A composite matte coating structure for a light-shielding ring and its multi-step film formation process via spin coating and ion plating.

Abstract

This invention discloses a composite matting coating structure for a light-shielding ring and its multi-step spin-coating-ion plating film preparation process. The structure, from the inside out, comprises a carrier base film, a functionalized spin-coating layer, and an ion-plated blackening layer. The functionalized spin-coating layer is composed of polymer resin, light-shielding filler, and functional additives containing organometallic compounds and active functional groups. Through plasma bombardment activation during the ion plating process, the functional additives react in situ, forming an interface transition layer with a compositional gradient between the functionalized spin-coating layer and the ion-plated blackening layer. This invention solves the problems of weak organic / inorganic layer adhesion and easy agglomeration of nanoparticles through the interface transition layer design, significantly improving the matting performance, weather resistance, and structural stability of the coating, making it suitable for high-end optical systems such as optical lenses and waveguide devices.

Description

Technical Field

[0001] This invention relates to the field of composite matte coating preparation technology, specifically to a composite matte coating structure with a light-shielding ring and its multi-step film formation process of spin coating-ion plating. Background Technology

[0002] Light-shielding materials, especially light-shielding rings or components used in optical systems, high-end display devices, and precision instruments, are key functional materials for suppressing stray light, improving imaging contrast, and enhancing the system signal-to-noise ratio. Ideal light-shielding materials must possess extremely high light-shielding efficiency, good environmental durability, and strong adhesion to the substrate.

[0003] Currently, the mainstream technical approaches to achieving high-performance shading mainly include the following two categories:

[0004] Multilayer composite structure technology: In existing technologies, multilayer material composites are commonly used to construct light-shielding structures, such as sequentially setting a light-shielding layer and a protective layer on a substrate. To balance flexibility and light-shielding properties, polymer resins are often chosen as the matrix, and a high proportion of light-shielding fillers are added. However, this physical blending method has inherent drawbacks: while the large addition of light-shielding fillers improves light-shielding performance, it often degrades the mechanical properties of the matrix material, leading to increased coating brittleness, decreased flexibility, and susceptibility to cracking under stress or thermal shock. Furthermore, simple physical blending cannot avoid filler agglomeration, which may result in uneven light shielding and performance fluctuations.

[0005] Surface blackening treatment technology: To address the insufficient light-shielding ability of the resin matrix itself or to improve surface durability, the industry often applies an additional blackening layer to the surface of the light-shielding layer. Ion plating is used to deposit inorganic blackening layers because it can produce dense, well-adhered thin films. However, there are significant differences in the physicochemical properties between organic polymer light-shielding layers and inorganic ion-plated blackening layers. This difference results in weak interfacial bonding between the two layers. Under long-term use or environmental testing, the blackening layer is prone to peeling and flaking, thus losing its protective function and affecting the stability of light-shielding.

[0006] Existing technologies, by pre-coating an organic layer on the light-shielding layer as an adhesion-promoting layer, can improve adhesion to some extent, but often introduce new weak points. The presence of the organic layer may even affect the performance of the final blackening layer or introduce instability.

[0007] This invention proposes a composite matte coating structure that constructs a transition layer with a compositional gradient at the organic / inorganic interface, achieving a smooth transition from the organic phase to the inorganic phase, thereby improving interlayer adhesion and the overall structural durability. Summary of the Invention

[0008] To address the aforementioned technical problems, this invention provides a composite matte coating structure for a light-shielding ring and its multi-step spin-coating-ion plating film preparation process. In the technical solution of this invention, a composite matte coating structure for a light-shielding ring comprises, from the inside out:

[0009] Carrier base membrane;

[0010] The functionalized spin coating is composed of polymer resin, light-shielding filler and functional additives. The functional additives include organometallic compounds and active functional groups that can undergo chemical reactions in a plasma environment.

[0011] The ion-plated blackening layer is an inorganic thin film deposited on a functionalized spin coating layer by an ion plating process.

[0012] Between the functionalized spin coating layer and the ion-plated blackening layer, there is an interface transition layer with a compositional gradient. This transition layer contains inorganic nanoparticles generated in situ by functional additives after being subjected to ion-plating plasma.

[0013] Furthermore, in the technical solution of the present invention, the organometallic compound is an alkoxysilane or a titanate compound; the active functional group includes at least one of hydroxyl, carboxyl, amino or epoxy groups.

[0014] Furthermore, in the technical solution of the present invention, the maximum thickness of the ion-plated blackening layer is less than the arithmetic mean roughness Ra value of the functionalized spin coating surface.

[0015] Furthermore, in the technical solution of the present invention, the thickness of the ion-plated blackening layer is 30-150 nanometers, and the surface roughness Ra of the functionalized spin coating layer is 0.2-1.0 micrometers.

[0016] Furthermore, in the technical solution of the present invention, the polymer resin of the functionalized spin coating is one or a mixture of several of epoxy resin, polyurethane resin, and acrylic resin; the light-shielding filler is carbon black, and includes a first black pigment with an average particle size D50 of 0.4-2.5 μm and a second black pigment with an average particle size D50 of 0.01-0.3 μm.

[0017] A multi-step film formation process for a composite matte coating structure with a light-shielding ring, comprising the following steps:

[0018] ① Perform surface pretreatment on the carrier base film;

[0019] ② On the pretreated carrier base film, a functionalized spin coating liquid containing functional additives is coated, and a functionalized spin coating layer is formed through spin coating process and subsequent curing.

[0020] ③ The substrate with the functionalized spin coating is placed in the vacuum chamber of the ion plating equipment, and the surface of the functionalized spin coating is activated by plasma bombardment.

[0021] ④ An inorganic blackening layer is deposited on the activated functionalized spin coating surface by ion plating to obtain a composite matte coating.

[0022] Furthermore, in the technical solution of the present invention, in step ②, the functionalized spin-coating liquid, by weight, comprises:

[0023] 30-60 parts of polymer resin;

[0024] 8-15 parts of light-shielding filler;

[0025] Functional additives: 1-5 parts;

[0026] 10-25 parts of curing agent;

[0027] 100 parts solvent;

[0028] The solvent consists of 50-70 parts of propylene glycol methyl ether acetate, 10-20 parts of dimethylformamide and 20-30 parts of butanone, and the application viscosity of the functionalized spin coating is 200-800 cP.

[0029] Furthermore, in the technical solution of the present invention, in step ③, the process conditions for plasma bombardment activation are as follows: under an argon atmosphere, the working pressure is 0.1-0.5 Pa, the applied substrate bias voltage is -200 to -50 V, and the bombardment time is 5-15 minutes.

[0030] Furthermore, in the technical solution of the present invention, in step ④, in the initial stage of depositing the blackened layer, a reactive gas is introduced into the vacuum chamber, and the reactive gas is oxygen or nitrogen.

[0031] Effective gain:

[0032] In the technical solution of this invention, a highly efficient light-shielding system is constructed by compounding carbon black of different particle sizes into a polymer resin matrix. Micron-sized carbon black primarily contributes to light scattering and blocking, while nano-sized carbon black effectively fills the gaps between micron-sized particles and enhances the absorption of infrared and other wavelengths of light. This "micro-nano synergy" mechanism achieves broad-spectrum, high-intensity absorption and scattering of visible to near-infrared waves, thereby achieving excellent physical light-shielding effects. An externally deposited inorganic blackening layer forms an extremely thin, continuous, and dense film that effectively blocks the penetration of water vapor, oxygen, and corrosive media from the environment, improving the coating's resistance to environmental aging. By combining physical light shielding with chemical coating, extremely low reflectivity and excellent stray light suppression capabilities are achieved.

[0033] Secondly, the introduced functional additives generate inorganic nanoparticles in situ within the plasma environment of the ion plating process. These nanoparticles then form an interfacial transition layer with a continuously varying compositional gradient between the organic functionalized spin coating and the inorganic ion-plated blackening layer. This gradient transition layer effectively alleviates the internal stress concentration caused by the mismatch in thermal expansion coefficients of the organic and inorganic materials, significantly improving interlayer adhesion and the overall structural durability.

[0034] Other features and advantages of the present invention will be set forth in the following description. Attached Figure Description

[0035] To more clearly illustrate the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 This is a flowchart illustrating the fabrication process of the composite matte coating structure of the light-shielding ring of the present invention. Detailed Implementation

[0037] To make the objectives, features, and advantages of this invention more apparent and understandable, the technical solutions of the embodiments of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the embodiments described below are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0038] This invention proposes a composite matte coating structure for a light-shielding ring, comprising, from the inside out:

[0039] Carrier base membrane;

[0040] The functionalized spin coating has a surface roughness Ra of 0.2-1.0 micrometers and is composed of polymer resin, light-shielding filler and functional additives. The functional additives include organometallic compounds and active functional groups that can undergo chemical reactions in a plasma environment.

[0041] The ion-plated blackening layer, with a thickness of 30-150 nanometers, is specifically an inorganic thin film deposited on the functionalized spin coating layer through an ion plating process.

[0042] Furthermore, between the functionalized spin coating layer and the ion-plated blackening layer, there exists an interface transition layer with a compositional gradient, which contains inorganic nanoparticles generated in situ by functional additives after being subjected to ion-plating plasma.

[0043] In this embodiment, the carrier base film is specifically any one of black polyethylene terephthalate, black polyimide, black polycarbonate, or black polyethylene naphthalate.

[0044] In this embodiment, the functionalized spin coating is formed by spin coating of functionalized spin coating liquid and subsequent curing.

[0045] The functionalized spin coating liquid, by weight, includes:

[0046] 30-60 parts of polymer resin;

[0047] 8-15 parts of light-shielding filler;

[0048] Functional additives: 1-5 parts;

[0049] 10-25 parts of curing agent;

[0050] 100 parts solvent;

[0051] The solvent consists of 50-70 parts of propylene glycol methyl ether acetate, 10-20 parts of dimethylformamide and 20-30 parts of butanone, and the application viscosity of the functionalized spin coating is 200-800 cP.

[0052] Understandably, propylene glycol methyl ether acetate, as the main solvent, has excellent solubility for polymer resins, a high boiling point, and moderate volatility, which helps the coating film level and reduces defects; dimethylformamide, as a strong solvent, has extremely strong solubility for polyurethanes, which can enhance the stability of the system and prevent local gelation; methyl ethyl ketone, as a fast-drying solvent, has a low boiling point and fast evaporation, which can effectively reduce the viscosity of the system, improve leveling, and adjust the overall evaporation rate.

[0053] In this embodiment, solids such as polymer resin, filler, and additives are added to a mixed solvent, and the application viscosity of the functionalized spin coating liquid is adjusted to 200-800 cP. Then, the mixture is spin-coated using a spin coater.

[0054] Specifically, the polymer resin is one or a mixture of epoxy resin, polyurethane resin, and acrylic resin. In this embodiment, the epoxy resin is selected from Guodu, model DER-331; the polyurethane resin is selected from Mitsubishi Chemical, specifically a solvent-based polyurethane resin; and the acrylic resin is selected from Dow Chemical, model UCAR™ Solution Vinyl ResinVAGH.

[0055] The light-shielding filler is carbon black, which comprises a first black pigment with an average particle size D50 of 0.4-2.5 μm and a second black pigment with an average particle size D50 of 0.01-0.3 μm. In this embodiment, the first black pigment is selected from Mitsubishi Chemical, model MA77, and the second black pigment is selected from Mitsubishi Chemical, model MA100. The mass ratio of the first black pigment to the second black pigment is 2-1:1-2.

[0056] The functional additives contain organometallic compounds and active functional groups that can undergo chemical reactions in a plasma environment, wherein the organometallic compounds are alkoxysilanes or titanate compounds; and the active functional groups include at least one of hydroxyl, carboxyl, amino or epoxy groups.

[0057] Specifically, the functional additive is a functionalized silane or a functionalized titanate, specifically one or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, di(dioctyl pyrophosphate) ethylene titanate, di(dioctyl phosphate) ethylene titanate, and di(dioctyl phosphite) ethylene titanate.

[0058] In this embodiment, the active functional groups in the functionalized silane, such as amino and epoxy groups, react with the polymer resin or form strong hydrogen bonds during the spin-coating stage, thereby significantly improving the compatibility and dispersion uniformity of silane molecules in the spin-coating layer and enhancing their bonding with the matrix. In a plasma environment, the plasma simultaneously bombards the active functional groups and surrounding polymer chains, causing them to break and generate active sites such as free radicals. These active sites combine with each other, allowing the silane molecules to form strong covalent bonds with the polymer matrix through the active functional groups.

[0059] Simultaneously, the alkoxy group at the other end of the functionalized silane undergoes hydrolysis and condensation under plasma conditions, generating inorganic silica nanoparticles or networks in situ. This newly generated inorganic phase will bond with the subsequently deposited ion-plated blackening layer through strong ionic and covalent bonds, thus forming a chemical bridge between the functionalized spin-coated layer and the ion-plated blackening layer. Specifically, the active ions and ultraviolet light in the plasma environment provide energy to promote the breaking of Si-OR bonds, generating highly active silanol groups -Si-OH. Dehydration condensation reactions occur between the -Si-OH groups, forming a Si-O-Si inorganic network structure. The continuous energy bombardment of the plasma promotes the reaction, ultimately resulting in the in-situ generation of silica nanoparticles.

[0060] Understandably, within the spin coating, functionalized silanes exist primarily in molecular form; the closer to the plasma-bombarded surface, the higher the density of the Si-O-Si inorganic network, with the composition gradually transitioning from organic polymers to inorganic SiOx. This forms a gradient transition layer with continuously changing chemical composition, improving interfacial adhesion and reducing coating peeling.

[0061] Moreover, the Si-O-Si network generated by the condensation reaction initially appears as nanoscale clusters and eventually forms silica nanoparticles. These in-situ generated particles are chemically bonded to the polymer matrix, exhibiting excellent compatibility and resistance to detachment. Simultaneously, these in-situ generated nanoparticles, along with the slight etching effect of plasma on the polymer surface, collectively construct a novel and more complex micro-nano composite rough structure on the spin-coated surface, enabling the coating to possess a better light-trapping effect.

[0062] In other embodiments, the alkoxy groups of the functionalized titanate ester hydrolyze to generate titanium hydroxyl groups, which then undergo a dehydration condensation reaction with hydroxyl groups on the substrate surface to form a strong Ti-OM covalent bond. Under high-energy ion bombardment by plasma, unreacted alkoxy groups in the titanate ester molecule are rapidly activated and completely decomposed. Titanium atoms combine with oxygen atoms to generate titanium dioxide nanoparticles in situ. A transition layer with a compositional gradient is constructed at the organic / inorganic interface, achieving a smooth transition from the organic phase to the inorganic phase.

[0063] Simultaneously, plasma bombardment of organic functional groups and surrounding polymer chains generates a large number of free radicals. These free radicals combine with each other, enabling titanate molecules to form a stronger covalent bond network with the polymer matrix through their organic ends, thus enhancing interfacial adhesion. Furthermore, the in-situ generated TiO2 nanoparticles, together with the plasma-etched organic phase, form a micro-nano composite structure, jointly constructing a novel and more complex surface microstructure, which significantly improves light scattering and absorption efficiency.

[0064] Specifically, the curing agent is one or more of methyltetrahydrophthalic anhydride, HDI trimer, and methylated melamine resin.

[0065] It should be noted that methyltetrahydrophthalic anhydride is selected as the catalyst for the epoxy resin system, HDI trimer is selected as the curing agent for the polyurethane resin, and methylated melamine resin is selected as the curing agent for the acrylic resin. When multiple resins are mixed as the matrix, curing agents corresponding to the resins must be selected and used together.

[0066] Another aspect of this invention proposes a multi-step film formation process for a composite matte coating structure with a light-shielding ring, consisting of spin coating and ion plating, comprising the following steps:

[0067] ① Perform surface pretreatment on the carrier base film;

[0068] Specifically, the pretreatment includes: ultrasonic cleaning with organic solvents such as acetone, ethanol, and isopropanol in sequence, each for 5-10 minutes. Then, ultrasonic cleaning is performed at 40-60°C for 5-15 minutes using a neutral surfactant or a weakly alkaline solution of 1-5% NaOH or KOH. Finally, the mixture is rinsed thoroughly with plenty of deionized water and dried completely with a hair dryer or oven.

[0069] ② On the pretreated carrier base film, a functionalized spin coating liquid containing functional additives is coated, and a functionalized spin coating layer is formed through spin coating process and subsequent curing.

[0070] The spin coating process is divided into a low-speed spreading stage: 500-800 rpm for 10-20 seconds.

[0071] High-speed homogenization and drying stage: rotation speed 1500-3000 rpm, time 30-60 seconds;

[0072] Temperature: 23±2℃; Humidity: 50±5% RH.

[0073] Understandably, the low-speed spreading stage utilizes centrifugal force to evenly spread the added droplets across the entire substrate surface. The high-speed spin coating and drying stage utilizes powerful centrifugal force to throw excess liquid away from the substrate, precisely controlling the final film thickness; at the same time, the airflow generated by high-speed rotation greatly accelerates solvent evaporation, forming a solid or semi-solid film.

[0074] Subsequent curing includes pre-curing at 60-80℃ for 5-10 minutes until the coating surface loses its gloss and is no longer sticky to the touch, then raising it to the curing temperature for a cross-linking reaction of 20-60 minutes.

[0075] Specifically, the curing temperature for the epoxy / anhydride system is 130-150 ℃;

[0076] Curing temperature for acrylic / amino resin systems: 140-160 ℃;

[0077] Curing temperature of polyurethane system: 70-90 ℃.

[0078] ③ The substrate with the functionalized spin coating is placed in the vacuum chamber of the ion plating equipment, and the surface of the functionalized spin coating is activated by plasma bombardment.

[0079] The plasma bombardment activation process conditions are as follows: under an argon atmosphere, the working pressure is 0.1-0.5 Pa, the applied substrate bias voltage is -200 to -50 V, and the bombardment time is 5-15 minutes; in this embodiment, the preferred applied substrate bias voltage is -200 to -100 V.

[0080] ④ An inorganic blackening layer is deposited on the activated functionalized spin coating surface by ion plating to obtain a composite matte coating.

[0081] Specifically, in the ion plating process, the target material is either a titanium target or an aluminum target. For titanium targets, the current density is 0.1 - 0.3 A / cm²; for aluminum targets, the current density is 0.05 - 0.15 A / cm². In the initial stage of blackening layer deposition, a reactive gas, either oxygen or nitrogen, is introduced into the vacuum chamber at a flow rate of 20-80 sccm and a pressure of 0.1-0.5 Pa. The bias voltage is -200 to -100 V, and the deposition time is 15-60 minutes. After the blackening layer is deposited, the composite matte coating is annealed at 100-200℃ for 20-40 minutes.

[0082] To further understand the present invention, the lightweight nanocomposite ceramic insulator provided by the present invention will be described below with reference to the embodiments. The scope of protection of the present invention is not limited by the following embodiments.

[0083] Example 1

[0084] ① Add 50 parts epoxy resin, 8 parts MA77, 7 parts MA100, 5 parts γ-aminopropyltriethoxysilane and 15 parts methyltetrahydrophthalic anhydride to a solvent composed of 70 parts propylene glycol methyl ether acetate, 10 parts dimethylformamide and 20 parts butanone, mix evenly to obtain a functionalized spin coating solution.

[0085] ② The black polyethylene terephthalate (PET) carrier film was ultrasonically cleaned sequentially with acetone and ethanol, each solvent for 10 minutes. Then, it was ultrasonically cleaned with a 1% NaOH solution at 40°C for 5 minutes, rinsed with plenty of deionized water, and thoroughly dried in an oven.

[0086] ③ On the pretreated carrier film, coat with the functionalized spin coating solution prepared in step ①, and spin coat using the following methods: 500 rpm for 10 seconds; 1500 rpm for 60 seconds; temperature: 23±2℃; humidity: 50±5% RH. Prepare a wet film and pre-cur it at 60℃ for 5 minutes until the coating surface loses its gloss and is no longer sticky to the touch. Then, increase the temperature to 130℃ and allow the cross-linking reaction to proceed for 30 minutes.

[0087] ④ Place the substrate with the functionalized spin coating in the vacuum chamber of the ion plating equipment. Under the argon atmosphere, the working pressure is 0.1 Pa, the applied substrate bias voltage is -200 V, and the bombardment time is 5 minutes to activate the surface of the functionalized spin coating.

[0088] ⑤ On the activated functionalized spin coating surface, a titanium target was selected, the current density was 0.1 A / cm², oxygen was introduced into the vacuum chamber at a flow rate of 20 sccm, a pressure of 0.1 Pa, a bias voltage of -100 V, and a deposition time of 30 minutes. After the blackening layer was deposited, the composite matte coating was annealed at 150℃ for 20 minutes to obtain the composite matte coating.

[0089] Example 2

[0090] ① Add 60 parts of polyurethane resin, 4 parts of MA77, 4 parts of MA100, 1 part of di(dioctyl pyrophosphate) ethylene titanate and 25 parts of HDI trimer to a solvent consisting of 50 parts of propylene glycol methyl ether acetate, 20 parts of dimethylformamide and 30 parts of butanone, mix evenly to obtain a functionalized spin coating solution.

[0091] ② The black polyimide carrier film was ultrasonically cleaned sequentially with acetone and ethanol, each solvent for 5 minutes. Then, a neutral surfactant was used for ultrasonic cleaning at 40°C for 15 minutes, followed by rinsing with plenty of deionized water and thorough drying in an oven.

[0092] ③ On the pretreated carrier film, coat with the functionalized spin coating solution prepared in step ①, and spin coat using the following methods: 800 rpm for 20 seconds; 3000 rpm for 30 seconds; temperature: 23±2℃; humidity: 50±5% RH. Prepare a wet film and pre-cur it at 80℃ for 5 minutes until the coating surface loses its gloss and is no longer sticky to the touch. Then, raise the temperature to 160℃ and allow the cross-linking reaction to proceed for 30 minutes.

[0093] ④ Place the substrate with the functionalized spin coating in the vacuum chamber of the ion plating equipment. Under the argon atmosphere, the working pressure is 0.1 Pa, the applied substrate bias voltage is -200 V, and the bombardment time is 5 minutes to activate the surface of the functionalized spin coating.

[0094] ⑤ On the activated functionalized spin coating surface, a titanium target was selected, the current density was 0.1 A / cm², nitrogen gas was introduced into the vacuum chamber at a flow rate of 50 sccm, gas pressure of 0.5 Pa, bias voltage of -200 V, and deposition time of 20 minutes. After the blackening layer was deposited, the composite matte coating was annealed at 180℃ for 30 minutes to obtain the composite matte coating.

[0095] Example 3

[0096] ① Add 30 parts of acrylic resin, 4 parts of MA77, 4 parts of MA100, 3 parts of γ-methacryloyloxypropyltrimethoxysilane and 10 parts of methyl etherified melamine resin to a solvent composed of 60 parts of propylene glycol methyl ether acetate, 10 parts of dimethylformamide and 30 parts of butanone, mix evenly to obtain a functionalized spin coating solution.

[0097] ② The black polycarbonate carrier film was ultrasonically cleaned sequentially with acetone and ethanol, each solvent for 10 minutes. Then, a neutral surfactant was used for ultrasonic cleaning at 40°C for 15 minutes, followed by rinsing with plenty of deionized water and thorough drying in an oven.

[0098] ③ On the pretreated carrier film, coat with the functionalized spin coating solution prepared in step ①, and spin coat using the following methods: 500 rpm for 10 seconds; 1800 rpm for 30 seconds; temperature: 23±2℃; humidity: 50±5% RH. Prepare a wet film and pre-cur it at 60℃ for 5 minutes until the coating surface loses its gloss and is no longer sticky to the touch. Then, increase the temperature to 70℃ and allow the cross-linking reaction to proceed for 30 minutes.

[0099] ④ Place the substrate with the functionalized spin coating in the vacuum chamber of the ion plating equipment. Under the argon atmosphere, the working pressure is 0.1 Pa, the applied substrate bias voltage is -200 V, and the bombardment time is 5 minutes to activate the surface of the functionalized spin coating.

[0100] ⑤ On the activated functionalized spin coating surface, select a titanium target, introduce oxygen into the vacuum chamber at a flow rate of 20 sccm, a pressure of 0.5 Pa, a bias voltage of -200 V, and a deposition time of 30 minutes. After the blackening layer is deposited, anneal the composite matte coating at 100℃ for 30 minutes to obtain the composite matte coating.

[0101] Example 4

[0102] ① Add 50 parts epoxy resin, 10 parts polyurethane resin, 5 parts MA77, 5 parts MA100, 3 parts di(octyl phosphate) ethylene titanate, 10 parts methyltetrahydrophthalic anhydride, and 5 parts HDI trimer to a solvent composed of 60 parts propylene glycol methyl ether acetate, 20 parts dimethylformamide, and 20 parts butanone, mix well, and obtain a functionalized spin coating solution;

[0103] ② The black polyethylene naphthalate (PEG) carrier film was ultrasonically cleaned sequentially with acetone and ethanol, each solvent for 5 minutes. Then, a neutral surfactant was used for ultrasonic cleaning at 40°C for 15 minutes. The film was rinsed thoroughly with deionized water and dried completely in an oven.

[0104] ③ On the pretreated carrier film, coat with the functionalized spin coating solution prepared in step ①, and spin coat using the following methods: 600 rpm for 15 seconds; 2000 rpm for 40 seconds; temperature: 23±2℃; humidity: 50±5% RH. Prepare a wet film and pre-cur it at 70℃ for 10 minutes until the coating surface loses its gloss and is no longer sticky to the touch. Then, increase the temperature to 150℃ and allow the cross-linking reaction to proceed for 60 minutes.

[0105] ④ The substrate with the functionalized spin coating is placed in the vacuum chamber of the ion plating equipment. Under the argon atmosphere, the working pressure is 0.3 Pa, the applied substrate bias voltage is -150 V, and the bombardment time is 10 minutes to activate the surface of the functionalized spin coating.

[0106] ⑤ On the activated functionalized spin coating surface, an aluminum target was selected, the current density was 0.05A / cm², nitrogen gas was introduced into the vacuum chamber at a flow rate of 20 sccm, gas pressure: 0.1Pa; bias voltage: -100 V, deposition time was 30 minutes, and after the blackening layer was deposited, the composite matte coating was annealed at 200℃ for 40 minutes to obtain the composite matte coating.

[0107] Comparative Example 1

[0108] The commercially available pre-coated black plastic light-shielding rings are from Sunny Optical.

[0109] Comparative Example 2

[0110] ① Add 50 parts epoxy resin, 8 parts MA77, 7 parts MA100 and 15 parts methyltetrahydrophthalic anhydride to a solvent consisting of 70 parts propylene glycol methyl ether acetate, 10 parts dimethylformamide and 20 parts butanone, mix evenly to obtain a functionalized spin coating solution.

[0111] ② The black polyethylene terephthalate (PET) carrier film was ultrasonically cleaned sequentially with acetone and ethanol, each solvent for 10 minutes. Then, it was ultrasonically cleaned with a 1% NaOH solution at 40°C for 5 minutes, rinsed with plenty of deionized water, and thoroughly dried in an oven.

[0112] ③ On the pretreated carrier film, coat with the functionalized spin coating solution prepared in step ①, and spin coat using the following methods: 500 rpm for 10 seconds; 1500 rpm for 60 seconds; temperature: 23±2℃; humidity: 50±5% RH. Prepare a wet film and pre-cur it at 60℃ for 5 minutes until the coating surface loses its gloss and is no longer sticky to the touch. Then, increase the temperature to 130℃ and allow the cross-linking reaction to proceed for 30 minutes.

[0113] ④ Place the substrate with the functionalized spin coating in the vacuum chamber of the ion plating equipment. Under the argon atmosphere, the working pressure is 0.1 Pa, the applied substrate bias voltage is -200 V, and the bombardment time is 5 minutes to activate the surface of the functionalized spin coating.

[0114] ⑤ On the activated functionalized spin coating surface, a titanium target was selected, the current density was 0.1 A / cm², oxygen was introduced into the vacuum chamber at a flow rate of 20 sccm, a pressure of 0.1 Pa, a bias voltage of -100 V, and a deposition time of 30 minutes. After the blackening layer was deposited, the composite matte coating was annealed at 150℃ for 20 minutes to obtain the composite coating.

[0115] Test example:

[0116] The average reflectance of the coatings in Examples 1 and 2, as well as Comparative Examples 1 and 2, was tested according to ASTM E179 standard. The specific results are shown in Table 1.

[0117] The optical density of the coatings in Examples 1 and 2, as well as Comparative Examples 1 and 2, was tested according to ISO 21501 standard. The specific results are shown in Table 1.

[0118] The adhesion of the coatings in Examples 1 and 2, as well as Comparative Examples 1 and 2, was tested according to ASTM D3359 standard. The specific results are shown in Table 1.

[0119] Abrasion resistance tests were performed on the coatings in Examples 1 and 2, and Comparative Examples 1 and 2, according to ASTM D4060 standard. The specific results are shown in Table 1.

[0120] The adhesion of the coatings in Examples 1 and 2 and Comparative Examples 1 and 2 after thermal cycling was tested according to IEC 60068-2-14 standard. The specific results are shown in Table 1.

[0121] The coatings in Examples 1 and 2, as well as Comparative Examples 1 and 2, were subjected to high temperature and high humidity appearance tests according to IEC 60068-2-78 standard. The specific results are shown in Table 1.

[0122] Table 1. Statistical Table of Parameters for Examples and Comparative Examples

[0123]

[0124] In summary, this invention provides a composite matte coating structure for a light-shielding ring and its spin-coating-ion plating multi-step film-forming process. By adding functional additives and using a spin-coating-ion plating composite process, an interface transition layer with a compositional gradient is constructed in situ between the organic light-shielding layer and the inorganic blackening layer, thereby achieving significant improvements in optical performance, interfacial adhesion, and environmental durability.

[0125] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely preferred examples and are not intended to limit the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A composite matte coating structure for a light-shielding ring, characterized in that, From the inside out, the following are included: Carrier base membrane; The functionalized spin coating is composed of a polymer resin, a light-shielding filler, and functional additives. The functional additives include alkoxysilanes or titanate organometallic compounds, and at least one active functional group selected from hydroxyl, carboxyl, amino, or epoxy groups. The light-shielding filler is carbon black and includes a first black pigment with an average particle size D50 of 0.4-2.5 μm and a second black pigment with an average particle size D50 of 0.01-0.3 μm. The ion-plated blackening layer is an inorganic thin film deposited on the functionalized spin coating layer by an ion plating process. Specifically, an interface transition layer is formed in situ between the functionalized spin coating layer and the ion-plated blackening layer through the plasma action of the ion plating process; the interface transition layer contains inorganic nanoparticles generated in situ by functional additives after ion plating plasma action, and its composition changes continuously in a gradient from one side of the functionalized spin coating layer to the side of the ion-plated blackening layer.

2. The composite matte coating structure of the light-shielding ring according to claim 1, characterized in that, The maximum thickness of the ion-plated blackening layer is less than the arithmetic mean roughness Ra value of the functionalized spin coating surface.

3. The composite matte coating structure of the light-shielding ring according to claim 2, characterized in that, The thickness of the ion-plated blackening layer is 30-150 nanometers, and the surface roughness Ra of the functionalized spin coating layer is 0.2-1.0 micrometers.

4. The composite matte coating structure of the light-shielding ring according to claim 1, characterized in that, The polymer resin of the functionalized spin coating is one or a mixture of epoxy resin, polyurethane resin, and acrylic resin.

5. A spin-coating-ion plating multi-step film-forming process for preparing a composite matte coating structure of a light-shielding ring as described in any one of claims 1-4, characterized in that, Includes the following steps: ① Perform surface pretreatment on the carrier base film; ② On the pretreated carrier base film, a functionalized spin coating liquid containing functional additives is coated, and a functionalized spin coating layer is formed through spin coating process and subsequent curing. ③ The substrate with the functionalized spin coating is placed in the vacuum chamber of the ion plating equipment, and the surface of the functionalized spin coating is activated by plasma bombardment. ④ An inorganic blackening layer is deposited on the activated functionalized spin coating surface by ion plating to obtain the composite matte coating.

6. The multi-step film preparation process of spin-coating-ion plating for a composite matte coating structure of a light-shielding ring according to claim 5, characterized in that, In step ②, the functionalized spin-coating liquid, by weight, comprises: 30-60 parts of polymer resin; 8-15 parts of light-shielding filler; Functional additives: 1-5 parts; 10-25 parts of curing agent; 100 parts solvent; The solvent is composed of 50-70 parts of propylene glycol methyl ether acetate, 10-20 parts of dimethylformamide and 20-30 parts of butanone, and the application viscosity of the functionalized spin coating liquid is 200-800 cP.

7. The multi-step film preparation process of spin-coating-ion plating for a composite matte coating structure of a light-shielding ring according to claim 5, characterized in that, In step ③, the process conditions for plasma bombardment activation are as follows: under an argon atmosphere, the working pressure is 0.1-0.5 Pa, the applied substrate bias voltage is -200 to -50 V, and the bombardment time is 5-15 minutes.

8. The multi-step film preparation process of spin-coating-ion plating for a composite matte coating structure of a light-shielding ring according to claim 5, characterized in that, In step ④, the target material is a titanium target or an aluminum target. The current density of the titanium target is 0.1 - 0.3 A / cm², and the current density of the aluminum target is 0.05 - 0.15 A / cm². In the initial stage of depositing the blackened layer, a reactive gas is introduced into the vacuum chamber. The reactive gas is oxygen or nitrogen, the flow rate is 20-80 sccm, and the pressure is 0.1-0.5 Pa. Bias voltage: -200 to -100 V, deposition time 15-60 minutes.

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