Organic silicon coating material and preparation method thereof, and wear-resistant LED display module with consistent high ink color and preparation method thereof

Abstract

The invention belongs to the technical field of LED display screens, and particularly relates to an organic silicon coating material and a preparation method thereof, and a wear-resistant LED display module with consistent high ink color and a preparation method of the wear-resistant LED display module. Compared with the prior art, the preparation method has the advantages that the melanin nanoparticle self-assembly body is wrapped in the thin silicon dioxide shell, so that the compatibility of the melanin nanoparticle self-assembly body and the organic silicon resin is effectively improved, and the phenomena of aggregation and sedimentation of the melanin nanoparticles are avoided; moreover, the black nano-particle self-assembly body has a spatial three-dimensional structure, can provide more light scattering and absorbing sites, has some microscopic gaps, holes or roughness, can destroy the propagation path of light and enables light to generate diffuse reflection, so that the haze is improved, the formula of a coating material can be simplified, the stability of the coating material is improved, and the service life of the coating material is prolonged. The particle concentration in the coating material is also reduced, and the wear resistance of the coating material is effectively improved.

Description

Technical Field

[0001] This invention belongs to the field of LED display technology, and particularly relates to an organosilicon coating material and its preparation method, as well as an LED display module with consistent high ink color and wear resistance, and its preparation method. Background Technology

[0002] LED displays, due to their long lifespan, high color saturation, high brightness, customizable assembly, and ability to incorporate interactive technologies such as touch and AR, are demonstrating increasingly high commercial value and are widely used in indoor and outdoor scenarios such as urban landmarks, commercial plazas, large-scale sporting events and performances, and highway display boards.

[0003] Large-area LED displays are composed of numerous small modules. This modularity, while offering flexibility in design, also introduces the risk of inconsistent ink color. Differences in ink color between modules can compromise the overall aesthetics and perceived quality when the screen is off, affecting both the display's appearance and overall display performance when illuminated. This has become, to some extent, the most direct standard for evaluating the quality of an LED display. To address this issue, the industry commonly uses a black coating material containing resin, matting agents, and melanin. However, the matting agents and melanin need to be added at a certain concentration to mask the ink color differences between modules. Due to compatibility issues, these materials tend to clump together in the coating material, resulting in black spots and streaks after spraying, further exacerbating the ink color inconsistencies. Furthermore, high concentrations of matting agents and melanin rapidly reduce the surface wear resistance of the modules, making them difficult to clean and reducing the product's competitiveness.

[0004] Therefore, it is necessary to design a new coating material, coupled with a simple process, to efficiently produce LED displays with high ink color consistency and high wear resistance. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide an organosilicon coating material and its preparation method, as well as an LED display module with consistent ink color and wear resistance, and its preparation method. The organosilicon coating material can not only solve the problem of ink color difference between different modules, but also provide effective protection for the module surface and improve its surface wear resistance.

[0006] The present invention provides an organosilicon coating material, comprising: organosilicon resin and hybrid material; the hybrid material includes a black nanoparticle self-assembled body; the surface of the black nanoparticle self-assembled body is coated with a silicon dioxide layer.

[0007] Preferably, the surface of the silica layer is modified with a silane coupling agent;

[0008] And / or, the particle size of the black nanoparticle self-assembled body is 30–1000 nm;

[0009] And / or, the black nanoparticle self-assembled body has a three-dimensional spatial structure; the three-dimensional spatial structure includes one or more of a solid sphere structure, a cubic structure, and a bowl-shaped structure.

[0010] Preferably, the black nanoparticle self-assembled body is formed by the self-assembly of black nanoparticles; the particle size of the black nanoparticles is 3-30 nm.

[0011] And / or, the silicone resin is formed from silicone oligomers; the silicone oligomers are formed by polymerization of silicon-containing monomers; the silicon-containing monomers include a first silicon-containing monomer, a second silicon-containing monomer, and a third silicon-containing monomer;

[0012] The molar ratio of the first silicon-containing monomer, the second silicon-containing monomer, and the third silicon-containing monomer is (10-80):(5-100):(0-30);

[0013] The first silicon-containing monomer has the general formula shown in formula (I);

[0014] The second silicon-containing monomer has the general formula shown in formula (II);

[0015] The third silicon-containing monomer has the general formula described in formula (III);

[0016] Si(OR 1 Formula 4 (I); R 2 Si(OR 1 Formula 3(II); R 2 2Si(OR 1 Formula 2(III);

[0017] Among them, R in equations (I), (II) and (III) 1 Each alkyl group is independently selected from C1 to C4;

[0018] R in equations (II) and (III) 2 Each group is independently selected from C1-C6 alkyl, C2-C6 alkenyl, acryloyloxy, methacryloxy, amino-substituted C1-C6 alkyl, C1-C6 alkoxy, or groups formed by two or more of the above groups through a single bond, and R 2 It is not an alkoxy group of C1 to C6.

[0019] Preferably, the black nanoparticles are selected from one or more of melanin, carbon black, iron oxide nanoparticles, manganese dioxide nanoparticles, copper sulfide nanoparticles, and quantum dots;

[0020] And / or, the first silicon-containing monomer is selected from tetraethoxysilane;

[0021] And / or, the second silicon-containing monomer is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane and 3-aminopropyltriethoxysilane;

[0022] And / or, the third silicon-containing monomer is selected from diethoxydimethylsilane.

[0023] Preferably, the mass of the hybrid material is 0.5% to 10% of the mass of the silicone resin.

[0024] Preferably, it also includes one or more of the following: solvent, leveling agent, antioxidant, UV absorber, superdispersant, and amino resin;

[0025] The mass of the solvent is 0 to 9 times the mass of the silicone resin;

[0026] The leveling agent is 0.1% to 1% of the mass of the silicone coating material;

[0027] The antioxidant is present in an amount of 0.1% to 3% of the mass of the silicone coating material.

[0028] The mass of the UV absorber is 0.1% to 3% of the mass of the silicone coating material;

[0029] The mass of the superdispersant is 0.1% to 3% of the mass of the organosilicon coating material.

[0030] The present invention also provides a method for preparing the above-mentioned organosilicon coating material, comprising the following steps:

[0031] Organosilicon oligomers are mixed with hybrid materials and heated to react, resulting in an organosilicon coating material; the hybrid material includes black nanoparticle self-assemblies; the surface of the black nanoparticle self-assemblies is coated with a silicon dioxide layer.

[0032] Preferably, the hybrid material is prepared according to the following method:

[0033] S1) provides a dispersion containing black nanoparticles and an organic solvent;

[0034] S2) The dispersion is aged at room temperature to obtain an aged dispersion;

[0035] S3) The aged dispersion is mixed and emulsified with an aqueous solution of a surfactant, and then the organic solvent is removed to obtain a black nanoparticle self-assembled body.

[0036] S4) Coating the surface of the black nanoparticle self-assembled body with a silica layer to obtain a hybrid material;

[0037] And / or, the organosilicon oligomer is prepared according to the following method:

[0038] Silicon-containing monomers are mixed in a solvent, and then a catalyst is added to carry out a polymerization reaction to obtain organosilicon oligomers;

[0039] The mass ratio of the silicon-containing monomer, catalyst, and solvent is 100:(0-5):(0-900);

[0040] The molar ratio of the first silicon-containing monomer, the second silicon-containing monomer, and the third silicon-containing monomer is (10-80):(5-100):(0-30);

[0041] The first silicon-containing monomer has the general formula shown in formula (I);

[0042] The second silicon-containing monomer has the general formula shown in formula (II);

[0043] The third silicon-containing monomer has the general formula described in formula (III);

[0044] Si(OR 1 Formula 4 (I); R 2 Si(OR 1 Formula 3(II); R 2 2Si(OR 1 Formula 2(III);

[0045] Among them, R in equations (I), (II) and (III) 1 Each alkyl group is independently selected from C1 to C4;

[0046] R in equations (II) and (III) 2 Each group is independently selected from C1-C6 alkyl, C2-C6 alkenyl, acryloyloxy, methacryloxy, amino-substituted C1-C6 alkyl, C1-C6 alkoxy, or groups formed by two or more of the above groups through a single bond, and R 2 It is not an alkoxy group of C1 to C6.

[0047] The present invention also provides an LED display module with high ink color consistency and wear resistance, comprising a substrate, a plurality of LED light-emitting chips disposed on the substrate, an encapsulating adhesive layer disposed between the plurality of LED light-emitting chips and on the surface of the encapsulating adhesive layer away from the substrate, and an organosilicon coating disposed on the surface of the encapsulating adhesive layer away from the substrate; the organosilicon coating is formed from the above-mentioned organosilicon coating material.

[0048] The present invention also provides a method for preparing the above-mentioned high ink color consistency and wear-resistant LED display module, comprising the following steps:

[0049] The aforementioned silicone coating material is transferred to the surface of the encapsulating adhesive layer of the encapsulated LED display module, and then heated and cured to obtain an LED display module with high ink uniformity and wear resistance.

[0050] Compared with the prior art, the organosilicon coating material provided by the present invention has the following advantages:

[0051] 1) To address the issue of ink color consistency in modules, the industry currently offers two main solutions: one is to apply a black semi-permeable film, such as PET film, to the surface; the other is to spray a black coating material. Black semi-permeable films are prone to edge warping during transportation, installation, or natural aging. Traditional black coating materials, due to their high carbon black and other melanin content, are prone to carbon black aggregation within the material, leading to uneven coating and new ink color problems. This invention self-assembles melanin nanoparticles into nanobowl shapes and encapsulates them in a thin silica shell, effectively improving their compatibility with silicone resin and preventing the aggregation and sedimentation of melanin nanoparticles.

[0052] 2) Unlike traditional black inks or black coatings that use black spherical nanoparticles, such as carbon black, this invention introduces for the first time in the field of ink color control coating material preparation the concept of adding black nanoparticles after they have self-assembled into assemblies with a three-dimensional spatial structure. After assembling into a three-dimensional spatial structure, it possesses a unique shape and a large specific surface area, providing more light scattering and absorption sites. Its asymmetrical geometry causes light to be reflected and scattered multiple times internally, extending the optical path, increasing the interaction between light and matter, and thus more effectively absorbing and scattering light, reducing reflectivity. In contrast, nanospherical structures are more regular, and the scattering and absorption of light on their surface are relatively weaker, making light more prone to specular reflection, resulting in higher reflectivity.

[0053] 3) The particle size of the black nanoparticles after self-assembly into an assembly with a three-dimensional spatial structure can be controlled between 30 and 1000 nm, which is sufficient to form an uneven microstructure on the module surface, thereby achieving an anti-glare effect. Moreover, the three-dimensional spatial structure may contain some microscopic gaps, pores, or roughness. These microstructures can disrupt the light propagation path, causing diffuse reflection of light and thus increasing haze. Therefore, there is no need to add large-diameter silica microspheres as a matting agent to the coating material, which simplifies the formulation, improves the stability of the coating material, and reduces the particle concentration in the coating material, effectively improving its wear resistance.

[0054] 4) Unlike traditional black ink or black coating materials, which involve directly adding silica to resin materials for physical mixing or simply modifying its surface with silane coupling agents before mixing with resin, this invention fully utilizes the silica shell wrapped around the three-dimensional structure, allowing it to participate in the bulk copolymerization of organosilicon resin. This better enhances the chemical bonding and compatibility between the three-dimensional structure and the organosilicon resin, thereby effectively improving its wear resistance.

[0055] 5) Since the self-assembled three-dimensional structure has multiple functions such as light diffusion, anti-reflection, enhanced blackness, and anti-glare, the multi-layer coating materials that originally needed to be covered during encapsulation are simplified and integrated into a single-layer coating material, avoiding the superposition of multiple layers of adhesive film or resin materials, effectively simplifying the production process and reducing production costs. Attached Figure Description

[0056] Figure 1 This invention provides a schematic diagram of a specific LED display module manufacturing process.

[0057] Figure 2 This is a TEM image of the Fe3O4 nanoparticles prepared in Example 1 of this invention;

[0058] Figure 3 This is a SEM image of the Fe3O4 nanoparticle assembly with a silica thin shell prepared in Example 1 of the present invention.

[0059] Figure 4 This is a SEM image of the carbon black nanoparticle assembly with a silica thin shell prepared in Example 2 of the present invention. Detailed Implementation

[0060] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0061] The present invention provides an organosilicon coating material, comprising: organosilicon resin and hybrid material; the hybrid material includes a black nanoparticle self-assembled body; the surface of the black nanoparticle self-assembled body is coated with a silicon dioxide layer.

[0062] This invention encapsulates melanin nanoparticle self-assemblies within a thin silica shell, effectively improving their compatibility with silicone resins and preventing the aggregation and sedimentation of melanin nanoparticles. Furthermore, the self-assemblies of black nanoparticles possess a three-dimensional spatial structure that provides more light scattering and absorption sites. They also contain microscopic gaps, pores, or roughness that can disrupt the light propagation path, causing diffuse reflection and thus increasing haze. This simplifies the formulation of coating materials, improves their stability, reduces the particle concentration in the coating material, and effectively enhances their wear resistance.

[0063] In a specific embodiment of the present invention, the organosilicon resin is formed from organosilicon oligomers; the organosilicon oligomers are formed by polymerization of silicon-containing monomers; the silicon-containing monomers include a first silicon-containing monomer, a second silicon-containing monomer, and a third silicon-containing monomer; the silicon-containing monomer is an alkoxysilane; the first silicon-containing monomer has 4 alkoxy groups; the second silicon-containing monomer has 3 alkoxy groups; and the third silicon-containing monomer has 2 alkoxy groups; the molar ratio of the first silicon-containing monomer, the second silicon-containing monomer, and the third silicon-containing monomer is preferably (10-80):(5-100):(0-30), more preferably (10-80):(10-100):(0-30). The molar ratios of the first silicon-containing monomer, the second silicon-containing monomer, and the third silicon-containing monomer are 50:70:20 or 30:100:0. In some embodiments of the present invention, the molar ratio of the first silicon-containing monomer, the second silicon-containing monomer, and the third silicon-containing monomer is 50:70:20 or 30:100:0.

[0064] In one specific embodiment of the present invention, the first silicon-containing monomer has the general formula shown in formula (I); the second silicon-containing monomer has the general formula shown in formula (II); and the third silicon-containing monomer has the general formula shown in formula (III).

[0065] R 2 Si(OR 1 Formula 3(II); R 2 2Si(OR 1 Formula 2(III);

[0066] Among them, R in equations (I), (II) and (III) 1 Each of the alkyl groups is independently a C1 to C4 alkyl group, more preferably a C1 to C3 alkyl group, and even more preferably a methyl or ethyl alkyl group;

[0067] R in equations (II) and (III) 2 Each of the following groups is independently a C1-C6 alkyl group, a C2-C6 alkenyl group, an acryloyloxy group, a methacryloxy group, an amino-substituted C1-C6 alkyl group, a C1-C6 alkoxy group, or a group formed by two or more of the above groups through a single bond, and R 2 The group is not a C1-C6 alkoxy group; preferably a C1-C4 alkyl group, a C2-C4 alkenyl group, acryloyloxy group, methacryloxy group, amino-substituted C1-C4 alkyl group, C1-C4 alkoxy group, or a group formed by two or more of the above groups through a single bond; more preferably a C1-C3 alkyl group, a C2-C3 alkenyl group, acryloyloxy group, methacryloxy group, amino-substituted C1-C3 alkyl group, C1-C3 alkoxy group, or a group formed by two or more of the above groups through a single bond; even more preferably a C1-C3 alkyl group, vinyl group, acryloyloxy group, methacryloxy group, amino-substituted C1-C3 alkyl group, C1-C3 alkoxy group, or a group formed by two or more of the above groups through a single bond.

[0068] In one specific embodiment of the present invention, the first silicon-containing monomer includes, but is not limited to, tetraethoxysilane (TEOS).

[0069] In one specific embodiment of the present invention, the second silicon-containing monomer includes, but is not limited to, one or more of methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), γ-methacryloyloxypropyltrimethoxysilane (KH-570), vinyltriethoxysilane (VTES), γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560) and 3-aminopropyltriethoxysilane (APS).

[0070] In one specific embodiment of the present invention, the second silicon-containing monomer includes a silicon-containing monomer containing an epoxy group; the molar number of the silicon-containing monomer containing the epoxy group is 10% to 50% of the molar number of the second silicon-containing monomer; optionally, the molar number of the silicon-containing monomer containing the epoxy group is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% of the molar number of the second silicon-containing monomer or a range between any two of the above values.

[0071] In one specific embodiment of the present invention, the second silicon-containing monomer includes a silicon-containing monomer containing an epoxy group; the molar number of the silicon-containing monomer containing the epoxy group is 20% to 28.6% of the molar number of the second silicon-containing monomer.

[0072] In one specific embodiment of the present invention, the third silicon-containing monomer includes, but is not limited to, diethoxydimethylsilane (DMDES).

[0073] In one specific embodiment of the present invention, the hybrid material includes a black nanoparticle self-assembled body; the black nanoparticle self-assembled body is formed by the self-assembly of black nanoparticles; the black nanoparticles are any black nanoparticles well known to those skilled in the art, and there are no special limitations, including but not limited to one or more of melanin, carbon black, iron oxide nanoparticles, manganese dioxide nanoparticles, copper sulfide nanoparticles, and quantum dots; the particle size of the black nanoparticles is preferably 3-30 nm; optionally, the particle size of the black nanoparticles is 3 nm, 5 nm, 8 nm, 10 nm, 11 nm, 13 nm, 15 nm, 18 nm, 20 nm, 21 nm, 23 nm, 25 nm, 28 nm, 30 nm, or any two of the above values.

[0074] In one specific embodiment of the present invention, the black nanoparticle self-assembled body has a three-dimensional spatial structure; the three-dimensional spatial structure includes, but is not limited to, one or more of a solid sphere structure, a cubic structure, and a bowl-shaped structure. After the black nanoparticles are assembled into a three-dimensional spatial structure, they possess a unique shape and a large specific surface area, providing more light scattering and absorption sites. Their asymmetrical geometry causes light to be reflected and scattered multiple times internally, extending the optical path, increasing the interaction between light and matter, thereby more effectively absorbing and scattering light and reducing reflectivity. In contrast, the nanosphere structure is more regular, and the scattering and absorption of light on its surface are relatively weaker, making it more prone to specular reflection, resulting in higher reflectivity.

[0075] In a specific embodiment of the present invention, the particle size of the black nanoparticle self-assembled body is preferably 30–1000 nm. Within this range, it is sufficient to form an uneven microstructure on the module surface, thereby achieving an anti-glare effect. Furthermore, the three-dimensional structure may contain some microscopic gaps, pores, or roughness, which can disrupt the light propagation path, causing diffuse reflection and increasing haze. Therefore, there is no need to further add large-particle silica microspheres as a matting agent to the coating material, which simplifies the formulation, improves the stability of the coating material, and reduces the particle concentration in the coating material, effectively improving its wear resistance. Optionally, the particle size of the black nanoparticle self-assembled body is 30nm, 50nm, 80nm, 100nm, 150nm, 200nm, 250nm, 280nm, 300nm, 350nm, 380nm, 400nm, 450nm, 480nm, 500nm, 550nm, 580nm, 600nm, 650nm, 680nm, 700nm, 750nm, 780nm, 800nm, 850nm, 880nm, 900nm, 950nm, 980nm, 1000nm, or any two of the above values.

[0076] In one specific embodiment of the present invention, the surface of the black nanoparticle self-assembled body is coated with a silica layer, which can effectively improve its compatibility with organosilicon resin, avoid the aggregation and sedimentation of black nanoparticles, and enable it to participate in the bulk copolymerization of organosilicon resin, thereby better improving the chemical bonding degree and compatibility between the three-dimensional structure and the organosilicon resin bulk, and thus effectively improving its wear resistance. The silica layer is preferably obtained by depositing silica on the surface of the black nanoparticle self-assembled body through alkaline catalytic hydrolysis of tetraalkoxysilane. The number of carbon atoms of the alkoxy group in the tetraalkoxysilane is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0077] In one specific embodiment of the present invention, the mass ratio of the black nanoparticle self-assembled body to the silica layer is preferably 1:(1 to 10); optionally, the mass ratio of the black nanoparticle self-assembled body to the silica layer is 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10 or any two of the above ratios.

[0078] In a specific embodiment of the present invention, the surface of the silica layer is modified with a silane coupling agent. The silane coupling agent can further improve the compatibility between the hybrid material and the organosilicon oligomer, enabling it to participate in the bulk copolymerization of the organosilicon resin, thereby better enhancing the chemical bonding and compatibility between the three-dimensional structure and the organosilicon resin bulk, and effectively improving its wear resistance. The silane coupling agent can be any silane coupling agent well-known to those skilled in the art, and there are no special limitations. In this invention, it is preferred to include, but not limited to, one or more of vinyl silane coupling agents, epoxy silane coupling agents, amino silane coupling agents, ureosilane coupling agents, and mercaptosilane coupling agents. The vinyl silane coupling agent includes, but is not limited to, vinyltriethoxysilane, vinyltrimethoxysilane, etc.; the epoxy silane coupling agent includes, but is not limited to, 2-(3... The aminosilane coupling agents include, but are not limited to, γ-aminopropyltriethoxysilane (KH550), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (KH602); the ureosilane coupling agents include, but are not limited to, γ-ureopropyl-trimethoxysilane and γ-ureopropyl-methyldimethoxysilane; and the mercaptosilane coupling agents include, but are not limited to, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane.

[0079] In one specific embodiment of the present invention, the mass of the hybrid material is preferably 0.5% to 10% of the mass of the organosilicon oligomer; optionally, the mass of the hybrid material is preferably 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% of the mass of the organosilicon oligomer or any two of the above values.

[0080] In one specific embodiment of the present invention, the organosilicon coating material further includes one or more of solvents, leveling agents, antioxidants, UV absorbers, superdispersants, and amino resins.

[0081] In one specific embodiment of the present invention, the mass of the solvent is 0 to 9 times the mass of the silicone resin; optionally, the mass of the solvent is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9 times the mass of the silicone resin, or a range between any two of the above values.

[0082] According to the present invention, the solvent can be any solvent well known to those skilled in the art, and can be a solvent added during the preparation of organosilicon oligomers or during the preparation of organosilicon coating materials. In a specific embodiment provided by the present invention, the solvent includes, but is not limited to, one or more of alcohol solvents, ether solvents, ketone solvents, ester solvents, toluene, and xylene; the alcohol solvent includes, but is not limited to, methanol, ethanol, isopropanol, etc.; the ether solvent includes, but is not limited to, phenyl glycidyl ether, propylene glycidyl ether, etc.; the ketone solvent includes, but is not limited to, acetone, butanone, methyl isobutyl ketone, etc.; and the ester solvent includes, but is not limited to, ethyl acetate, butyl acetate, etc.

[0083] In one specific embodiment of the present invention, the mass of the leveling agent is preferably 0.1% to 1% of the mass of the silicone coating material; optionally, the mass of the leveling agent is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% of the mass of the silicone coating material, or a range between any two of the above values.

[0084] In one specific embodiment of the present invention, the leveling agent includes, but is not limited to, one or more of silicone leveling agents, acrylate leveling agents, and fluorocarbon leveling agents; the silicone leveling agent includes, but is not limited to, polyether-modified polysiloxane, polyester-modified polysiloxane, long-chain alkyl-modified polysiloxane, etc.; the acrylate leveling agent includes, but is not limited to, pure acrylate leveling agents, fluorinated acrylate leveling agents, etc.; more specifically, the leveling agent includes, but is not limited to, BYK-333 from BYK Corporation, EFKA-3777 from BASF, etc.

[0085] In one specific embodiment of the present invention, the antioxidant is preferably 0.1% to 3% of the mass of the silicone coating material; optionally, the antioxidant is 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% of the mass of the silicone coating material or a range between any two of the above values.

[0086] In one specific embodiment of the present invention, the antioxidant can be any antioxidant well known to those skilled in the art, including but not limited to BASF's Irganox 1076, Songwon's Songnox 1010, etc.

[0087] In one specific embodiment of the present invention, the mass of the UV absorber is preferably 0.1% to 3% of the mass of the silicone coating material; optionally, the mass of the UV absorber is 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% of the mass of the silicone coating material or a range between any two of the above values.

[0088] In one specific embodiment of the present invention, the UV absorber may be any UV absorber well known to those skilled in the art, including but not limited to BASF's Tinuvin 360, Tinuvin 770, Chemtura's UV-5411, etc.

[0089] In one specific embodiment of the present invention, the mass of the superdispersant is preferably 0.1% to 3% of the mass of the organosilicon coating material; optionally, the mass of the superdispersant is 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% of the mass of the organosilicon coating material or a range between any two of the above values.

[0090] In one specific embodiment of the present invention, the superdispersant includes, but is not limited to, BYK-2000 from BYK Corporation and Flowlen-33 from Kyoeisha Corporation.

[0091] The present invention also provides a method for preparing the above-mentioned organosilicon coating material, comprising the following steps: mixing organosilicon oligomers with hybrid materials, heating and reacting to obtain organosilicon coating materials; wherein the hybrid materials include black nanoparticle self-assemblies; and wherein the surface of the black nanoparticle self-assemblies is coated with a silicon dioxide layer.

[0092] In this invention, there are no special restrictions on the source of any raw materials; they can be commercially available.

[0093] In one specific embodiment of the present invention, the organosilicon oligomer is prepared by the following method: mixing silicon-containing monomers in a solvent, and then adding a catalyst to carry out a polymerization reaction to obtain the organosilicon oligomer; the silicon-containing monomers are the same as described above, and will not be repeated here.

[0094] In a specific embodiment of the present invention, the mass ratio of the silicon-containing monomer to the solvent is preferably 100:(0-900); optionally, the mass ratio of the silicon-containing monomer to the solvent is 100:0, 100:10, 100:50, 100:100, 100:200, 100:300, 100:400, 100:500, 100:600, 100:700, 100:800, 100:900, or any range between two of the above values.

[0095] In a specific embodiment of the present invention, the solvent can be any solvent well known to those skilled in the art, and there are no special limitations, including but not limited to one or more of alcohol solvents, ether solvents, ketone solvents, ester solvents, toluene, and xylene; the alcohol solvents include but are not limited to methanol, ethanol, isopropanol, etc.; the ether solvents include but are not limited to phenyl glycidyl ether, propenyl glycidyl ether, etc.; the ketone solvents include but are not limited to acetone, butanone, methyl isobutyl ketone, etc.; and the ester solvents include but are not limited to ethyl acetate, butyl acetate, etc.

[0096] In one specific embodiment of the present invention, silicon-containing monomers are mixed and stirred in a solvent; the stirring speed is preferably 500 to 1000 rpm; optionally, the stirring speed is 500 rpm, 600 rpm, 700 rpm, 800 rpm, 900 rpm, 1000 rpm or any two of the above values.

[0097] In a specific embodiment of the present invention, the mass ratio of the silicon-containing monomer to the catalyst is preferably 100:(0-5); optionally, the mass ratio of the silicon-containing monomer to the catalyst is 100:0, 100:0.5, 100:1, 100:2, 100:3, 100:4, 100:5 or any two of the above values.

[0098] In one specific embodiment of the present invention, the catalyst can be any condensation catalyst well known to those skilled in the art, and there are no special limitations. In the present invention, it is preferred to include, but not limited to, organotin compounds, acids or bases; the acid is preferably an inorganic acid, and more preferably HCl.

[0099] In one specific embodiment of the present invention, the polymerization reaction system further includes water; the mass ratio of the silicon-containing monomer to water is preferably 100:(10-50); optionally, the mass ratio of the silicon-containing monomer to water is preferably 100:10, 100:20, 100:30, 100:40, 100:50 or any two of the above values.

[0100] In one specific embodiment of the present invention, the temperature of the polymerization reaction is preferably 40°C to 80°C; optionally, the temperature of the polymerization reaction is 40°C, 50°C, 60°C, 70°C, 80°C or any two of the above values; the time of the polymerization reaction is 1 to 5 hours; optionally, the time of the polymerization reaction is 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or any two of the above values.

[0101] In one specific embodiment of the present invention, after the polymerization reaction, a solution containing organosilicon oligomers is obtained, which can be used directly without post-treatment.

[0102] In a specific embodiment of the present invention, the hybrid material is prepared by the following method: S1) providing a dispersion containing black nanoparticles and an organic solvent; S2) aging the dispersion at room temperature to obtain an aged dispersion; S3) mixing and emulsifying the aged dispersion with an aqueous solution of a surfactant, and then removing the organic solvent to obtain a self-assembled black nanoparticle; S4) coating the surface of the self-assembled black nanoparticle with a silica layer to obtain the hybrid material.

[0103] In a specific embodiment of the present invention, the black nanoparticles are as described above and will not be repeated here; the concentration of the black nanoparticles in the dispersion is preferably 1-20 mg / mL; optionally, the concentration of the black nanoparticles in the dispersion is 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, 10 mg / mL, 11 mg / mL, 12 mg / mL, 13 mg / mL, 14 mg / mL, 15 mg / mL, 16 mg / mL, 17 mg / mL, 18 mg / mL, 19 mg / mL, 20 mg / mL or any two of the above values; the organic solvent in the dispersion can be any organic solvent well known to those skilled in the art, and there are no special limitations, including but not limited to one or more of chloroform, dichloromethane, dichloroethane, ethyl acetate, butyl acetate, tetrahydrofuran, toluene and xylene.

[0104] In one specific embodiment of the present invention, due to the hydrophobicity and high surface energy of nanoparticles, they are prone to aggregation. Therefore, it is preferable to modify them with hydrophilicity, and more preferably, oleylamine is used for modification. This hydrophilic modification can be carried out during the preparation of black nanoparticles or can be performed directly on the black nanoparticles.

[0105] According to the present invention, the preparation of the black nanoparticles is carried out according to methods well known to those skilled in the art, without any special limitations. The sol-gel method or the high-temperature pyrolysis method can be used. In a specific embodiment provided by the present invention, taking iron oxide nanoparticles as an example, they are preferably prepared according to the following method: An iron precursor, benzyl ether, and oleylamine are mixed, and after dehydration by heating in a protective atmosphere, a further heating is carried out to perform a pyrolysis reaction to obtain iron oxide nanoparticles. The iron precursor can be any iron precursor well known to those skilled in the art, without any special limitations. In the present invention, it preferably includes, but is not limited to, iron acetylacetone. The volume ratio of benzyl ether to oleylamine is preferably 1:(0.5-2), more preferably 1:(0.8-1.5), even more preferably 1:(0.8-1.2), and most preferably 1:1. The concentration of the iron precursor in the mixed system is preferably 0.05-0.5 mmol / mL, more preferably 0.05-0.3 mmol / mL, even more preferably 0.05-0.2 mmol / mL, and even more preferably 0.08-0.15 mmol / mL. / mL, most preferably 0.1mmol / mL; the protective atmosphere can be any protective atmosphere known to those skilled in the art, and there are no special limitations, nitrogen is preferred in this invention; the dehydration temperature is preferably 100℃~110℃; the dehydration time is preferably 0.5~2h, more preferably 0.5~1.5h, and even more preferably 1h; the heating rate for continued heating is preferably 10~20℃ / min; the pyrolysis reaction temperature is preferably 250℃~350℃, more preferably 280℃~320℃, and even more preferably 300℃; the pyrolysis reaction time is preferably 0.5~3h, more preferably 0.8~2h, and even more preferably 1~1.5h; after the pyrolysis reaction, it is preferred to cool to room temperature, add an alcohol solvent for extraction, and obtain iron oxide nanoparticles after solid-liquid separation; the alcohol solvent can be any alcohol solvent known to those skilled in the art, and there are no special limitations, ethanol is preferred in this invention; the solid-liquid separation method can be any method known to those skilled in the art, and there are no special limitations, centrifugation is preferred in this invention.

[0106] In a specific embodiment of the present invention, if the black nanoparticles are carbon black, the hydrophilic modification of the black nanoparticles is carried out according to the following method: the carbon black is oxidized to obtain carbon black oxide; the carbon black oxide is dispersed in a benzene solvent, and then oleylamine, a condensing agent and an alkaline catalyst are added, and the reaction is carried out under a protective atmosphere to obtain hydrophilically modified black nanoparticles.

[0107] In a specific embodiment of the present invention, the oxidation treatment method can be any method well known to those skilled in the art and is not particularly limited. In the present invention, concentrated nitric acid is preferably used for oxidation treatment. The oxidation treatment temperature is preferably 60℃~100℃, more preferably 70℃~90℃, and even more preferably 80℃. The oxidation treatment time is preferably 1~3h, more preferably 1.5~2.5h, and even more preferably 2h. After oxidation treatment, it is preferably cooled to room temperature, and after centrifugation, washing and drying, carbon black oxide is obtained. The drying method can be any method well known to those skilled in the art and is not particularly limited. In the present invention, vacuum drying is preferred. The drying temperature is preferably 60℃~80℃. The drying time is preferably 8~20h, more preferably 10~15h, and even more preferably 12h.

[0108] In one specific embodiment of the present invention, carbon black oxide is dispersed in a benzene-based solvent, then oleylamine, a condensing agent, and an alkaline catalyst are added, and the reaction is carried out under a protective atmosphere by heating to obtain hydrophilically modified black nanoparticles. The benzene-based solvent can be any benzene-based solvent well-known to those skilled in the art, and there are no special limitations; toluene is preferred in this invention. The mass ratio of carbon black oxide to oleylamine is preferably 1:(1-5), more preferably 1:(1-3), even more preferably 1:(1.5-2.5), and most preferably 1:2. The condensing agent can be any condensing agent well-known to those skilled in the art, and there are no special limitations; dicyclohexylcarbodiimide (DCC) is preferred in this invention. The mass ratio of carbon black oxide to the condensing agent is preferably 1:(0.05-0.5), more preferably 1:(0.08-0.3), even more preferably 1:(0.1-0.2), and most preferably 1:0.1. The alkaline catalyst can be any alkaline catalyst well-known to those skilled in the art, and there are no special limitations. With particular restrictions, the catalyst used in this invention is preferably a pyridine-based catalyst, more preferably 4-dimethylaminopyridine; the mass ratio of carbon black oxide to alkaline catalyst is preferably 1:(0.01-0.1), more preferably 1:(0.03-0.08), even more preferably 1:(0.04-0.06), and most preferably 1:0.05; the reaction temperature is preferably 60℃-100℃, more preferably 70℃-90℃, and even more preferably 80℃; the reaction time is preferably 15-20h, more preferably 16-18h; after the reaction, it is preferably cooled to room temperature, and after centrifugation, washing, and drying, hydrophilic modified black nanoparticles are obtained; the washing is preferably carried out sequentially using a benzene-based solvent and ethanol; the drying method can be any method known to those skilled in the art and is not particularly limited, but vacuum drying is preferred in this invention; the drying temperature is preferably 60℃-80℃; the drying time is preferably 8-20h, more preferably 10-15h, and even more preferably 12h.

[0109] The dispersion is aged at room temperature to obtain an aged dispersion; during this process, the black nanoparticles undergo self-assembly. In a specific embodiment of the present invention, the aging time is preferably 5 to 20 days, more preferably 10 to 20 days; optionally, the aging time is 10 days, 11 days, 12 days, 13 days, 14 days, 15 days, 16 days, 17 days, 18 days, 19 days, 20 days, or any two of the above values.

[0110] The aging dispersion is emulsified with an aqueous solution of a surfactant, and then the organic solvent is removed to obtain a black nanoparticle self-assembled body. The concentration of the surfactant in the aqueous solution is preferably 10–50 mg / mL. Optionally, the concentration of the surfactant in the aqueous solution is 10 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL, or any two of the above values. The surfactant can be any surfactant well-known to those skilled in the art and is not particularly limited. In this invention, it is preferred to include, but is not limited to, one or more of, dodecyltrimethylammonium bromide (DTAB), hexadecyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium chloride (CTAC), tetradecyltrimethylammonium bromide (TTAB), octadecyltrimethylammonium bromide (OTAB), and hexadecylpyridine chloride (CPC). The volume ratio of the aging dispersion to the aqueous solution of the surfactant is preferably 1:(1–3). Optionally, the concentration of the aging dispersion to the aqueous solution of the surfactant is... The volume ratio of the surfactant aqueous solution is 1:1, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, or any two of the above ratios; the mixing and emulsification time is preferably 0.5 to 2 hours; optionally, the mixing and emulsification time is 0.5 hours, 0.8 hours, 1 hour, 1.5 hours, 2 hours, or any two of the above values; the mixing and emulsification speed is preferably 800 to 1500 rpm; optionally, the mixing and emulsification speed is 800 rpm, 900 rpm, 1000 rpm, or 1500 rpm. The rpm range is 0 rpm, 1100 rpm, 1200 rpm, 130 rpm, 1400 rpm, 1500 rpm, or any two of the above values; the method for removing the organic solvent is any method well known to those skilled in the art and is not particularly limited. In this invention, the organic solvent is preferably removed by heating and evaporation; the heating and evaporation temperature is preferably 60℃~80℃; the heating and evaporation time is preferably 60~180 min, more preferably 80~120 min, and even more preferably 100 min.

[0111] A silica layer is coated onto the surface of the black nanoparticle self-assembled body to obtain a hybrid material. The method for coating the silica layer can be any method well-known to those skilled in the art and is not particularly limited. In this invention, silica is preferably obtained by alkaline catalytic hydrolysis of tetraalkoxysilane to deposit silica on the surface of the black nanoparticle self-assembled body. The number of carbon atoms in the alkoxy group of the tetraalkoxysilane is preferably 1-4, more preferably 1-3, and even more preferably 1 or 2. The mass ratio of the black nanoparticle self-assembled body to the tetraalkoxysilane is preferably 1:(1-10). Optionally, The mass ratio of the self-assembled black nanoparticles to tetraalkoxysilane is 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, or any two of the above ratios; the preferred ratio of tetraalkoxysilane to alkaline substance in the alkaline catalytic hydrolysis of tetraalkoxysilane is 30 mL: (0.01–0.05) mol; optionally, the ratio of tetraalkoxysilane to alkaline substance is 30 mL: 0.01 mol, 30 mL: 0.02 mol, or 30 mL: 0.03 mol. The solvent ratio is 30 mL: 0.035 mol, 30 mL: 0.038 mol, 30 mL: 0.04 mol, 30 mL: 0.05 mol, or any two of the above values; an alcohol solvent is also added during the alkaline catalytic hydrolysis of tetraalkoxysilane; the alcohol solvent can be any solvent well known to those skilled in the art and is not particularly limited, but methanol is preferred in this invention; the volume ratio of tetraalkoxysilane to alcohol solvent is preferably 1:(3-5), more preferably 1:4; the alkaline catalytic hydrolysis of tetraalkoxysilane is preferably carried out under stirring conditions. The stirring speed is preferably 500–2000 rpm; optionally, the stirring speed is 500 rpm, 800 rpm, 1000 rpm, 1500 rpm, 2000 rpm or any two of the above values; the alkaline catalytic hydrolysis time of tetraalkoxysilane is preferably 10–60 min; optionally, the alkaline catalytic hydrolysis time of tetraalkoxysilane is 10 min, 20 min, 30 min, 40 min, 50 min, 60 min or any two of the above values.

[0112] In a specific embodiment of the present invention, a silica layer is preferably coated on the surface of the black nanoparticle self-assembly according to the following method: the black nanoparticle self-assembly, water, and an alkaline solution are mixed, and an alcoholic solution of tetraalkoxysilane is added under stirring conditions, and the reaction is continued to obtain a hybrid material; the alkaline solution can be any alkaline solution known to those skilled in the art, and there are no special limitations. In the present invention, an aqueous solution of an alkali metal hydroxide is preferred; the alkali metal hydroxide is preferably sodium hydroxide and / or potassium hydroxide; the concentration of the alkaline solution is preferably 0.1-0.5 mol / L, more preferably 0.1-0.2 mol / L.

[0113] In a specific embodiment of the present invention, a silica layer is coated on the surface of the black nanoparticle self-assembly, and a silane coupling agent is modified on the surface of the silica layer to obtain a hybrid material; specifically, the following method is followed: the black nanoparticle self-assembly coated with silica is dispersed in an alcohol-water mixed solvent, a silane coupling agent is added to react, and then an organic amine is added to continue the reaction to obtain the hybrid material; the volume ratio of alcohol solvent to water in the alcohol-water mixed solvent is preferably (5-10):1, more preferably (8-10):1, and even more preferably 9:1; the ratio of the black nanoparticle self-assembly coated with silica to the silane coupling agent is preferably 1g:(5-10)mL; optionally, the ratio of the black nanoparticle self-assembly coated with silica to the silane coupling agent is 1g:5mL. The ratios are 1g:6mL, 1g:7mL, 1g:8mL, 1g:9mL, 1g:10mL, or any two of the above ratios; the reaction is preferably carried out at room temperature; the reaction time is preferably 3-10h, more preferably 5-8h, and even more preferably 6h; the organic amine is any organic amine well known to those skilled in the art, including but not limited to triethylamine (TEA); the volume ratio of the silane coupling agent to the organic amine is preferably 7:(1-5), more preferably 7:(2-4), and even more preferably 7:3; the continued reaction is preferably carried out at room temperature; the continued reaction time is preferably 12-24h, more preferably 14-22h, even more preferably 16-20h, and most preferably 18h; after the continued reaction is completed, the supernatant is preferably removed by centrifugation, and the mixture is washed to obtain the hybrid material.

[0114] The organosilicon oligomer is mixed with the hybrid material. The mixing method can be any method well-known to those skilled in the art and is not particularly limited. In this invention, ultrasonic dispersion or magnetic stirring is preferred. The ultrasonic power is preferably 20–60 kHz; optionally, the ultrasonic power is 20 kHz, 30 kHz, 40 kHz, 50 kHz, 60 kHz, or any two of the above values. The mixing time is preferably 10–60 min; optionally, the mixing time is 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, or any two of the above values. During the mixing process, one or more of a solvent, leveling agent, antioxidant, UV absorber, and superdispersant are preferably added. The solvent, leveling agent, antioxidant, UV absorber, and superdispersant are as described above and will not be repeated here.

[0115] In one specific embodiment of the present invention, in order to improve the chemical resistance of the organosilicon coating material, an amino resin may be added simultaneously in this step.

[0116] After mixing, the mixture is heated to react and obtain an organosilicon coating material. The preferred temperature for the heating reaction is 40℃ to 80℃. Optionally, the temperature for the heating reaction is 40℃, 50℃, 60℃, 70℃, 80℃, or any two of the above values. The preferred heating reaction time is 2 to 10 hours. Optionally, the heating reaction time is 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or any two of the above values.

[0117] The present invention also provides an LED display module with high ink color consistency and wear resistance, comprising a substrate, a plurality of LED light-emitting chips disposed on the substrate, an encapsulating adhesive layer disposed between the plurality of LED light-emitting chips and on the surface of the encapsulating adhesive layer away from the substrate, and an organosilicon coating disposed on the surface of the encapsulating adhesive layer away from the substrate; the organosilicon coating is formed from the above-mentioned organosilicon coating material.

[0118] In one specific embodiment of the present invention, the thickness of the organosilicon coating is preferably 3 to 30 μm; optionally, the thickness of the organosilicon coating is 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 26 μm, 28 μm, 30 μm or any two of the above values.

[0119] In one specific embodiment of the present invention, the overall light loss of the high-color-consistency and wear-resistant LED display module is between 20% and 50%.

[0120] In one specific embodiment of the present invention, the surface hardness of the high-color-consistent and wear-resistant LED display module is ≥4H (under 500g load), and there are no scratches after 3000 cycles of wool felt friction (1000g load, 40mm stroke).

[0121] The organosilicon coating provided by this invention includes a three-dimensional structure of black nanoparticles after self-assembly, which has multiple functions such as light diffusion, anti-reflection, enhanced blackness, and anti-glare. It simplifies and integrates the multi-layer coating material that originally needed to be covered during encapsulation into a single-layer coating material, avoiding the superposition of multiple layers of adhesive film or resin material, effectively simplifying the production process and reducing production costs.

[0122] The present invention also provides a method for preparing the above-mentioned high ink color consistency and wear-resistant LED display module, comprising the following steps: transferring the above-mentioned organosilicon coating material to the surface of the encapsulation adhesive layer of the encapsulated LED display module, heating and curing to obtain the high ink color consistency and wear-resistant LED display module.

[0123] See Figure 1 , Figure 1 This is a schematic diagram illustrating a specific manufacturing process of an LED display module provided by the present invention.

[0124] In one specific embodiment of the present invention, the packaged LED display module can be an LED display module produced by different packaging processes such as SMD, GOB, COB, and MIP.

[0125] In a specific embodiment of the present invention, in order to improve the adhesion between the silicone coating and the encapsulating adhesive layer, it is preferable to first perform plasma treatment on the encapsulated LED display module, and then transfer the silicone coating material to the surface of the encapsulating adhesive layer of the encapsulated LED display module; the power of the plasma treatment is preferably 100-300W, more preferably 150-250W, and even more preferably 200W; the plasma treatment time is preferably 10-30s; optionally, the plasma treatment time is 10s, 15s, 20s, 25s, 30s or any two of the above values.

[0126] In one specific embodiment of the present invention, the silicone coating material is preferably transferred to the surface of the encapsulation adhesive layer of the encapsulated LED display module by inkjet printing process.

[0127] In a specific embodiment of the present invention, the heating and curing temperature is preferably 80℃ to 150℃; optionally, the heating and curing temperature is 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃ or any two of the above values; the heating and curing time is preferably 10 to 30 minutes; optionally, the heating and curing time is 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes or any two of the above values.

[0128] In one specific embodiment of the present invention, the silicone coating material can be transferred to the surface of the encapsulating adhesive layer of the encapsulated LED display module in a single transfer or multiple transfers; when transferred to the surface of the encapsulating adhesive layer of the encapsulated LED display module in multiple transfers, the thickness of a single transfer is preferably 3 to 15 μm; optionally, the thickness of a single transfer is 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 14 μm, 15 μm or any two of the above values; when transferred to the surface of the encapsulating adhesive layer of the encapsulated LED display module in multiple transfers, it is preferable to heat-cure after each transfer before performing the next transfer.

[0129] In one specific embodiment of the present invention, after the final heating and curing, it is preferable to continue curing at room temperature to obtain an LED display module with consistent ink color and wear resistance; by continuing curing at room temperature, the surface hardness and wear resistance of the module can be further improved; the curing time is preferably 1 to 10 days; optionally, the curing time is 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days or any two of the above values.

[0130] To further illustrate the present invention, the following describes in detail, with reference to embodiments, an organosilicon coating material and its preparation method, and an LED display module with consistent ink color and wear resistance and its preparation method.

[0131] All reagents used in the following examples are commercially available.

[0132] Example 1

[0133] 1.1 Preparation of black Fe3O4 nanoparticle assemblies

[0134] First, Fe3O4 nanoparticles with a particle size of 10 nm were prepared. The specific experimental conditions were as follows: 30 mmol of ferric acetylacetone (Maclean, I811767) was dissolved in 150 mL of benzyl ether (Sinopharm Group, C148400010) and 150 mL of oleylamine (Maclean, O815176). Under a nitrogen atmosphere, the solution was heated to 100 °C for 1 h to dehydrate. Then, the solution was rapidly heated to 300 °C at a heating rate of 20 °C / min and aged at this temperature for 1 h before being cooled to room temperature. 500 mL of ethanol (Maclean, E708489) was added for extraction, and centrifugation was performed to obtain Fe3O4 nanoparticles with an average particle size of 10 nm. The transmission electron microscope (TEM) image is shown below. Figure 2 As shown.

[0135] Fe3O4 nanoparticle assemblies with a bowl-shaped structure and a SiO2 thin shell were prepared under the following experimental conditions: Fe3O4 nanoparticles were dispersed in chloroform (Sinopharm Group, HW049401) to prepare a dispersion with a concentration of 8 mg / mL, and aged at room temperature for 10 days. After aging, 500 mL of the dispersion was added to 1 L of a 20 mg / mL hexadecyltrimethylammonium bromide (CTAB) aqueous solution (Sigma-Aldrich, 219374) and stirred at 1000 rpm for 1 h. Then, the emulsion was heated at 60 °C for 100 min to evaporate and remove the chloroform, forming Fe3O4 nanoparticle assemblies in water. Subsequently, 4 L of water and 350 mL of 0.1 M NaOH solution were added to the above solution. The stirring speed was controlled at 1000 rpm. Then, 120 mL of a 20% TEOS (Maclean, T819506) solution (TEOS to methanol volume ratio 1:4) was added, and the reaction was continued for 30 min to obtain an assembly of Fe3O4 nanoparticles (average particle size 450 nm) coated with a silica thin shell. Its SEM image is shown below. Figure 3 As shown.

[0136] KH560 was modified on the surface of the assembly. The specific experimental conditions were as follows: 0.1 g of Fe3O4 nanoparticle assembly coated with a silica shell was dispersed in a mixed solvent of 9 mL anhydrous ethanol and 1 mL deionized water. 0.7 mL of silane coupling agent KH560 (Maclean, G810441) was added dropwise under continuous stirring. The reaction was carried out at room temperature for 6 h. Then, 0.3 mL of triethylamine TEA (Maclean, T818772) was added. The reaction was continued at room temperature for 18 h. After centrifugation to remove the supernatant and washing, Fe3O4 nanoparticle assembly with KH560 surface modification was obtained.

[0137] 1.2 Preparation of organosilicon coating materials with Fe3O4 nanoparticle assemblies

[0138] Preparation of organosilicon oligomers: 50g of tetraethyl silicate TEOS (Maclean, T819506), methyltriethoxysilane MTES (Maclean, T818809), dimethyldiethoxysilane DMDES (Maclean, D742926), and KH560 (Maclean, G810441) in a molar ratio of 5:5:2:2 were added to 300g of anhydrous ethanol. The magnetic stirring speed was controlled at 800rpm. 2.1g of 1M HCl (Sinopharm Group, 10011018) and 14g of deionized water were added, and the mixture was stirred continuously at 50℃ for 3h to prepare organosilicon oligomers.

[0139] Preparation of Fe3O4 nanoparticle assembly hybrid organosilicon coating material: 3g of Fe3O4 nanoparticle assembly with KH560 surface modified and 0.5g of BYK-2000 were added to the above organosilicon oligomer, ultrasonically dispersed for 20min (40kHz), and heated to 50℃ to continue the reaction for 6h to obtain Fe3O4 nanoparticle assembly hybrid organosilicon coating material.

[0140] 1.3 Fabrication of LED displays with high ink color consistency and high wear resistance

[0141] The packaged COB display module was subjected to surface plasma treatment at 200W power for 20 seconds.

[0142] Using inkjet technology, a layer of Fe3O4 nanoparticle assembly hybrid organosilicon coating material with a wet thickness of 8μm is sprayed onto the module surface. After curing at 100℃ for 30min, another layer of Fe3O4 nanoparticle assembly hybrid organosilicon coating material with a wet thickness of 8μm is sprayed onto the module surface. After curing at 100℃ for 30min, it is then cured at room temperature for 72h to obtain an LED display module with high ink color consistency and high wear resistance.

[0143] Example 2

[0144] 2.1 Preparation of black nanoparticle carbon black assemblies

[0145] 10 g of carbon black nanoparticles CB (COLOUR BLACK FW 255) with a particle size of 11 nm were added to a round-bottom flask, and 500 mL of concentrated nitric acid (Sinopharm Group, 10014508) was injected. The mixture was heated in an oil bath at 500 rpm to 80 °C and refluxed for 2 h. After cooling to room temperature, the mixture was centrifuged, and the precipitate was washed with deionized water until neutral. The precipitate was then dried under vacuum at 60 °C for 12 h to obtain carbon black oxide.

[0146] 10 g of carbon black oxide was added to a round-bottom flask, and 200 mL of toluene (Sinopharm Group, 10022818) was injected. The mixture was ultrasonically dispersed for 30 min (40 kHz). Then, 20 g of oleylamine (Maclean, O815176), 1 g of dicyclohexylcarbodiimide DCC (Maclean, N806920), and 0.5 g of 4-dimethylaminopyridine (Maclean, D742560) were added sequentially. The mixture was stirred at 500 rpm for 10 min, and nitrogen gas (flow rate 15 mL / min) was purged for 10 min to remove oxygen from the system. The mixture was then continuously stirred and heated in an oil bath to 80 °C for 18 h. After cooling to room temperature, the mixture was centrifuged. The precipitate was washed three times with toluene, then twice with ethanol, and finally dried under vacuum at 60 °C for 12 h to obtain oleylamine-modified carbon black nanoparticles.

[0147] The oleylamine-modified carbon black nanoparticles were dispersed in chloroform (Sinopharm Group, HW049401) to prepare a dispersion with a concentration of 8 mg / mL, and aged at room temperature for 13 days. After aging, 550 mL of the dispersion was added to 1 L of a 20 mg / mL aqueous solution of hexadecyltrimethylammonium bromide (CTAB) (Sigma-Aldrich, 219374), and stirred at 1000 rpm for 1 h. The emulsion was then heated at 60 °C for 100 min to evaporate the chloroform, forming carbon black nanoparticle assemblies in water. Subsequently, 4 L of water and 380 mL of 0.1 M NaOH solution were added to the above solution. The stirring speed was controlled at 1000 rpm. Then, 150 mL of a 20% TEOS (Maclean, T819506) solution (TEOS to methanol volume ratio 1:4) was added, and the reaction was continued for 30 min to obtain a carbon black nanoparticle assembly (average particle size 380 nm) with a silica thin shell. Its SEM image is shown below. Figure 4 As shown.

[0148] The specific experimental conditions for modifying the surface of the assembly with KH560 are the same as in Example 1.

[0149] 2.2 Preparation of organosilicon coating materials with carbon black nanoparticle assemblies

[0150] Same as in Example 1.

[0151] 2.3 Fabrication of LED displays with high ink color consistency and high wear resistance

[0152] Same as in Example 1.

[0153] Example 3

[0154] 3.1 Preparation of black nanoparticle carbon black assemblies

[0155] Same as Example 2.

[0156] 3.2 Preparation of organosilicon coating materials with carbon black nanoparticle assemblies

[0157] Preparation of organosilicon oligomers: 50g of tetraethyl silicate TEOS (Maclean, T819506), methyltrimethoxysilane MTMS (Maclean, T743030), vinyltriethoxysilane VTES (Maclean, T742512), and KH560 (Maclean, G810441) in a molar ratio of 3:5:3:2 were added to a mixed solvent consisting of 200g xylene (Maclean, X821391) and 100g butanone (Sinopharm Group, C389570010). The magnetic stirring speed was controlled at 800rpm. 2.1g of 1M HCl (Sinopharm Group, 10011018) and 14g of deionized water were added, and the mixture was stirred continuously at 60℃ for 3h to prepare organosilicon oligomers.

[0158] Preparation of a carbon black nanoparticle assembly hybrid organosilicon coating material: 3g of carbon black nanoparticle assembly with KH560 surface modified, 0.5g of superdispersant BYK-2000, 0.5g of antioxidant (BASF, Irganox1076), and 0.5g of UV absorber (BASF, Tinuvin360) were added to the above organosilicon oligomer, ultrasonically dispersed for 20min (40kHz), and heated to 50℃ for 6h to continue the reaction to obtain a carbon black nanoparticle assembly hybrid organosilicon coating material.

[0159] 3.3 Fabrication of LED displays with high ink color consistency and high wear resistance

[0160] Same as in Example 1.

[0161] Comparative Example 1

[0162] 1.1 Preparation of black Fe3O4 nanoparticle assemblies

[0163] Same as in Example 1.

[0164] 1.2 Preparation of organosilicon coating materials with Fe3O4 nanoparticle assemblies

[0165] Weigh 50g of silicone resin (Shin-Etsu, KER-2100) and add it to 200g of xylene (Maclean, X821391) solvent. Stir at 3000rpm, add 3g of Fe3O4 nanoparticle assembly with KH560 surface modified and 0.5g of BYK-2000 to the above silicone resin solution, sonicate for 20min (40kHz), heat to 50℃ and continue to react for 6h to obtain a silicone coating material with Fe3O4 nanoparticle assembly hybridization.

[0166] 3) Fabrication of LED displays with high ink color consistency and high wear resistance

[0167] Same as in Example 1.

[0168] Comparative Example 2

[0169] 2.1 Preparation of Carbon Black and SiO2 Doped Organosilicon Coating Materials

[0170] Weigh 50g of silicone resin (Shin-Etsu, KER-2100) and add it to 200g of xylene (Maclean, X821391) solvent. Stir at 3000rpm. Add 1.5g of carbon black (COLOUR BLACK FW 255), 1.5g of SiO2 (Evonik, OK520) and 0.5g of BYK-2000 to the above silicone resin solution. Disperse ultrasonically for 20min (40kHz), and continue the reaction at 50℃ for 6h to obtain a carbon black and SiO2 doped silicone coating material.

[0171] 2) Fabrication of LED displays with high ink color consistency and high wear resistance

[0172] Same as in Example 1.

[0173] Performance comparison test

[0174] 1. Ink color consistency test:

[0175] Three LED displays were prepared using the above-described embodiments and three using the comparative process methods. The ink color consistency was tested. The L value at nine different positions on the lamp board was measured using a colorimeter. The ink color consistency inside the lamp board and between lamp boards was compared. The results are shown in Table 1.

[0176] Table 1 Results of Ink Color Consistency Test

[0177]

[0178]

[0179] Results Analysis: As shown in the table above, the ink color consistency within the modules and between modules of Examples 1, 2, 3 and Comparative Example 1 are better than that of Comparative Example 2. This indicates that compared with adding both black carbon black and matting agent SiO2 to the coating material, adding only nanoparticle assemblies is more beneficial for controlling the ink color differences within and between modules.

[0180] 2. Gloss test: The gloss of the module surface at 60° was measured using a Sanenshi YG60s gloss meter. The results are shown in Table 2.

[0181] Surface hardness test: The light panel was fixed on the cabinet and the surface hardness of each group of light panels was measured using a pencil hardness tester. The load weight was 500g. The test results are shown in Table 2.

[0182] Abrasion resistance test: Using a wool felt test head, a load of 1000g was applied and the surface of each group of lamp panels was rubbed back and forth 3000 times at a constant rate (40 cycles / min) with a stroke of 40mm. After the test, the surface was observed for any whitening or scratches. The results are shown in Table 2.

[0183] Table 2 Surface hardness and wear resistance test results

[0184]

[0185]

[0186] Results Analysis: As shown in the table above, the surface gloss of the modules prepared in Examples 1, 2, 3 and Comparative Example 1 is almost the same as that of the module prepared in Comparative Example 2. This indicates that the black nanoparticles, after self-assembling into an assembly with a three-dimensional spatial structure, can effectively achieve the same matte effect as micron-sized SiO2. The surface hardness and wear resistance of the modules prepared in Examples 1, 2, and 3 are significantly higher than those in Comparative Example 2 and Comparative Example 1. This indicates that compared with directly mixing nanoparticles with organosilicon resin (Comparative Example 2) or grafting them onto the side chains of organosilicon resin after modifying KH560 (Comparative Example 1), the hybrid organosilicon coating material of the black nanoparticle assembly prepared in this invention can significantly improve the chemical bonding degree between nanoparticles and organosilicon resin, thereby effectively improving the hardness and wear resistance of the material after curing.

[0187] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An organosilicon coating material, characterized in that, include: Organosilicon resin and hybrid material; the hybrid material includes a black nanoparticle self-assembled body; the surface of the black nanoparticle self-assembled body is coated with a silicon dioxide layer.

2. The organosilicon coating material according to claim 1, characterized in that, The surface of the silica layer is modified with a silane coupling agent; And / or, the particle size of the black nanoparticle self-assembled body is 30–1000 nm; And / or, the black nanoparticle self-assembled body has a three-dimensional spatial structure; the three-dimensional spatial structure includes one or more of a solid sphere structure, a cubic structure, and a bowl-shaped structure.

3. The organosilicon coating material according to claim 1, characterized in that, The black nanoparticle self-assembled body is formed by the self-assembly of black nanoparticles; the particle size of the black nanoparticles is 3-30 nm. And / or, the silicone resin is formed from silicone oligomers; the silicone oligomers are formed by polymerization of silicon-containing monomers; the silicon-containing monomers include a first silicon-containing monomer, a second silicon-containing monomer, and a third silicon-containing monomer; The molar ratio of the first silicon-containing monomer, the second silicon-containing monomer, and the third silicon-containing monomer is (10-80):(5-100):(0-30); The first silicon-containing monomer has the general formula shown in formula (I); The second silicon-containing monomer has the general formula shown in formula (II); The third silicon-containing monomer has the general formula described in formula (III); Si(OR 1 )4 of formula (I); R 2 Si(OR 1 )3 of formula (II); R 2 2Si(OR 1 )2 of formula (III); Among them, R in equations (I), (II) and (III) 1 Each alkyl group is independently selected from C1 to C4; R in equations (II) and (III) 2 Each group is independently selected from C1-C6 alkyl, C2-C6 alkenyl, acryloyloxy, methacryloxy, amino-substituted C1-C6 alkyl, C1-C6 alkoxy, or groups formed by two or more of the above groups through a single bond, and R 2 It is not an alkoxy group of C1 to C6.

4. The organosilicon coating material according to claim 3, characterized in that, The black nanoparticles are selected from one or more of melanin, carbon black, iron oxide nanoparticles, manganese dioxide nanoparticles, copper sulfide nanoparticles, and quantum dots. And / or, the first silicon-containing monomer is selected from tetraethoxysilane; And / or, the second silicon-containing monomer is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane and 3-aminopropyltriethoxysilane; And / or, the third silicon-containing monomer is selected from diethoxydimethylsilane.

5. The organosilicon coating material according to claim 1, characterized in that, The mass of the hybrid material is 0.5% to 10% of the mass of the silicone resin.

6. The organosilicon coating material according to claim 1, characterized in that, It also includes one or more of the following: solvents, leveling agents, antioxidants, UV absorbers, superdispersants, and amino resins; The mass of the solvent is 0 to 9 times the mass of the silicone resin; The leveling agent is 0.1% to 1% of the mass of the silicone coating material; The antioxidant is present in an amount of 0.1% to 3% of the mass of the silicone coating material. The mass of the UV absorber is 0.1% to 3% of the mass of the silicone coating material; The mass of the superdispersant is 0.1% to 3% of the mass of the organosilicon coating material.

7. A method for preparing the organosilicon coating material according to claim 1, characterized in that, Includes the following steps: Organosilicon oligomers are mixed with hybrid materials and heated to react, resulting in an organosilicon coating material; the hybrid material includes black nanoparticle self-assemblies; the surface of the black nanoparticle self-assemblies is coated with a silicon dioxide layer.

8. The preparation method according to claim 7, characterized in that, The hybrid material is prepared according to the following method: S1) provides a dispersion containing black nanoparticles and an organic solvent; S2) The dispersion is aged at room temperature to obtain an aged dispersion; S3) The aged dispersion is mixed and emulsified with an aqueous solution of a surfactant, and then the organic solvent is removed to obtain a black nanoparticle self-assembled body. S4) Coating the surface of the black nanoparticle self-assembled body with a silica layer to obtain a hybrid material; And / or, the organosilicon oligomer is prepared according to the following method: Silicon-containing monomers are mixed in a solvent, and then a catalyst is added to carry out a polymerization reaction to obtain organosilicon oligomers; The mass ratio of the silicon-containing monomer, catalyst, and solvent is 100:(0-5):(0-900); The molar ratio of the first silicon-containing monomer, the second silicon-containing monomer, and the third silicon-containing monomer is (10-80):(5-100):(0-30); The first silicon-containing monomer has the general formula shown in formula (I); The second silicon-containing monomer has the general formula shown in formula (II); The third silicon-containing monomer has the general formula described in formula (III); Si(OR 1 )4 of formula (I); R 2 Si(OR 1 )3 of formula (II); R 2 2Si(OR 1 )2 of formula (III); Among them, R in equations (I), (II) and (III) 1 Each alkyl group is independently selected from C1 to C4; R in equations (II) and (III) 2 Each group is independently selected from C1-C6 alkyl, C2-C6 alkenyl, acryloyloxy, methacryloxy, amino-substituted C1-C6 alkyl, C1-C6 alkoxy, or groups formed by two or more of the above groups through a single bond, and R 2 It is not an alkoxy group of C1 to C6.

9. A high-consistency and wear-resistant LED display module, characterized in that, The invention includes a substrate, a plurality of LED light-emitting chips disposed on the substrate, an encapsulating adhesive layer disposed between the plurality of LED light-emitting chips and on the surface of the encapsulating adhesive layer away from the substrate, and an organosilicon coating disposed on the surface of the encapsulating adhesive layer away from the substrate; the organosilicon coating is formed from the organosilicon coating material according to any one of claims 1 to 6 or the organosilicon coating material prepared by the preparation method according to claim 7 or 8.

10. A method for preparing an LED display module with high ink color consistency and wear resistance as described in claim 9, characterized in that, Includes the following steps: The silicone coating material according to any one of claims 1 to 6 or the silicone coating material prepared by the preparation method according to claim 7 or 8 is transferred to the surface of the encapsulation adhesive layer of the encapsulated LED display module, and then heated and cured to obtain an LED display module with high ink color consistency and wear resistance.

Images