuit described in the third aspect of the present invention, in an electronic device is provided.
[0079] Since the application employs all the technical solutions of the photosensitive resin composition or metal circuit of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments.
[0080] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Attached Figure Description
[0081] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 This is a schematic flowchart illustrating the overall process of the embodiments and application examples of the present invention.
[0082] Figure 2 This is a visual diagram of the metal circuit obtained in Application Example 1 of the present invention.
[0083] Figure 3 This is a visual diagram of the metal circuit obtained in Application Example 2 of the present invention.
[0084] Figure 4 (a) and (b) are appearance diagrams of the metal circuit obtained by application example 3 of the present invention.
[0085] Figure 5 This is an appearance diagram of the product obtained in Comparative Application Example 1 of the present invention.
[0086] Figure 6 This is an appearance diagram of the product obtained in Comparative Application Example 2 of the present invention. Detailed Implementation
[0087] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.
[0088] Example 1 refer to Figure 1 In part of the process, this invention prepares a photosensitive resin composition. The specific raw materials are shown in Table 1, and the specific preparation method is as follows: S1. Mix functional monomers and acrylate monomers, then add a crosslinking agent; wherein, the raw materials used to synthesize the functional monomers are shown in Table 2, and their synthesis methods are as follows: The first raw material was weighed and dissolved in 13 parts by mass of deionized water, followed by the addition of the second monomer. The mixture was stirred at room temperature (25±2℃) for 24 hours. After standing, the system separated into layers. The lower organic phase was collected, washed five times with deionized water to remove residual impurities, and finally dried under vacuum at 60℃ for 12 hours to obtain the functional monomer.
[0089] S2. Add 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and the light absorber Sudan I to the mixture obtained in step S1, and stir until completely dissolved to obtain a photosensitive resin composition.
[0090] Table 1. Raw materials (parts by weight) for preparing the photosensitive resin compositions in the examples.
[0091] Table 2. Raw materials (parts by weight) for preparing functional monomers in the examples.
[0092] Comparative Example 1 This example prepares a photosensitive resin composition, which differs from Example 2 in that: Excluding functional monomers, the amount of acrylate monomers is supplemented to 100 parts by weight, while excluding the synthesis process of functional monomers.
[0093] Comparative Example 2 This example prepares a photosensitive resin composition, which differs from Example 2 in that: (1) Excluding the preparation process of functional monomers, the functional monomers are directly replaced by an equal amount of acryloyloxyethyltrimethylammonium chloride in Example 2.
[0094] Application Example 1 refer to Figure 1 In this example, a metal circuit was manufactured using the photosensitive resin composition obtained in Example 1 as a raw material. The specific steps are as follows: D1. Using a photosensitive resin composition as raw material, a photosensitive resin layer is 3D printed on the surface of a substrate (polydimethylsiloxane (Dow Corning 184)); wherein, Before use, the substrate was sonicated in ethanol for 20 minutes, rinsed with deionized water and dried.
[0095] The specific process of 3D printing is as follows: the photosensitive resin composition is poured into the resin tank of the 3D printing equipment with a 385nm light source, the model is printed onto the substrate surface according to the preset pattern, rinsed with ethanol, and cured under ultraviolet light for 5 minutes. D2. At room temperature, immerse the component obtained in step D1 in a catalytic activation solution for 5 minutes, then rinse and dry; wherein, the catalytic activation solution is a 1 g / L (NH4)2PdCl4 solution; the photosensitive resin layer adsorbed with catalytically active ions is called the activation layer.
[0096] D3. Immerse the component obtained in step D2 in a copper plating solution (the composition of the copper plating solution is: 25 g / L copper sulfate, 8 mL / L formaldehyde, 20 g / L disodium EDTA, pH=12) and treat at 35°C for 10 min to form a copper conductive pattern. A high-power microscope image of this copper conductive pattern is shown below. Figure 2 As shown, from Figure 2 It can be seen that the line width of the copper conductive pattern is approximately 10 μm; D4. The copper conductive pattern is rinsed with deionized water and dried at 80°C, then immersed in passivation solution for 2 minutes to complete the preparation.
[0097] The passivation solution consisted of 1.0 g / L benzotriazole, 50 mL / L anhydrous ethanol, and 15 mL / L acetate-sodium acetate buffer solution, with a pH of 6; the solvent was water.
[0098] Application Example 2 This example uses the photosensitive resin composition obtained in Example 2 as a raw material to manufacture a metal circuit. The specific difference from Application Example 1 is as follows: (1) The photosensitive resin composition used is from Example 1.
[0099] (2) The plating solution used in step D3 is a nickel plating solution with the following components: nickel sulfate 30g / L, sodium hypophosphite 15g / L, sodium citrate 20g / L, and pH=5.
[0100] (3) The physical drawing of the obtained component is as follows Figure 3 As shown.
[0101] Application Example 3 This example uses the photosensitive resin composition obtained in Example 3 as a raw material to manufacture a metal circuit. The specific difference between this example and Example 1 is as follows: (1) The photosensitive resin composition used is from Example 3.
[0102] (2) This example was conducted Figure 4 Electroless deposition of the pattern in the middle, and the actual physical image of the resulting component are shown below. Figure 4 As shown.
[0103] Comparative Application Example 1 This example uses the photosensitive resin composition obtained in Comparative Example 1 as a raw material to manufacture a metal circuit. The specific steps differ from those in Application Example 2 in that: (1) The photosensitive resin composition obtained in Comparative Example 1 was used.
[0104] (2) No nickel deposition pattern was formed. The actual product is shown in the figure below. Figure 5 As shown.
[0105] Comparative Application Example 2 This example uses the photosensitive resin composition obtained in Comparative Example 2 as a raw material to manufacture a metal circuit. The specific steps differ from those in Application Example 2 in the following ways: (1) The photosensitive resin composition obtained in Comparative Example 2 was used.
[0106] (2) The target patterns are different, specifically as follows: Figure 6 As shown. Figure 6 The pattern shown indicates that a uniform nickel deposition pattern was not formed. This is because, compared to the functional monomer, acryloyloxyethyltrimethylammonium chloride has poor compatibility with other components in the photosensitive resin composition. In step D2, there is less adsorption of catalytically active ions, making subsequent nickel deposition difficult and uneven.
[0107] Test case This example tests the conductivity of the conductive metal patterns obtained in the embodiments and comparative examples. Specifically: The resistance was tested using a multimeter, and the conductivity was calculated using the formula σ=L / (S*R), where σ is the conductivity, L is the length, S is the cross-sectional area, and R is the resistance. The test revealed that the conductivity of Example 1 was 6.4 × 10⁻⁶. 6 S m -1 The conductivity of Example 2 is 2.7 × 10⁻⁶. 6 S m -1 The comparative example shows almost no conductivity. This indicates that the photosensitive resin composition provided by the present invention can adsorb catalytically active metal ions and induce electroless deposition in precise local areas, ultimately enabling the rapid fabrication of highly conductive metal patterns at room temperature. This is suitable for various flexible electronic devices, from simple circuits and sensors to complex structures, providing a universal solution for the large-scale, low-cost, and high-performance manufacturing of flexible electronics.
[0108] The photosensitive resin compositions prepared in Examples 1-3 were stored for 12 months in a conventional laboratory environment (room temperature, protected from light). It was found that they could be stored stably without precipitation, viscosity change or attenuation of UV-Vis absorption characteristics. Therefore, the photosensitive resin compositions of the present invention solve the stability problem of existing electrodeposition inks.
[0109] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof can be combined with each other unless otherwise specified.
Claims
1. A photosensitive resin composition, characterized in that, The raw materials for preparing the photosensitive resin composition include: Functional monomers, acrylate monomers, crosslinking agents, photoinitiators, and light absorbers; The functional monomer is an ionic compound composed of a quaternary ammonium cation and a fluorosulfonyl imide anion; the quaternary ammonium cation includes a UV-curable group.
2. The photosensitive resin composition according to claim 1, characterized in that, The UV-curable group includes at least one of acryloyloxy and acrylamide.
3. The photosensitive resin composition according to claim 1, characterized in that, The acrylate monomers include at least one of butyl acrylate, methyl acrylate, ethyl acrylate, benzyl acrylate, isooctyl acrylate, hexyl acrylate, isobornyl acrylate, tert-butyl acrylate, epoxy acrylate, butyl methacrylate, and benzyl methacrylate.
4. The photosensitive resin composition according to any one of claims 1 to 3, characterized in that, The photosensitive resin composition comprises, by weight, the following: 10-30 parts of functional monomer; 70-90 parts of acrylate monomers; Crosslinking agent 0.1~1 part; Photoinitiator 0.5-2 parts; 0.02~0.5 parts of light absorber.
5. A method for preparing the photosensitive resin composition according to any one of claims 1 to 4, characterized in that, The preparation method includes the following steps: S1. After mixing the functional monomer and the acrylate monomer, continue mixing with the crosslinking agent; S2. Mix the mixture obtained in step S1 with the photoinitiator and the light absorber.
6. The preparation method according to claim 5, characterized in that, In step S1, the method for synthesizing the functional monomer includes a reaction of a first raw material and a second raw material. The first raw material includes a quaternary ammonium cation; the second raw material includes a fluorosulfonamide anion.
7. The preparation method according to claim 6, characterized in that, The first raw material includes at least one of acryloyloxyethyltrimethylammonium chloride and (3-acrylamidopropyl)trimethylammonium chloride; And / or, the second raw material includes lithium bis(trifluoromethanesulfonyl)imide.
8. A metal circuit, characterized in that, The metal circuit includes a substrate, an activation layer, and a metal conductive pattern stacked together; the activation layer includes a photosensitive resin layer and catalytically active ions adsorbed thereon; the raw materials for preparing the photosensitive resin layer include the photosensitive resin composition according to any one of claims 1 to 5.
9. A method for fabricating a metal circuit as described in claim 8, characterized in that, The manufacturing method includes the following steps: D1. Using the photosensitive resin composition as raw material, print the photosensitive resin layer on the surface of the substrate; D2. Immerse the component obtained in step D1 in a catalytic activation solution to obtain the activation layer; D3. No conductive metal pattern is electrodeposited on the surface of the activated layer.
10. The photosensitive resin composition as described in any one of claims 1 to 5, or the application of the metal circuit as described in claim 8 in an electronic device.