Transparent protective layer, uvioresistant and impact-resistant coating, exterior metal part and vehicle

Abstract

The invention relates to a transparent protective layer, an anti-ultraviolet impact-resistant coating, an exterior metal part and a vehicle. The transparent protective layer is formed by curing a transparent ceramic composite material; the transparent ceramic composite material comprises the following components in percentage by mass: 15%-50% of a framework material, 0.01%-8% of an ultraviolet absorbent and 0.01%-5% of a light stabilizer, the framework material comprises 3%-20% of a first framework material and 12%-40% of a second framework material; the general formula of the first framework material is R1 Si < X > < 14-a >; and the general formula of the second framework material is R2 SiX < 2 > < c > P < 4-b-c >. The invention further provides an anti-ultraviolet impact-resistant coating with the transparent protective layer, an exterior metal part and a vehicle. According to the technical scheme, the service life of the electroluminescent layer can be prolonged, the overall light aging performance and mechanical performance can be improved on the premise that the color of the colored paint layer is not changed, and the application process of the electroluminescent effect on automobile metal exterior trimming parts is accelerated.

Description

Technical Field

[0001] This invention relates to a transparent protective layer, an anti-ultraviolet and impact-resistant coating, exterior metal parts and vehicles, belonging to the field of automotive exterior accessories technology. Background Technology

[0002] With the development of the automotive industry, not only are there appearance requirements for car bodies and glass designs, but exterior trim components, as an important part of the vehicle's image, are also increasingly being required to become highlights of automotive fashion. Simply adjusting paint color and increasing pearlescent brightness is insufficient to meet the demands of a rich and diverse future appearance; it is necessary to introduce appropriate light effects to enhance the overall fashion sense of the vehicle.

[0003] The method of creating luminous patterns by punching holes has limitations in terms of the patterns that can be created, and it cannot achieve an invisibility effect when the patterns are not luminous.

[0004] When using electroluminescent multilayer composite paint, the aluminum profile lacks transparency, so the luminescent composite paint must be placed on the outside. Furthermore, since the luminescent composite paint is mostly opaque, a layer of colored paint needs to be sprayed over it to maintain the appearance of the aluminum profile exterior parts and the vehicle body even when no electricity is applied. The painting of aluminum profile exterior parts is rapidly developing towards a spray-and-bake process; currently, black spray-and-bake paint is in mass production, and other colors are under development.

[0005] However, current non-black paints applied by spraying and baking cannot meet the requirements for light aging resistance and poor mechanical properties. A layer of transparent protective paint needs to be added to the outer layer of the paint to protect it without changing its color. This requires the outer transparent paint to have excellent light aging resistance and mechanical properties. For example, CN115515268A describes an electroluminescent paint for automotive interior and exterior trim parts and its preparation method. This electroluminescent paint can be applied to composite electroluminescent coatings inside and outside the vehicle body. The composite luminescent layer includes an electrode layer, a luminescent layer, an insulating layer, and a conductive layer. The method primarily addresses the weather resistance and stone chip resistance issues of the electroluminescent paint through a transparent substrate back-side application process.

[0006] Therefore, providing an exterior metal part with an electroluminescent coating that has high aging resistance and mechanical properties is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0007] To address the aforementioned technical problems, the present invention aims to provide a transparent protective layer that offers superior aging resistance and mechanical properties.

[0008] Another objective of this invention is to provide an anti-ultraviolet and impact-resistant coating having the aforementioned transparent protective layer.

[0009] The present invention also aims to provide an exterior metal part having the above-mentioned UV-resistant and impact-resistant coating and a vehicle having the exterior metal part.

[0010] To achieve the above objectives, the present invention provides a transparent protective layer, wherein the transparent protective layer is formed by curing a transparent ceramic composite material (or transparent ceramic paint);

[0011] By weight percentage, the transparent ceramic composite material comprises 15%-50% structural material, 0.01%-8% ultraviolet absorber, and 0.01%-5% light stabilizer;

[0012] The structural materials comprise 3%-20% of the first structural material and 12%-40% of the second structural material.

[0013] According to a specific embodiment of the present invention, the first structural material can form a Si-O-Si inorganic framework through a hydrolysis-condensation reaction, providing rigidity for the coating. Preferably, the first structural material contains alkoxy groups and may optionally contain inactive groups of the general formula R. 1 a SiX 1 4-a Among them, R 1 It is an inactive group (i.e., does not undergo hydrolysis), selected from C1-C7 alkyl, C6-C10 aryl, C2-C7 alkenyl, C2-C7 ether, and C1-C7 fluoroalkyl, where a = 0, 1, 2, or 3; X 1 -OC n H 2n+1 n = 1, 2, 3, or 4. The first structural material is preferably selected from one or more combinations of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltriethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, and trimethoxy(2-methoxyethoxy)silane. The first structural material preferably contains alkoxy groups and inactive groups.

[0014] According to a specific embodiment of the present invention, preferably, the transparent ceramic composite material further comprises, by mass percentage, 10%-50% catalyst, 10%-50% solvent, 2%-20% silica sol, and 2%-10% resin.

[0015] According to a specific embodiment of the present invention, preferably, the content of the first structural material in the transparent ceramic composite material is 5%-15%.

[0016] According to a specific embodiment of the present invention, the second structural material can form an organic-inorganic hybrid network, enhancing interfacial adhesion and improving the flexibility of the coating. Preferably, the second structural material has the general formula R. 2 b SiX 2 c P 4-b-c , where R 2 It is an inactive group (i.e., does not undergo hydrolysis), selected from C1-C7 alkyl, C6-C10 aryl, C2-C7 alkenyl, C2-C7 ether, and C1-C7 fluoroalkyl, b=0, 1, or 2, c=1, 2, or 3, and b+c<4; X 2 -OC m H 2m+1 m = 1, 2, 3, or 4; P represents other active groups selected from methacryloyloxy, acetoxy, oxime, amino, and epoxy groups. More preferably, the second structural material is selected from one or more combinations of γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyletheroxypropylmethyldiethoxysilane, γ-glycidyletheroxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidyletheroxypropyltrimethoxysilane, methylallyloxytrimethoxysilane, methyltrimethoxysilane oxime, and γ-oximepropyltriethoxysilane. The second structural material is preferably selected from silanes having two or more active groups.

[0017] According to a specific embodiment of the present invention, preferably, the content of the second structural material in the transparent ceramic composite material is 15%-30%.

[0018] According to a specific embodiment of the present invention, preferably, in the transparent ceramic composite material, the sum of the contents of the first structural material and the second structural material is 20%-40%.

[0019] According to a specific embodiment of the present invention, preferably, the content of the second structural material is higher than that of the first structural material. Additives such as UV absorbers and light stabilizers are incorporated into the network structure formed by the structural materials. By using a higher content of the second structural material, the flexibility of the network structure formed in the coating can be improved. If the content of the first structural material is higher than that of the second structural material, the network structure may become excessively rigid, leading to problems such as coating cracking in corrosive environments after the introduction of additives such as UV absorbers and light stabilizers. By controlling the content of the second structural material to be higher than that of the first structural material, these problems can be effectively avoided.

[0020] According to a specific embodiment of the present invention, the ultraviolet absorber, as the main functional material for ultraviolet absorption, can absorb the energy of ultraviolet rays and convert it into harmless heat or low-energy radiation for release; preferably, the ultraviolet absorber is selected from benzotriazole ultraviolet absorbers, more preferably from 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol ...(2H-benzotriazole-2-yl)-(2H- One or more combinations of triazol-2-yl)-4,6-di-tert-pentylphenol, etc.; more preferably, acid-resistant benzotriazoles, such as: 3-[3-(2-H-benzotriazol-2-yl)-4-hydroxy-5-tert-butylphenyl]-propionic acid-polyethylene glycol 300, 2,2'-methylene-bis[4-tert-octyl-6-(2H-benzotriazolyl-2)]phenol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, etc., one or more combinations of benzotriazoles, etc.

[0021] According to a specific embodiment of the present invention, preferably, the content of the ultraviolet absorber in the transparent ceramic composite material is 0.1%-5%; more preferably, it is 0.5%-3%.

[0022] According to a specific embodiment of the present invention, the light stabilizer, as a supplement to the ultraviolet absorber, inhibits the photo-oxidation reaction chain process by capturing free radicals (such as peroxide free radicals) or decomposing hydrogen peroxide, thereby reducing the risk of high-temperature yellowing of the coating; preferably, the light stabilizer is selected from hindered amine light stabilizers, more preferably from bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate. The light stabilizer is one or more of the following: esters, polymers of 1,3,5-triazine-2,4,6-triamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, polymers of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol; more preferably, a non-basic hindered amine light stabilizer, such as one or more of the following: 2,2,6,6-tetramethyl-4-piperidinyl stearate, copolymers of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methacrylate.

[0023] According to a specific embodiment of the present invention, preferably, the content of the ultraviolet absorber in the transparent ceramic composite material is 0.1%-3%, more preferably 0.3%-2%.

[0024] According to a specific embodiment of the present invention, preferably, the mass ratio of the ultraviolet absorber to the light stabilizer in the transparent ceramic composite material is 1:1 to 2:1. The ultraviolet absorber directly absorbs ultraviolet light, but long-term use can lead to saturation; the light stabilizer repairs light damage and is recyclable. By controlling the mass ratio of the ultraviolet absorber to the light stabilizer within the range of 1:1 to 2:1, the synergistic effect of the ultraviolet absorber and the light stabilizer can be balanced, taking into account both protective efficiency and durability. Controlling it within this range also avoids overloading a single protective mechanism. If there is too much light stabilizer, it will cause a decrease in film transparency, an increase in haze, affecting the appearance, and the cost of the light stabilizer is relatively high.

[0025] According to a specific embodiment of the present invention, the catalyst is used to regulate the hydrolysis rate of active groups, thereby forming a coating with a uniform structure. The catalyst is preferably an acidic solution with a pH of 1.5-3; the acid used can be an inorganic acid, such as hydrochloric acid or nitric acid, or an organic acid, such as formic acid, acetic acid, citric acid, or oxalic acid. The catalyst can be obtained by diluting the acid with deionized water.

[0026] According to a specific embodiment of the present invention, preferably, the content of the catalyst in the transparent ceramic composite material is 20%-40%.

[0027] According to a specific embodiment of the present invention, the solvent can form a homogeneous reaction system with silicates and silanes, and its evaporation rate is crucial to the film quality. Preferably, the solvent is selected from alcohols and ethers with boiling points of 75-140°C, such as two or a combination of two or three of ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, tert-butanol, allyl alcohol, propylene glycol methyl ether, and propylene glycol ethyl ether.

[0028] According to a specific embodiment of the present invention, preferably, the solvent content in the transparent ceramic composite material is 15%-45%.

[0029] According to a specific embodiment of the present invention, silica sol can improve the mechanical properties of the coating, such as hardness and wear resistance. Preferably, the particle size (particle size of silica in the silica sol) is 5-50 nm. More preferably, the pH of the silica sol is 2.0-5.0, and the solid content is 10-40%. The silica sol used in the present invention can be, for example, Snowtex O-40, Snowtex O-20, Ludox TM-40, JNT-AS30, JH-202, etc.

[0030] According to a specific embodiment of the present invention, preferably, the content of the silica sol in the transparent ceramic composite material is 5%-15%.

[0031] According to a specific embodiment of the present invention, the resin is a dilution resin, capable of pretreating the ultraviolet absorber and light stabilizer, diluting the ultraviolet absorber and light stabilizer in the corresponding resin before adding them to the system. This enhances the compatibility with the network structure formed by the first and second structural materials, avoiding aggregation and sedimentation in the system when the ultraviolet absorber and light stabilizer are used directly. Preferably, the resin is a resin capable of reacting with the active group P in the second structural material. For example:

[0032] For methacryloyloxy, such as γ-methacryloyloxypropyltrimethoxysilane, the resin for dilution can be an unsaturated polyester resin, such as 3301 type bisphenol A type unsaturated polyester resin.

[0033] For acetoxy groups, such as methyltriacetoxysilane, the diluent resin can be hydroxyl acrylic resin (W4315), etc.

[0034] For oxime groups, such as methyltris(butanone oxime)silane, the diluent resin can be 3450-2 hydroxyl acrylic resin, etc.

[0035] For amino compounds, such as γ-aminopropyltriethoxysilane, epoxy resins (E44) can be selected for dilution.

[0036] For epoxy groups, such as γ-glycidoxypropyltrimethoxysilane, epoxy resins (E44) can be selected for dilution.

[0037] According to a specific embodiment of the present invention, preferably, the dilution ratio of the resin used to dilute the ultraviolet absorber and the light stabilizer is 5%-10%.

[0038] According to a specific embodiment of the present invention, preferably, the curing temperature is 60-150℃.

[0039] According to a specific embodiment of the present invention, preferably, the transparent ceramic composite material is prepared by the following steps:

[0040] Add the first structural material and the second structural material to the solvent in sequence, and stir for 10-30 minutes to form a mixture A;

[0041] Premix the catalyst with silica sol and stir for 10-30 minutes to form mixture B;

[0042] The ultraviolet absorber and the light stabilizer were diluted separately using a diluent resin to obtain diluent A (ultraviolet absorber diluent) and diluent B (light stabilizer diluent), with mass concentrations of 5%-10% for diluent A and diluent B, respectively.

[0043] Add mixture B to mixture A, stir for 6-10 hours, and let stand and mature for 24-96 hours to form mixture C;

[0044] Add diluent A and diluent B to mixture C, stir for 10-30 minutes to obtain a transparent ceramic composite material, i.e., a transparent protective coating.

[0045] According to a specific embodiment of the present invention, the ultraviolet absorbers and light stabilizers added to the transparent ceramic composite material will affect the hydrolysis-condensation reaction of the transparent ceramic composite material. If ultraviolet absorbers and light stabilizers are added during the hydrolysis-condensation reaction, the sol particles generated by hydrolysis will become coarser, precipitate, and destroy the original network structure of the transparent ceramic composite material. The present invention avoids the above problems by adding ultraviolet absorbers and light stabilizers that have undergone resin pretreatment after the hydrolysis-condensation reaction is completed.

[0046] The present invention also provides an anti-ultraviolet and impact-resistant coating, wherein the anti-ultraviolet and impact-resistant coating comprises an electroluminescent layer, a color paint layer, and a transparent protective layer;

[0047] The transparent protective layer is the transparent protective layer provided by the present invention.

[0048] According to a specific embodiment of the present invention, preferably, the hardness of the UV-resistant and impact-resistant coating is greater than or equal to 1H.

[0049] The host material in the electroluminescent layer, such as some luminescent materials, is temperature-sensitive. During fabrication, excessively high temperatures can cause bandgap shrinkage, leading to a redshift in the emission wavelength and affecting color coordinate stability. When the temperature exceeds its tolerance limit (typically around 150°C), thermal degradation can cause lattice damage, resulting in permanent light decay. Furthermore, ultraviolet aging can also lead to lattice breakage and molecular chain degradation, resulting in loss of luminescence.

[0050] In addition, most luminescent materials use epoxy resin or other polymer binders as carriers, which will turn yellow when the temperature is high (some have a temperature limit of 125°C), resulting in a significant decrease in light transmittance.

[0051] The transparent protective layer in the UV-resistant and impact-resistant coating provided by this invention is a low-temperature curing transparent ceramic layer. It can be cured at low temperatures, which can avoid structural damage or aging damage to the luminescent material in the electroluminescent layer caused by high-temperature curing. Moreover, the transparent protective layer can provide good adhesion and mechanical properties. At the same time, the transparent protective layer contains UV absorbers and light stabilizers, which can provide good UV absorption performance, further improving the light aging resistance of the paint layer and the electroluminescent layer, thereby avoiding yellowing of the luminescent material and avoiding a decrease in light transmittance.

[0052] According to a specific embodiment of the present invention, preferably, the transmittance of the UV-resistant and impact-resistant coating to ultraviolet rays with wavelengths in the range of 300nm-370nm is less than or equal to 2%, more preferably 0.8-1.5%.

[0053] According to a specific embodiment of the present invention, preferably, the transmittance of the UV-resistant and impact-resistant coating to visible light with wavelengths in the range of 380nm-780nm is greater than or equal to 90%.

[0054] According to a specific embodiment of the present invention, preferably, the thickness of the transparent protective layer is 1-10 μm, more preferably 5-8 μm.

[0055] According to a specific embodiment of the present invention, preferably, the color difference of the UV-resistant and impact-resistant coating before and after thermal aging is less than or equal to 1.5; the thermal aging is to place the UV-resistant and impact-resistant coating in an environment of 90±2℃ for 500h.

[0056] According to a specific embodiment of the present invention, preferably, the hardness of the UV-resistant and impact-resistant coating is greater than or equal to 2H, which is the hardness of a pencil. Generally, the hardness of the transparent protective layer is equal to the hardness of the paint layer + 1~2H.

[0057] According to a specific embodiment of the present invention, preferably, the adhesion of the UV-resistant and impact-resistant coating is grade 0 or grade 1.

[0058] According to a specific embodiment of the present invention, in the UV-resistant and impact-resistant coating of the present invention, the transparent protective layer is located on the outermost side, and the positions of the electroluminescent layer and the paint layer can be arbitrary. That is, the UV-resistant and impact-resistant coating may include an electroluminescent layer, a paint layer, and a transparent protective layer arranged in sequence, or it may include a paint layer, an electroluminescent layer, and a transparent protective layer arranged in sequence.

[0059] According to a specific embodiment of the present invention, when the electroluminescent layer cannot be completely transparent, the electroluminescent layer, the colored paint layer, and the transparent protective layer are sequentially disposed in the UV-resistant and impact-resistant coating. This ensures that the coating, in a non-luminescent state, only presents the color of the colored paint layer, thereby achieving a good decorative effect.

[0060] According to a specific embodiment of the present invention, the electroluminescent layer can also be called an electroluminescent multilayer composite paint layer, which is used to provide an electroluminescent effect. When energized, it can realize the desired luminescent pattern according to the settings.

[0061] Preferably, the electroluminescent layer comprises a backplate layer, a dielectric layer, a light-emitting layer, a sub-wire, and a conductive layer arranged sequentially.

[0062] According to a specific embodiment of the present invention, preferably, the thickness of the backsheet layer in the electroluminescent layer is 20-60 μm.

[0063] According to a specific embodiment of the present invention, preferably, the material of the backing layer is selected from one or more combinations of silver, copper, carbon, PEDOT:PSS, gold, etc., wherein silver can be in the form of silver paste, silver nanowires, etc., copper can be copper paste, carbon can be carbon adhesive or carbon nanotube film, gold can be gold plating, and the backing layer can also be a composite electrode of silver paste and copper mesh.

[0064] According to a specific embodiment of the present invention, preferably, the thickness of the dielectric layer in the electroluminescent layer is 30-100 μm.

[0065] According to a specific embodiment of the present invention, preferably, the dielectric layer is a composite dielectric material formed by filling a polymer matrix with inorganic nanoparticles, nanowires, nanosheets, etc., which have excellent dielectric properties. The polymer matrix is ​​preferably selected from one or more combinations of epoxy resin, acrylic resin, water-based resin, etc. The inorganic nanoparticles are preferably selected from one or more combinations of nanoparticles made of titanium dioxide (TiO2), lead zirconate titanate (PZT), barium titanate (BaTiO3), calcium copper titanate (CCTO), potassium sodium niobate (KNN), etc.; the nanowires are preferably selected from BaTiO3, PbTiO3, CCTO, TiO2, PZT, alumina (Al2O3), silicon carbide (SiC), lithium lanthanum zirconium oxide (LLZO), Na3Zr2Si2PO4, etc. 12 The nanosheets are made of one or more of the following materials: (NASICON) nanowires; the nanosheets are preferably two-dimensional ceramic nanosheets, such as those selected from BaTiO3, boron nitride (BN), LaNb2O7, (Ca,Sr)2Nb3O 10 One or more combinations of nanosheets made of materials such as MoS2 and NbSe2.

[0066] According to a specific embodiment of the present invention, preferably, the thickness of the electroluminescent layer is 20-60 μm.

[0067] According to a specific embodiment of the present invention, preferably, the material of the light-emitting layer comprises a polymer matrix and an electroluminescent host material, wherein the electroluminescent host material is dispersed within the polymer matrix. To improve the compatibility of the light-emitting layer with the upper and lower layers, appropriate modifying agents may be added as needed. The polymer matrix is ​​preferably one or a combination of two or more selected from epoxy resin, acrylic resin, water-based resin, silicone, etc. The polymer matrix provides good compatibility with the upper and lower connecting layers and provides encapsulation of the light-emitting host material. The light-emitting host material is preferably selected from one or a combination of two or more selected from inorganic phosphors, perovskite system materials, etc.

[0068] According to a specific embodiment of the present invention, preferably, the thickness of the conductive layer in the electroluminescent layer is 10-100 μm.

[0069] According to a specific embodiment of the present invention, preferably, the material of the conductive layer is selected from one or more combinations of indium tin oxide (ITO), silver nanowires (AgNW), PEDOT:PSS, graphene, etc.

[0070] According to a specific embodiment of the present invention, preferably, the electroluminescent layer further includes a sub-wire and a bus (i.e., a backplane layer), wherein the bus and the sub-wire are used to connect to the positive and negative terminals of the power supply, so that the current can pass through the entire light-emitting surface, providing a good conduction path for the current and ensuring that the current can be evenly distributed in the area where light is needed. Specifically, the bus is connected to the dielectric layer, and the sub-wire is connected to the light-emitting layer and the conductive layer.

[0071] According to a specific embodiment of the present invention, the color paint layer is used to cover the color of the electroluminescent layer and to achieve consistency with the appearance color of other non-electroluminescent aluminum trim strips of the automobile in the non-electrically powered state. Preferably, the paint used in the color paint layer is one or more combinations of polyurethane system, acrylic system and modified paint with a curing temperature of 40-100℃, such as BASF Glasurit 90-9410, Axalta Imron 7000, Kansai Paint Kansai 8000, Nippon Paint 9000, PPG D8080 (metallic color), DuPont Spies Hecker 9000, Xiangjiang Paint XJ-800, etc.

[0072] According to a specific embodiment of the present invention, preferably, the hardness range of the paint layer is HB-H.

[0073] This invention also provides a method for preparing an anti-UV and impact-resistant coating, which includes the following steps:

[0074] A colored paint layer is formed on the surface of the electroluminescent layer;

[0075] The raw material for the transparent protective layer (i.e., low-temperature transparent ceramic composite material) is coated onto the surface of the paint layer or the electroluminescent layer (the side without the paint layer), and then cured at 60-150℃ to form the transparent protective layer, thus obtaining the UV-resistant and impact-resistant coating.

[0076] According to a specific embodiment of the present invention, preferably, the low-temperature curing time is 10-40 minutes.

[0077] According to a specific embodiment of the present invention, preferably, the thickness of the formed transparent protective layer is 1-10 μm.

[0078] According to a specific embodiment of the present invention, preferably, the ultraviolet blocking rate of the formed transparent protective layer is 90%-99.99%.

[0079] The present invention also provides an exterior metal part, which includes a substrate and a protective layer, wherein the protective layer is a transparent protective layer or an anti-ultraviolet and impact-resistant coating provided by the present invention.

[0080] When a transparent protective layer is applied separately, it can provide protection for the exterior metal parts. When a low-temperature curing, UV-resistant, and impact-resistant coating is applied, the transparent protective layer can reduce the damage of ultraviolet rays to the paint layer, electroluminescent layer, etc., and improve the overall performance of the electroluminescent exterior metal parts in terms of light aging resistance, mechanical resistance, and environmental corrosion resistance.

[0081] According to a specific embodiment of the present invention, the substrate serves as a carrier for the electroluminescent layer, the paint layer, and the transparent protective layer; preferably, the substrate is selected from aluminum and / or anodized aluminum.

[0082] When the exterior metal parts provided by this invention are not powered on, they look no different from ordinary exterior parts; when powered on, they can display bright patterns, such as car logos and fashion icons, in the design pattern area, thereby enhancing the overall fashion of the car.

[0083] The present invention also provides a vehicle having the exterior metal parts provided by the present invention.

[0084] According to a specific embodiment of the present invention, preferably, the exterior metal parts are located in the corner windows, trim strips, etc. of the vehicle.

[0085] The technical solution provided by this invention can increase the lifespan of the electroluminescent layer, and improve the overall photoaging performance and mechanical properties without changing the color of the paint layer, thereby accelerating the application of electroluminescent effects in automotive metal exterior parts. Attached Figure Description

[0086] Figure 1 The transmittance curves are for Examples 1-4 and Comparative Example 1.

[0087] Figure 2 The image shows the luminescence of an electroluminescent aluminum exterior part with a coating formed by the paint of Example 1.

[0088] Figure 3 The image shows the luminescence of an electroluminescent aluminum exterior part with a coating formed by the paint of Comparative Example 1.

[0089] Figure 4 The image shows the adhesion test results of the test specimen corresponding to Example 2.

[0090] Figure 5 The image shows the adhesion test results for the corresponding test specimen in Comparative Example 2.

[0091] Figure 6 The figure shows the adhesion test results for the corresponding test specimen of Comparative Example 6.

[0092] Figure 7 The corrosion resistance test results are for the test sample corresponding to Example 3.

[0093] Figure 8 The corrosion resistance test results are for the test sample corresponding to Comparative Example 3.

[0094] Figure 9 The image shows the surface microstructure of the test sample corresponding to Example 3 after a corrosion resistance test.

[0095] Figure 10 This is a microscopic image of the failure area of ​​the test sample corresponding to Comparative Example 3.

[0096] Figure 11 The results of the car wash resistance test are for the test samples corresponding to Examples 1-4 and Comparative Example 4.

[0097] Figure 12 This is a schematic diagram of the exterior metal part with an electroluminescent coating in Example 5.

[0098] Figure 13 This is a schematic diagram of the structure of the electroluminescent multilayer composite paint layer in Example 5.

[0099] Figure 14 This is a schematic diagram of the bus and sub-bus arrangement of the electroluminescent multilayer composite coating layer in Example 5. Detailed Implementation

[0100] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0101] Examples 1-4 and Comparative Examples 1-6 each provide a transparent ceramic composite material (or transparent ceramic paint), the composition and content of which are shown in Tables 1-3:

[0102] Table 1

[0103]

[0104] Table 2

[0105]

[0106] Table 3

[0107]

[0108] The transparent ceramic composite materials of Examples 1-4 were prepared by the following steps:

[0109] Add the first structural material and the second structural material sequentially to the mixed solvent, and stir for 15±5 minutes to form a mixture A;

[0110] The catalyst was premixed with silica sol and stirred for 30±10 minutes to form mixture B.

[0111] The ultraviolet absorber and light stabilizer were diluted separately using a diluent resin to obtain diluent A and diluent B.

[0112] Add mixture B to mixture A, stir for 12±4 hours, and let stand for 72±24 hours to form mixture C;

[0113] Add diluent A and diluent B to mixture C, stir for 30±10 minutes to obtain low-temperature transparent ceramic composite material.

[0114] The composite materials of Comparative Examples 1-5 can be prepared by referring to the above method.

[0115] The transparent ceramic composite materials of Examples 1-4 can be used to manufacture exterior metal parts according to the following steps:

[0116] An electroluminescent layer is formed on the surface of the aluminum substrate of the exterior metal parts;

[0117] A colored paint layer is formed on the surface of the electroluminescent layer;

[0118] The raw material for the transparent protective layer is sprayed onto the surface of the colored paint layer and cured at 90±10℃ for 50±10 minutes to form a transparent protective layer, thus forming a low-temperature curing, UV-resistant, and impact-resistant coating, resulting in an exterior metal part.

[0119] The composite materials of Comparative Examples 1-6 can be used to prepare exterior metal parts by referring to the above method. Among them, Comparative Example 6 is the same in terms of raw materials, content and production parameters, except that the curing temperature is 180±10℃ and the curing time is 50±10 minutes.

[0120] I. Optical Performance Testing

[0121] Equipment: Spectrophotometer (Model: LAMBDA1050, Manufacturer: PerkinElmer), Film thickness gauge (Model: MCPD-9800(916C, Manufacturer: Otsuka Electric Co., Ltd.)

[0122] Because the aluminum parts are opaque, the coating was attached to a transparent carrier for testing optical performance. In this optical test, the coatings from the examples and comparative examples were sprayed onto clean, 2.1mm thick white glass.

[0123] Spraying process: Control conditions: Spraying overlap rate (the overlapping area of ​​the first sprayed row when the second row is sprayed is 60±5%); Spraying thickness is shown in Table 1.

[0124] Film thickness: The thickness of the film layer after heating and curing, which is measured by a film thickness gauge.

[0125] Ultraviolet transmittance: The overall transmittance is obtained by integrating the transmittance of the sample in the 300-380nm wavelength range using a spectrophotometer.

[0126] The test results are shown in Table 4.

[0127] Table 4

[0128]

[0129] As can be seen from the experimental data in Table 4, the UV transmittance of the coatings formed by the transparent ceramic paints in Examples 1-4 is less than 1%, while the UV transmittance of the coatings made by the paints in Comparative Example 1 (without adding diluents A and B) is as high as 76%, and the transmittance curves ( Figure 1 It can be clearly seen that the coatings made from the paints in Examples 1-4 have a transmittance of less than 2% for ultraviolet light with wavelengths of 300nm-370nm, and a transmittance of more than 90% for visible light (380-780nm), and will not cause light path and color interference to the paint layer and the light-emitting layer.

[0130] II. Photoaging Test

[0131] Equipment: Xenon lamp test chamber, manufacturer: Atlas Material Testing Technology LLC, model: Ci3000+.

[0132] The test was conducted on an aluminum component with an electroluminescent multilayer composite paint layer and a color paint layer as a carrier. The paints of Example 1 and Comparative Example 1 were sprayed onto the surface of the carrier for comparative testing. The spraying method was the same as that used in the optical performance test, and the spraying thickness was 2-5 micrometers.

[0133] Among them, the structure of the electroluminescent multilayer composite paint layer is as follows: Figure 13 and Figure 14 As shown, it includes a busbar (i.e., backplane layer), sub-wires, a dielectric layer, a light-emitting layer, and a conductive layer, wherein:

[0134] The busbar is located in the middle part of the substrate surface and is connected to the dielectric layer;

[0135] Sub-wires are positioned around the light-emitting layer and connected to the light-emitting layer and the conductive layer;

[0136] The dielectric layer is located above the busbar and covers the surrounding area of ​​the busbar;

[0137] The light-emitting layer is positioned above the dielectric layer;

[0138] The conductive layer is located above the light-emitting layer;

[0139] The busbar and the daughter line are made of silver paste PEDOT:pss, with a thickness of 30±5 micrometers, respectively.

[0140] The dielectric layer is a composite dielectric material formed by nano-barium carbonate and epoxy resin in a weight ratio of 2:100, with a thickness of 40±5 micrometers.

[0141] The material of the light-emitting layer is a composite light-emitting coating formed by zinc sulfide inorganic phosphor and epoxy resin in a weight ratio of 18:100; the thickness is 30±5 micrometers.

[0142] The conductive layer is a composite conductive material formed by indium tin oxide (ITO) and epoxy resin in a weight ratio of 15:100, with a thickness of 20±5 micrometers.

[0143] The paint layer is made of BASF Parrot 90-9410 and has a thickness of 40-50 micrometers.

[0144] Test method: Electroluminescent aluminum exterior parts with coatings formed from the paints of Example 1 and Comparative Example 1 were subjected to a xenon lamp aging test. Test standard: SAE J2527, irradiance 0.55 W / (m²). 2 ×nm)@340nm, with a testing cycle of 2000h.

[0145] The results showed that the electroluminescent aluminum exterior parts with the coating formed by the paint of Example 1 ( Figure 2 The luminescent layer has a uniform color and consistent brightness;

[0146] The luminescent layer of the electroluminescent aluminum exterior component having a coating formed by the paint of Comparative Example 1 ( Figure 3 Dark spots appeared. Figure 3 (marked by the middle circle), and the color uniformity at the edges is poor, with dark patches appearing in certain areas.

[0147] III. Thermal Aging Test

[0148] equipment:

[0149] Oven: Model: WGL-230D;

[0150] Colorimeter: Model: BYK 6807, Manufacturer: BYK (BYK Chemicals);

[0151] Paint film adhesion crisscross board: Model: BGD 503, Manufacturer: Biaogeda Precision Instruments (Guangzhou) Co., Ltd.

[0152] The test was conducted on an aluminum component with an electroluminescent multilayer composite paint and a colored paint layer as a substrate. The paint from Example 2 was sprayed onto the substrate surface to form a transparent protective layer, creating a test piece for comparison with Comparative Example 2. The specific spraying method was the same as in the optical performance test, with a spray thickness of 2-5 micrometers. The difference between Example 2 and Comparative Example 2 is that the diluent B in Example 2 contains a light stabilizer, while Comparative Example 2 uses only pure E-44 bisphenol A epoxy resin. The difference between Example 2 and Comparative Example 6 is that the curing temperature of Example 2 is 90±10℃, while the curing temperature of Comparative Example 6 is 180±10℃.

[0153] Test method: Place the test specimen in an environment of 90±2℃ for 500h. The color difference ΔE of the test specimen before and after heat aging is measured, and ΔE ≤ 1.5 is required. Color difference reference method: SAE J1545.

[0154] Adhesion after thermal aging: The test method is in accordance with GB / T 9286.

[0155] The test results are shown in Table 5.

[0156] Table 5

[0157]

[0158] Standard parts refer to samples without a transparent protective layer.

[0159] Figure 4 This is a graph showing the adhesion test results of the test specimen corresponding to Example 2. Figure 5 The image shows the adhesion test results for the corresponding test specimen in Comparative Example 2. Figure 6 The image shows the adhesion test results for the corresponding test specimen of Comparative Example 6.

[0160] By comparison Figure 4 , Figure 5 , Figure 6 It can be seen that the test specimens corresponding to Example 2 have good adhesion, while the adhesion of Comparative Example 6 is significantly reduced. Specifically, the curing temperature of Comparative Example 6 is too high, which weakens or even deactivates the light stabilizer. Furthermore, the higher temperature increases the risk of discoloration in the internal paint layer, thus leading to reduced adhesion.

[0161] IV. Corrosion Resistance Test

[0162] Equipment used: Salt spray test chamber, model: SF08, manufacturer: GWS Guangzhou Wusuo Environmental Instrument Co., Ltd.;

[0163] Zeiss metallurgical microscope: Model: Zeiss Lab A1, Manufacturer: Zeiss, Germany.

[0164] Neutral salt spray test method: The test shall be conducted in accordance with the method specified in GB / T 10125.

[0165] Test specimen: The test was conducted on an aluminum part with an electroluminescent multilayer composite paint and a color paint layer as a carrier. The paint of Example 3 was sprayed on the surface of the carrier to form a transparent protective layer to form a test specimen, which was compared with Comparative Example 3. The specific spraying method was the same as that for the optical performance test, and the spraying thickness was 2-5 micrometers.

[0166] Compared with Example 3, the content of the first structural material in Comparative Example 3 was at the maximum allowable value, while the content of the second structural material was 11%, which was lower than the allowable value of 12%. The overall coating structure was too rigid and cracked.

[0167] Figure 7 The results are from the test sample corresponding to Example 3 after 1000 hours of neutral salt spray environment. Figure 7 It can be seen that the surface of the test sample remains smooth and free of corrosion.

[0168] Figure 8 The results are from the test of the sample corresponding to Comparative Example 3 after 480 hours in a neutral salt spray environment. Figure 8 It can be seen that the surface of the test sample exhibits a fish-scale-like corrosion phenomenon.

[0169] Figure 9 The image shows the surface microstructure of the test sample corresponding to Example 3 after 1000 hours of neutral salt spray testing. Figure 9 It can be seen that the surface of the test sample has no cracks.

[0170] Figure 10 This is a microscopic image of the neutral salt spray failure region of the test sample corresponding to Comparative Example 3. Figure 10 It can be seen that the surface film layer in the fish-scale corrosion area has developed large-scale cracks.

[0171] Based on the above experimental results, it can be seen that the corrosion resistance time of the test sample corresponding to Example 3 can reach more than 1,000 hours, which is far higher than the 480 hours usually required by the automotive industry.

[0172] V. Mechanical Property Testing

[0173] equipment:

[0174] Simulated car wash machine: Manufacturer: AMTEC, Model: 220-240VAC / 50HZ / PE;

[0175] Pencil hardness tester: Model: QHQ-A, Manufacturer: Dongguan Huaguo Precision Instruments Co., Ltd.;

[0176] Gloss meter: Model: BYK4586, Manufacturer: BYK (BYK Chemicals), measures the gloss of the test sample at a 60° angle.

[0177] The test used an aluminum component with an electroluminescent multilayer composite paint layer and a colored paint layer as a carrier. The coating from Example 4 was sprayed onto the carrier surface to form a transparent protective layer, creating a test piece for comparison with Comparative Example 4. The specific spraying method was the same as in the optical performance test, with a coating thickness of 2-5 micrometers. The difference between Comparative Example 4 and Example 4 lies in the content of the first structural material. The content of the first structural material in Comparative Example 4 was 2.5%, lower than the required 3%, which prevented improvement in the product's hardness test and resulted in noticeable scratches during the car wash experiment. The difference between Comparative Example 5 and Example 4 lies in the content of silica sol. Comparative Example 5 did not contain silica sol, preventing improvement in the product's hardness test and also resulting in noticeable scratches during the car wash experiment.

[0178] Test item 1: Car wash resistance test, test standard reference: ISO 20566-2020.

[0179] The gloss resistance of the sample in the car wash test is evaluated by comparing the ratio of the gloss of the sample after the car wash test to the gloss of the sample before the car wash test. The gloss test method refers to GB / T 9754-2007.

[0180] Test Item 2: Pencil Hardness. Reference Standard: GB / T 6739-2022.

[0181] The test results are shown in Table 6.

[0182] Table 6

[0183]

[0184] Figure 11 The results of the car wash resistance test are for the test samples corresponding to Examples 3 and 4 and Comparative Examples 4 and 5.

[0185] Depend on Figure 11 It can be seen that there are tiny scratches in the test samples corresponding to Comparative Examples 4 and 5, which is not allowed in the car wash resistance test. This indicates that when the content of the first structural material is lower than the allowable content, the coating formed cannot meet the required mechanical properties.

[0186] Example 5

[0187] This embodiment provides an exterior metal component with the following structure: Figure 12 As shown.

[0188] The exterior metal component includes a substrate, an electroluminescent multilayer composite paint layer, a colored paint layer, and a transparent protective layer arranged sequentially.

[0189] The transparent protective layer can be formed by low-temperature curing of the transparent ceramic composite material provided in Examples 1-4;

[0190] like Figure 13 and Figure 14 As shown, the electroluminescent multilayer composite coating includes a busbar (i.e., backplane layer), a sub-wire, a dielectric layer, a light-emitting layer, and a conductive layer, wherein:

[0191] The busbar is located in the middle part of the substrate surface and is connected to the dielectric layer;

[0192] Sub-wires are positioned around the light-emitting layer and connected to the light-emitting layer and the conductive layer;

[0193] The dielectric layer is located above the busbar and covers the surrounding area of ​​the busbar;

[0194] The light-emitting layer is positioned above the dielectric layer;

[0195] The conductive layer is located above the light-emitting layer;

[0196] in:

[0197] The busbar and the daughter line are made of silver paste PEDOT:pss, with a thickness of 30±5 micrometers, respectively.

[0198] The dielectric layer is a composite dielectric material formed by nano-barium carbonate and epoxy resin in a weight ratio of 2:100, with a thickness of 40±5 micrometers.

[0199] The material of the light-emitting layer is a composite light-emitting coating formed by zinc sulfide inorganic phosphor and epoxy resin in a weight ratio of 18:100; the thickness is 30±5 micrometers.

[0200] The conductive layer is a composite conductive material formed by indium tin oxide (ITO) and epoxy resin, with a thickness of 20±5 micrometers;

[0201] The paint layer is made of BASF Parrot 90-9410 and has a thickness of 40-50 micrometers.

Claims

1. A transparent protective layer, wherein, The transparent protective layer is formed by curing a transparent ceramic composite material. By weight percentage, the transparent ceramic composite material comprises 15%-50% structural material, 0.01%-8% ultraviolet absorber, and 0.01%-5% light stabilizer; The structural materials comprise 3%-20% of the first structural material and 12%-40% of the second structural material; The general formula for the first structural material is R 1 a SiX 1 4-a Among them, R 1 Selected from C1-C7 alkyl, C6-C10 aryl, C2-C7 alkenyl, C2-C7 ether, and C1-C7 fluoroalkyl, a = 0, 1, 2, or 3; X 1 -OC n H 2n+1 n = 1, 2, 3 or 4; The general formula for the second structural material is R 2 b SiX 2 c P 4-b-c , where R 2 Selected from C1-C7 alkyl, C6-C10 aryl, C2-C7 alkenyl, C2-C7 ether, and C1-C7 fluoroalkyl, b = 0, 1, or 2, c = 1, 2, or 3, and b + c < 4; X 2 -OC m H 2m+1 m = 1, 2, 3 or 4; P is selected from methacryloyloxy, acetoxy, oxime, amino, and epoxy groups.

2. The transparent protective layer according to claim 1, wherein, By weight percentage, the transparent ceramic composite material also contains 10%-50% catalyst, 10%-50% solvent, 2%-20% silica sol, and 2%-10% resin.

3. The transparent protective layer according to claim 1, wherein, The content of the second architecture material is higher than that of the first architecture material.

4. The transparent protective layer according to claim 1, wherein, The first structural material is selected from one or more combinations of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltriethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, and trimethoxy(2-methoxyethoxy)silane.

5. The transparent protective layer according to claim 1, wherein, The second structural material is selected from one or more combinations of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyl etheroxypropylmethyldiethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, methylallyloxytrimethoxysilane, methyltrimethoxysilane oxime, and γ-oxime propyltriethoxysilane.

6. The transparent protective layer according to claim 1, wherein, The ultraviolet absorber is selected from benzotriazole ultraviolet absorbers.

7. The transparent protective layer according to claim 1, wherein, The light stabilizer is selected from hindered amine light stabilizers.

8. The transparent protective layer according to claim 1, wherein, The mass ratio of the ultraviolet absorber to the light stabilizer is 1:1 to 2:

1.

9. The transparent protective layer according to claim 2, wherein, The particle size of the silica sol is 5-50 nm.

10. The transparent protective layer according to claim 1, wherein, The curing temperature is 60-150℃.

11. A UV-resistant and impact-resistant coating, wherein, The UV-resistant and shock-resistant coating includes an electroluminescent layer, a colored paint layer, and a transparent protective layer; The transparent protective layer is the transparent protective layer described in any one of claims 1-10.

12. The UV-resistant and impact-resistant coating according to claim 11, wherein, The hardness of the UV-resistant and impact-resistant coating is greater than or equal to 1H.

13. The UV-resistant and impact-resistant coating according to claim 11, wherein, The UV-resistant and impact-resistant coating has a transmittance of less than or equal to 2% for ultraviolet rays with wavelengths between 300nm and 370nm.

14. The UV-resistant and impact-resistant coating according to claim 12, wherein, The UV-resistant and impact-resistant coating has a transmittance of 0.8-1.5% for ultraviolet rays with wavelengths between 300nm and 370nm.

15. The UV-resistant and impact-resistant coating according to claim 11, wherein, The UV-resistant and impact-resistant coating has a transmittance of 90% or more for visible light with wavelengths in the range of 380nm-780nm.

16. The UV-resistant and impact-resistant coating according to claim 11, wherein, The thickness of the transparent protective layer is 1-10 μm.

17. The UV-resistant and impact-resistant coating according to claim 16, wherein, The thickness of the transparent protective layer is 5-8 μm.

18. The UV-resistant and impact-resistant coating according to claim 11, wherein, The color difference of the UV-resistant and impact-resistant coating before and after thermal aging is less than or equal to 1.

5. The thermal aging process involves placing the UV-resistant and impact-resistant coating in an environment at 90±2℃ for 500 hours.

19. The UV-resistant and impact-resistant coating according to claim 11, wherein, The adhesion of the UV-resistant and impact-resistant coating is grade 0 or grade 1.

20. The UV-resistant and impact-resistant coating according to claim 11, wherein, The electroluminescent layer comprises a backplate layer, a dielectric layer, a light-emitting layer, and a conductive layer arranged sequentially.

21. The UV-resistant and impact-resistant coating according to claim 20, wherein, The thickness of the backsheet layer is 20-60 μm; The thickness of the dielectric layer is 30-100 μm; The thickness of the light-emitting layer is 20-60 μm; The thickness of the conductive layer is 10-100 μm.

22. An exterior metal component, comprising a substrate and a protective layer; The protective layer is the transparent protective layer according to any one of claims 1-10, or the UV-resistant and impact-resistant coating according to any one of claims 11-21.

23. The exterior metal component according to claim 22, wherein, The substrate is selected from aluminum and / or aluminum alloys with an insulating coating on the surface.

24. The exterior metal fitting according to claim 23, wherein, The surface resistance of the substrate is greater than or equal to 50 MΩ.

25. A vehicle having an exterior metal trim as described in any one of claims 22-24.

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