A high temperature resistant and high reflectivity diffuse reflective silicon ink and its preparation and application

Abstract

The present invention relates to a high temperature resistant, high reflectivity and diffuse reflective silicon ink and its preparation and application. The silicon ink comprises the following raw material components in parts by weight: 20-40 parts of nano hybrid modified silicone resin, 30-60 parts of reflective filler, 10-20 parts of curing agent, 0.5-5 parts of high temperature resistant additive, 0.3-3 parts of leveling agent, 0.5-5 parts of silane coupling agent, 1-10 parts of solvent, and 1-10 parts of silicon dioxide. Compared with the prior art, the silicon reflective ink prepared by the present invention not only has excellent high temperature resistance, aging resistance, anti-yellowing, high reflectivity and diffuse reflection performance, but also has the characteristics of high adhesion and high hardness, and can be used for the reflective layer of LCD and Mini LED backlight modules to achieve the functional characteristics of high light efficiency, high stability and ultra-thin display.

Description

Technical Field

[0001] The invention belongs to the technical field of silicon-based inks, and relates to a high-temperature-resistant, high-reflectivity diffuse-reflective silicon-based ink and a preparation method thereof. Background Art

[0002] As people's demands for display technology become increasingly stringent, FPD flat panel displays (FPD) are developing in the direction of being thinner, lighter, higher brightness, and higher contrast. In LCD and Mini LED display products, high-performance backlight technology must be used in conjunction with them. The reflective material on the substrate in the backlight module directly affects the display performance, stability, and light efficiency of the display.

[0003] Most of the existing reflective inks use mirror reflection. The brightness is too high in the direction of light emission, which makes people feel dazzling. When it deviates from the direction of light emission, the light is too dim and cannot reflect the light well. A scattering film is often required, which increases the cost of the panel. In addition, traditional reflective inks have a large coating thickness and often use epoxy resin as the matrix. After being exposed to LED light sources for a long time and other reasons, the coating ages, turns yellow, and cracks, resulting in defects in the display. In addition, it will cause a significant attenuation of reflectivity in the reflow soldering process of Mini-LED, affecting the display performance. Although the existing silicon-based reflective inks on the market can achieve high temperature and anti-yellowing effects, the coatings prepared by this type of ink often have problems with poor adhesion and low hardness. Therefore, it has become an urgent problem to develop a high-reflectivity diffuse reflective silicon-based ink with high temperature resistance. Summary of the invention

[0004] The purpose of the present invention is to provide a high temperature resistant and high reflectivity diffuse reflective silicon ink and its preparation and application.

[0005] The silicon-based reflective ink prepared by the present invention not only has excellent high temperature resistance, aging resistance, yellowing resistance, high reflectivity and diffuse reflection properties, but also has the characteristics of high adhesion and high hardness. It can be used for the reflective layer of LCD and Mini LED backlight modules to achieve the functional characteristics of high light efficiency, high stability and ultra-thin display.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] One of the technical solutions of the present invention provides a high-temperature resistant and high-reflectivity diffuse reflective silicon-based ink, comprising the following raw material components in parts by weight: 20-40 parts of nano-hybrid modified silicone resin, 30-60 parts of reflective filler, 10-20 parts of curing agent, 0.5-5 parts of high-temperature resistant additives, 0.3-3 parts of leveling agents, 0.5-5 parts of silane coupling agents, 1-10 parts of solvents, and 1-10 parts of silicon dioxide.

[0008] Furthermore, the nano-hybrid modified silicone resin is formed by organic hybridization and inorganic hybridization of a modified resin having a main chain of Si-O-Si, a side group containing phenyl, and a polyester resin grafted at the end. Specifically, the nano-hybrid modified silicone resin of the present invention is a self-made modified resin having a main chain of Si-O-Si, a side group containing phenyl, and a polyester resin grafted at the end, so that the coating has excellent heat resistance, yellowing resistance, high pencil hardness, and after a cold and hot shock test, the coating does not have body cracking or cracking caused by a large difference in expansion coefficient with the substrate. At the same time, the resin undergoes organic hybridization, and by introducing Ti atoms into the Si-O-Si main chain, a hybrid block of Si-O-Ti-O-Si is formed, and the Ti atoms introduced in the form of coordination bonds (two lone pairs of electrons provided by the O atoms in the chain segment enter the empty orbit of the Ti atom to form an O→Ti coordination bond) form an organic-inorganic hybrid structure, thereby greatly improving the refractive index of the resin. According to the Fresnel reflection principle, the reflectivity increases with the increase of the refractive index under certain conditions, thereby improving the reflectivity of the coating and further improving the light efficiency. In addition, the resin undergoes inorganic hybridization, and by introducing titanium nanogel particles with a double electric layer structure into the resin, the particles can be stably dispersed in the system, and the refractive index of the resin is greatly improved. According to the Fresnel reflection principle, the reflectivity increases with the increase of the refractive index under certain conditions, thereby improving the reflectivity of the coating. Generally speaking, the particle size of the titanium nanogel particles doped with a double electric layer structure in the structure of the present invention is 1 nm-50 nm, the solid content of the nano-hybrid modified silicone resin is 100%, and the viscosity is 8000-12000 mPa·s (25° C.).

[0009] Furthermore, the nano-hybrid modified silicone resin is prepared by the following process:

[0010] (A) putting diphenyldimethoxysilane and water into a reaction kettle, adding a chelating agent, a dispersant, and a hydrolysis inhibitor, then dropping butyl titanate and a catalyst, performing a preliminary reaction, continuously adding hydroxy silicone oil, and heating to perform a condensation reaction to obtain an organic / inorganic hybrid terminal hydroxy phenyl silicone resin;

[0011] (B) placing a dibasic acid, a diol and a polyol into a reaction kettle, heating the reaction kettle under the protection of an inert gas to melt the materials, adding a catalyst butyl titanate, and continuing to heat the reaction kettle to carry out an esterification reaction;

[0012] (C) After the esterification is completed, the catalyst butyl titanate is added again, the temperature is raised to react, and then the temperature is lowered and the organic / inorganic hybrid terminal hydroxy phenyl silicone resin obtained in step (A) is added, and the reaction is continued to obtain a nano hybrid modified silicone resin.

[0013] Furthermore, in step (A), the mass ratios of diphenyldimethoxysilane, water, chelating agent, dispersant, hydrolysis inhibitor, catalyst, butyl titanate and hydroxy silicone oil are 25-30:1, 8-10:1, 0.1-0.2:1, 0.1-0.2:1, 5-10:1, 0.5-1.5:1 and 4-15:1 respectively.

[0014] Furthermore, in step (A), the chelating agent is selected from one of acetylacetone and polyvinyl alcohol.

[0015] Furthermore, in step (A), the dispersant is selected from hexadecyltrimethylammonium bromide or sodium dodecylbenzenesulfonate.

[0016] Furthermore, in step (A), the hydrolysis inhibitor is selected from one of ethanol and ethylene glycol.

[0017] Furthermore, in step (A), the catalyst is selected from hydrochloric acid or acetic acid.

[0018] Furthermore, in step (B), the dibasic acid is selected from one or more combinations of adipic acid, isophthalic acid or phthalic acid;

[0019] Furthermore, in step (B), the diol is selected from neopentyl glycol, diethylene glycol, or a combination of both.

[0020] Furthermore, in step (B), the polyol is 1,1,1-trimethylolpropane.

[0021] Furthermore, in step (B), the ratio of the added amount of the dibasic acid to the diol and polyol satisfies the following molar ratio OH / COOH=1.5-1.8.

[0022] Furthermore, in step (A), the temperature of the initial reaction is 70-80°C, the time is 3-5h, and the temperature of the temperature-raising condensation reaction is 90-100°C, the time is 1-2h.

[0023] Furthermore, in step (B), the esterification reaction process is: first react at 160-200° C. for 1 hour, then continue to heat up to 220-240° C. and react until the acid value is less than 5 mgKOH / g.

[0024] Furthermore, in step (C), the temperature-raising reaction process is: reacting at 220-240° C. for 20-40 min, and the continuing reaction process is: reacting at 160-200° C. for 1-2 h.

[0025] Further, the reflective filler is compounded by 30-60 parts of surface modified titanium dioxide, 30-60 parts of barium sulfate and 1-15 parts of aluminum oxide, wherein the surface modified titanium dioxide is selected from any one or a combination of surface aluminum modified titanium dioxide, surface zirconium modified titanium dioxide and surface zinc modified titanium dioxide. In addition, the particle size of the surface modified titanium dioxide is 100-500nm, the modified titanium dioxide is preferably rutile, the particle size of the barium sulfate is 300-500nm, and the microstructure of the aluminum oxide is flaky, with a particle size of 1-3μm.

[0026] Furthermore, the solvent is prepared by compounding one or more of propylene glycol methyl ether acetate, diethylene glycol butyl ether, and ethylene glycol butyl ether.

[0027] Furthermore, the high temperature resistant additive is selected from one or both of lanthanum oxide and cerium oxide, and its particle size is preferably 500-800nm, more preferably 600nm.

[0028] Furthermore, the leveling agent is polyether-modified silicone oil, and its viscosity may preferably be 500cp-1000cp.

[0029] Furthermore, the coupling agent is one of γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, preferably γ-glycidyloxypropyltrimethoxysilane.

[0030] Furthermore, the curing agent is a trimer of isocyanate, with an NCO mass fraction of 20%-22% and a viscosity of 2000cp-3000cp.

[0031] Furthermore, the particle size of the silicon dioxide is 50nm-80nm.

[0032] The second technical solution of the present invention provides a method for preparing a high-temperature resistant and high-reflectivity diffuse reflective silicon-based ink, wherein each raw material component is mixed in a non-invasive homogenizer in turn, and then dispersed and ground by a three-roll mill, and then filtered through a filter membrane at a positive pressure to obtain the target product.

[0033] Furthermore, the gap of the three-roll mill dispersion grinding is 5 to 10 μm.

[0034] Furthermore, the filter membrane has a filter diameter of 5 μm.

[0035] The third technical solution of the present invention provides an application of a high-temperature resistant and high-reflectivity diffuse reflective silicon-based ink, which is applied to a Mini-LED or LCD panel backlight module.

[0036] Furthermore, the specific process of applying the silicon-based ink to the substrate in the Mini-LED or LCD panel backlight module is as follows:

[0037] Step 1: coating the high-temperature resistant, high-reflectivity, diffuse-reflective silicon-based ink on a substrate, with a coating thickness of 30 to 80 μm, more preferably 30 to 50 μm, and most preferably 30 μm.

[0038] Step 2: curing by stepwise heating, the curing scheme is: curing at an oven temperature of 80-100°C for 5-10 minutes, and then curing at 120-150°C for 1-2 hours to obtain a reflective coating. The most preferred curing method is curing at an oven temperature of 100°C for 10 minutes, and then curing at 150°C for 2 hours.

[0039] Compared with the prior art, the present invention has the following advantages:

[0040] (1) The present invention uses a modified hybrid silicone resin as a matrix, adds a reflective filler, a high temperature resistant additive, a leveling agent, a solvent, and silicon dioxide to prepare a high temperature resistant, high reflectivity diffuse reflective silicon-based ink.

[0041] (2) The silicone resin containing phenyl is used as the main body, which gives the resin high temperature resistance and yellowing resistance, and its linear expansion coefficient is close to that of glass, making it have excellent resistance to cold and hot shock. By grafting polyester resin at the end of the main chain, the adhesion and pencil hardness of the resin are improved. By introducing hybrid blocks of Ti atoms in the form of covalent bonds and Ti atoms in the form of coordination bonds into the chain segments and doping titanium nanogel particles with a double electric layer structure into the structure, the titanium nanogel particles can be stably dispersed in the system, which greatly improves the refractive index of the resin and the reflectivity of the ink.

[0042] (3) The reflectivity and shielding properties of visible light are improved by surface modification of titanium dioxide; the reflectivity of long-wavelength bands is improved by adding barium sulfate; the shielding properties are further improved by adding flaky aluminum oxide, and the structural combination is optimized by optimizing the ratio and particle size selection to achieve an excellent reflective effect. The reflectivity can reach more than 97% at a thickness of 30 μm.

[0043] (4) Through the volatilization effect of the solvent during heating and curing and the bulk thixotropy brought by silica, a balance is achieved between the two, so that when the solvent overflows the surface, the coating forms an irregular surface and finally maintains the corresponding shape, and then solidifies to form a diffuse reflective effect.

[0044] (5) The silicon-based ink of the present invention can be self-leveling during the coating process and prevent the ink from spreading and overflowing after coating. In a high shear state (such as when the ink contacts the substrate during printing and spraying; when the scraper scrapes the screen onto the substrate during screen printing), the ink viscosity decreases and the fluidity increases. In a static state (when the ink is coated on the substrate), the ink viscosity gradually recovers and the fluidity decreases. According to this mechanism, the ink of the present invention is in a high shear state when coated on the substrate, and has fluidity in a short time, which can make the ink level, and then the viscosity and fluidity are restored, and the ink will be fixed to the substrate, solving the problem of spreading and overflowing.

[0045] (6) The silicon-based ink of the present invention is used on the substrate of the Mini-LED panel backlight module and the LCD panel backlight module. The coating can meet the Mini LED reflow soldering process. At 280°C for 10 minutes, the reflectivity drops within 5%. It also has excellent anti-yellowing, anti-cold and hot shock, and anti-aging effects. The diffuse reflectivity improves the uniformity of the LED backlight source, enhances the display performance, and meets the requirements of the display in terms of weather resistance, stability, and high light efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 Schematic diagram of applying the ink in Example 1 to MiniLED. DETAILED DESCRIPTION

[0047] The present invention is described in detail below in conjunction with specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0048] The ink provided by the present invention is used for the substrate in the field of Mini-LED panel backlight module and LCD panel backlight module, and has a series of parameter requirements for the reflective coating after the reflective ink is cured, specifically including: reflectivity, adhesion, pencil hardness, reflow resistance, yellowing resistance, and resistance to cold and hot shocks.

[0049] In order to improve the reflectivity of the ink, the present invention uses an organic-inorganic hybridized resin. Organic hybridization: by introducing Ti atoms into the Si-O-Si main chain to form a hybrid block of Si-O-Ti-O-Si. Inorganic hybridization: by introducing 1-50nm titanium oxide gel particles into the resin, and Ti atoms introduced in the form of coordination bonds (two lone pairs of electrons provided by the O atoms in the chain segment enter the empty orbit of the Ti atom to form an O→Ti coordination bond). Thereby, the refractive index of the resin is greatly improved. According to the Fresnel reflection principle, the reflectivity increases with the increase of the refractive index under certain conditions, thereby improving the reflectivity of the coating.

[0050] In order to make the coating have excellent heat resistance, yellowing resistance, high pencil hardness, and no body cracking or cracking of the glass due to excessive difference in expansion coefficient with the substrate after hot and cold shock tests, the present invention uses a homemade modified resin with a main chain of Si-O-Si, a side group containing phenyl, and a polyester resin grafted at the end.

[0051] In order to improve the reflectivity of the ink, the present invention selects surface-modified titanium dioxide.

[0052] In order to improve the heat resistance of the ink, after the high temperature of reflow soldering, the reflectivity drops within 5%. The present invention selects cerium oxide or lanthanum oxide as a high temperature resistant additive. The mechanism is that under high temperature environment, high-valent metal ions can capture free radicals generated during the oxidation process of silicone rubber side groups, so that the metal ions are reduced and the chain growth reaction is terminated within a certain temperature range, thereby improving the thermal stability of silicone rubber.

[0053] In order to make the ink form diffuse reflectivity after curing, the present invention controls the amount of leveling agent added to change the surface tension of the coating and the thixotropy of the ink caused by the filler, and the two are balanced, so that the solvent forms an irregular surface during the volatilization process to achieve diffuse reflectivity.

[0054] The present invention is further described below in conjunction with specific embodiments.

[0055] In the following embodiments, the preparation process of the nano-hybrid modified silicone resin is as follows:

[0056] (A) putting diphenyldimethoxysilane and water into a reaction kettle, adding a chelating agent and a dispersant, and then dropping butyl titanate, a hydrolysis inhibitor and a catalyst, for a preliminary reaction, and then adding hydroxy silicone oil, heating and condensing reaction to obtain an organic / inorganic hybrid terminal hydroxy phenyl silicone resin;

[0057] (B) placing a dibasic acid, a diol and a polyol into a reaction kettle, heating the reaction kettle under the protection of an inert gas to melt the materials, adding a catalyst butyl titanate, and continuing to heat the reaction kettle to carry out an esterification reaction;

[0058] (C) After the esterification is completed, the catalyst butyl titanate is added again, the temperature is raised to react, and then the temperature is lowered and the organic / inorganic hybrid terminal hydroxyl phenyl silicone resin obtained in step (A) is added, and the reaction is continued to obtain a nano hybrid modified silicone resin;

[0059] In step (A), 18 parts of diphenyldimethoxysilane, 5 parts of water, 0.1 parts of chelating agent, 0.1 parts of dispersant, and 10 parts of hydrolysis inhibitor are added to the reactor, and then 0.5 parts of catalyst and 7 parts of butyl titanate are slowly dripped into the reactor respectively, and the dripping time is controlled within 3 hours. The temperature of the initial reaction is 75° C. and the time is 4 hours. After the reaction, 0.6 parts of hydroxy silicone oil are continuously added, and the temperature of the temperature-raising condensation reaction is 95° C. and the time is 1.5 hours. After the reaction is completed, the organic / inorganic hybrid terminal hydroxy phenyl silicone resin is obtained by washing and rotary evaporation;

[0060] In step (B), the esterification reaction process is: add 20 parts of neopentyl glycol, 6 parts of diethylene glycol, 17 parts of terephthalic acid, 6 parts of isophthalic acid, 5 parts of adipic acid, and 4 parts of 1,1,1-trimethylolpropane into a reaction kettle, continuously introduce nitrogen, react at 180° C. for 1 hour, add 0.5 parts of butyl titanate, continue to heat to 230° C. and react until the acid value is less than 5 mgKOH / g;

[0061] In step (C), the temperature-raising reaction process is: continue to add 0.2 parts of butyl titanate to step (B), react at 230° C. for 30 minutes, and continue the reaction process: cool to 180° C., add the organic / inorganic hybrid terminal hydroxy phenyl silicone resin obtained in step (A), and continue the reaction for 1-2 hours to obtain a nano-hybrid modified silicone resin.

[0062] The modified titanium dioxide used was Huntsman TR52, the curing agent used was DESMODUR N100, and the leveling agent used was BYK-333.

[0063] The rest of the raw materials or processing techniques, unless otherwise specified, are conventional commercially available raw materials or conventional processing techniques in the art.

[0064] Example 1

[0065] Preparation of nano-hybrid modified silicone resin:

[0066] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 17.4 parts of diphenyldimethoxysilane, 5.3 parts of water, 5.0 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of acetylacetone, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to obtain an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin obtained by reacting 22.2 parts of neopentyl glycol, 5.9 parts of diethylene glycol, 1.0 parts of 1,1,1-trimethylolpropane, 18.3 parts of terephthalic acid, 12.1 parts of isophthalic acid, 1.0 parts of adipic acid, and 0.5 parts of butyl titanate.

[0067] Ink preparation:

[0068] The following materials were selected: 25.0 parts of nano-hybrid modified silicone resin, 24.0 parts of modified titanium dioxide, 20.0 parts of barium sulfate, 5.0 parts of flaky aluminum oxide, 1.0 parts of cerium oxide, 10.0 parts of curing agent, 1.0 parts of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide.

[0069] According to the formula, add homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, propylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether, and silicon dioxide in sequence, use a high-speed disperser at 3000rpm, stir for 1 hour, then add the curing agent, use a non-intrusive homogenizer to mix, and then grind and disperse it with a three-roller machine for 3-5 times, filter it with a filter to obtain the ink.

[0070] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0071] The schematic diagram of the ink of this embodiment applied to MiniLED can be referred to Figure 1 As shown, the specific ink 2 is coated on the substrate 3 encapsulating the LED chip 1 .

[0072] Example 2

[0073] Preparation of nano-hybrid modified silicone resin:

[0074] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. An organic / inorganic hybrid terminal hydroxy phenyl silicone resin is prepared by reacting 17.6 parts of diphenyl dimethoxy silane, 5.0 parts of water, 2.8 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of acetylacetone, 0.1 parts of hexadecyl trimethyl ammonium bromide, and 10 parts of ethanol, and then polycondensed with a polyester resin prepared by reacting 16.7 parts of neopentyl glycol, 15.0 parts of diethylene glycol, 1.0 parts of 1,1,1-trimethylolpropane, 17.5 parts of terephthalic acid, 11.6 parts of isophthalic acid, 1.0 parts of adipic acid, and 0.5 parts of butyl titanate to obtain the product.

[0075] Ink preparation:

[0076] The following materials were selected: 25.0 parts of nano-hybrid modified silicone resin, 24.0 parts of modified titanium dioxide, 20.0 parts of barium sulfate, 5.0 parts of flaky aluminum oxide, 1.0 parts of cerium oxide, 10.0 parts of curing agent, 1.0 parts of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide.

[0077] According to the formula, add homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, propylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether, and silicon dioxide in sequence, use a high-speed disperser at 3000rpm, stir for 1 hour, then add the curing agent, use a non-intrusive homogenizer to mix, and then grind and disperse it with a three-roller machine for 3-5 times, filter it with a filter to obtain the ink.

[0078] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0079] Example 3

[0080] Preparation of nano-hybrid modified silicone resin:

[0081] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 16.8 parts of diphenyldimethoxysilane, 5.7 parts of water, 7.2 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of acetylacetone, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to prepare an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin prepared by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate.

[0082] Ink preparation:

[0083] The following materials were selected: 25.0 parts of nano-hybrid modified silicone resin, 24.0 parts of modified titanium dioxide, 20.0 parts of barium sulfate, 5.0 parts of flaky aluminum oxide, 1.0 parts of cerium oxide, 10.0 parts of curing agent, 1.0 parts of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide.

[0084] According to the formula, add homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, propylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether, and silicon dioxide in sequence, use a high-speed disperser at 3000rpm, stir for 1 hour, then add the curing agent, use a non-intrusive homogenizer to mix, and then grind and disperse it with a three-roller machine for 3-5 times, filter it with a filter to obtain the ink.

[0085] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0086] Example 4

[0087] Preparation of nano-hybrid modified silicone resin:

[0088] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 16.8 parts of diphenyldimethoxysilane, 5.7 parts of water, 7.2 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of polyvinyl alcohol, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to obtain an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin obtained by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate.

[0089] Ink preparation:

[0090] The following materials were selected: 25.0 parts of nano-hybrid modified silicone resin, 24.0 parts of modified titanium dioxide, 20.0 parts of barium sulfate, 5.0 parts of flaky aluminum oxide, 1.0 parts of cerium oxide, 10.0 parts of curing agent, 1.0 parts of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide.

[0091] According to the formula, add homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, propylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether, and silicon dioxide in sequence, use a high-speed disperser at 3000rpm, stir for 1 hour, then add the curing agent, use a non-intrusive homogenizer to mix, and then grind and disperse it with a three-roller machine for 3-5 times, filter it with a filter to obtain the ink.

[0092] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0093] Example 5

[0094] Preparation of nano-hybrid modified silicone resin:

[0095] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 16.8 parts of diphenyldimethoxysilane, 5.7 parts of water, 7.2 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of polyvinyl alcohol, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to obtain an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin obtained by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate.

[0096] Ink preparation:

[0097] The following materials were selected: 30.0 parts of nano-hybrid modified silicone resin, 21.6 parts of modified titanium dioxide, 18.0 parts of barium sulfate, 4.4 parts of flaky aluminum oxide, 1.0 parts of cerium oxide, 10.0 parts of curing agent, 1.0 parts of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide.

[0098] According to the formula, add homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, propylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether, and silicon dioxide in sequence, use a high-speed disperser at 3000rpm, stir for 1 hour, then add the curing agent, use a non-intrusive homogenizer to mix, and then grind and disperse it with a three-roller machine for 3-5 times, filter it with a filter to obtain the ink.

[0099] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0100] Example 6

[0101] Preparation of nano-hybrid modified silicone resin:

[0102] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 16.8 parts of diphenyldimethoxysilane, 5.7 parts of water, 7.2 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of polyvinyl alcohol, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to obtain an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin obtained by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate.

[0103] Ink preparation:

[0104] The following materials were selected: 35.0 parts of nano-hybrid modified silicone resin, 19.1 parts of modified titanium dioxide, 16.0 parts of barium sulfate, 3.9 parts of flaky aluminum oxide, 1.0 parts of cerium oxide, 10.0 parts of curing agent, 1.0 parts of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide.

[0105] According to the formula, add homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, propylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether, and silicon dioxide in sequence, use a high-speed disperser at 3000rpm, stir for 1 hour, then add the curing agent, use a non-intrusive homogenizer to mix, and then grind and disperse it with a three-roller machine for 3-5 times, filter it with a filter to obtain the ink.

[0106] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0107] Example 7

[0108] Preparation of nano-hybrid modified silicone resin:

[0109] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 16.8 parts of diphenyldimethoxysilane, 5.7 parts of water, 7.2 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of polyvinyl alcohol, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to obtain an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin obtained by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate.

[0110] Ink preparation:

[0111] 30.0 parts of nano-hybrid modified silicone resin, 30.8 parts of modified titanium dioxide, 9.4 parts of barium sulfate, 3.8 parts of flaky aluminum oxide, 1.0 part of cerium oxide, 10.0 parts of curing agent, 1.0 part of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide were selected.

[0112] According to the formula, add homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, propylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether, and silicon dioxide in sequence, use a high-speed disperser at 3000rpm, stir for 1 hour, then add the curing agent, use a non-intrusive homogenizer to mix, and then grind and disperse it with a three-roller machine for 3-5 times, filter it with a filter to obtain the ink.

[0113] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0114] Example 8

[0115] Preparation of nano-hybrid modified silicone resin:

[0116] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 16.8 parts of diphenyldimethoxysilane, 5.7 parts of water, 7.2 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of polyvinyl alcohol, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to obtain an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin obtained by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate.

[0117] Ink preparation:

[0118] The following materials were selected: 30.0 parts of nano-hybrid modified silicone resin, 32.0 parts of modified titanium dioxide, 10.8 parts of barium sulfate, 1.2 parts of flaky aluminum oxide, 1.0 parts of cerium oxide, 10.0 parts of curing agent, 1.0 parts of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide.

[0119] According to the formula, add homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, propylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether, and silicon dioxide in sequence, use a high-speed disperser at 3000rpm, stir for 1 hour, then add the curing agent, use a non-intrusive homogenizer to mix, and then grind and disperse it with a three-roller machine for 3-5 times, filter it with a filter to obtain the ink.

[0120] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0121] Example 9

[0122] Preparation of nano-hybrid modified silicone resin:

[0123] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 16.8 parts of diphenyldimethoxysilane, 5.7 parts of water, 7.2 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of polyvinyl alcohol, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to prepare an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin prepared by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate to prepare the product.

[0124] Ink preparation:

[0125] The following materials were selected: 30.0 parts of nano-hybrid modified silicone resin, 21.1 parts of modified titanium dioxide, 19.4 parts of barium sulfate, 3.5 parts of flaky aluminum oxide, 1.0 parts of cerium oxide, 10.0 parts of curing agent, 1.0 parts of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide.

[0126] According to the formula, add homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, propylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether, and silicon dioxide in sequence, use a high-speed disperser at 3000rpm, stir for 1 hour, then add the curing agent, use a non-intrusive homogenizer to mix, and then grind and disperse it with a three-roller machine for 3-5 times, filter it with a filter to obtain the ink.

[0127] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0128] Comparative Example 1

[0129] Referring to Example 9, the difference is that the resin is prepared without undergoing organic / inorganic hybridization, and the other proportions and preparation methods are the same.

[0130] Preparation of modified silicone resin:

[0131] It is obtained by modifying terminal hydroxy phenyl silicone resin. 22.2 parts of diphenyl dimethoxy silane, 7.5 parts of water, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, and 10 parts of ethanol are used to react to obtain terminal hydroxy phenyl silicone resin, which is then polycondensed with polyester resin obtained by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate to obtain the product.

[0132] Select 30 parts of modified silicone resin without nano-hybridization, 21.5 parts of modified titanium dioxide, 19.5 parts of barium sulfate, 5.5 parts of flaky aluminum oxide, 1 part of cerium oxide, 5 parts of curing agent, 1 part of leveling agent, 1.5 parts of silane coupling agent, 3 parts of propylene glycol methyl ether acetate, 1 part of diethylene glycol butyl ether, 1 part of ethylene glycol butyl ether, and 10 parts of silicon dioxide.

[0133] According to the formula, homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, solvent and silicon dioxide were added in sequence, stirred for 1 hour using a high-speed disperser at 3000 rpm, and then a curing agent was added. After mixing evenly using a non-intervention homogenizer, the mixture was ground and dispersed using a three-roller machine for 3-5 times and filtered through a filter to obtain the ink.

[0134] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0135] Comparative Example 2

[0136] Referring to Example 9, the difference is that the resin is not modified by polyester during preparation, and the other proportions and preparation methods are the same.

[0137] Preparation of Nano-hybrid Silicone Resin:

[0138] 41.0 parts of diphenyldimethoxysilane, 13.9 parts of water, 17.6 parts of butyl titanate, 1.2 parts of hydrochloric acid, 1.5 parts of hydroxy silicone oil, 0.2 parts of acetylacetone, 0.2 parts of hexadecyltrimethylammonium bromide and 24.4 parts of ethanol were reacted to prepare an organic / inorganic hybrid terminal hydroxy phenyl silicone resin.

[0139] Select 30 parts of modified silicone resin without nano-hybridization, 21.5 parts of modified titanium dioxide, 19.5 parts of barium sulfate, 5.5 parts of flaky aluminum oxide, 1 part of cerium oxide, 5 parts of curing agent, 1 part of leveling agent, 1.5 parts of silane coupling agent, 3 parts of propylene glycol methyl ether acetate, 1 part of diethylene glycol butyl ether, 1 part of ethylene glycol butyl ether, and 10 parts of silicon dioxide.

[0140] According to the formula, homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, solvent and silicon dioxide were added in sequence, stirred for 1 hour using a high-speed disperser at 3000 rpm, and then a curing agent was added. After mixing evenly using a non-intervention homogenizer, the mixture was ground and dispersed using a three-roller machine for 3-5 times and filtered through a filter to obtain the ink.

[0141] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0142] Comparative Example 3

[0143] Refer to Example 9, except that no high temperature resistant additive is added to the formula, and the other proportions and preparation methods are the same.

[0144] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 16.8 parts of diphenyldimethoxysilane, 5.7 parts of water, 7.2 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of polyvinyl alcohol, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to prepare an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin prepared by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate to prepare the product.

[0145] Ink preparation:

[0146] 30.0 parts of nano-hybrid modified silicone resin, 21.1 parts of modified titanium dioxide, 19.4 parts of barium sulfate, 3.5 parts of flaky aluminum oxide, 10.0 parts of curing agent, 1.0 parts of leveling agent BYK333, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, 0.5 parts of ethylene glycol butyl ether, and 7.5 parts of silicon dioxide were selected.

[0147] According to the formula, homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, solvent and silicon dioxide were added in sequence, stirred for 1 hour using a high-speed disperser at 3000 rpm, and then a curing agent was added. After mixing evenly using a non-intervention homogenizer, the mixture was ground and dispersed using a three-roller machine for 3-5 times and filtered through a filter to obtain the ink.

[0148] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0149] Comparative Example 4

[0150] Refer to Example 9, except that no leveling agent and silicon dioxide are added to the formula, and the other proportions and preparation methods are the same.

[0151] It is prepared by modifying an organic / inorganic hybrid terminal hydroxy phenyl silicone resin. 16.8 parts of diphenyldimethoxysilane, 5.7 parts of water, 7.2 parts of butyl titanate, 0.5 parts of hydrochloric acid, 0.6 parts of hydroxy silicone oil, 0.1 parts of polyvinyl alcohol, 0.1 parts of hexadecyltrimethylammonium bromide, and 10 parts of ethanol are used to react to prepare an organic / inorganic hybrid terminal hydroxy phenyl silicone resin, which is then polycondensed with a polyester resin prepared by reacting 20.6 parts of neopentyl glycol, 6.0 parts of diethylene glycol, 3.8 parts of 1,1,1-trimethylolpropane, 17.0 parts of terephthalic acid, 5.9 parts of isophthalic acid, 5.2 parts of adipic acid, and 0.5 parts of butyl titanate to prepare the product.

[0152] Ink preparation:

[0153] 35.4 parts of nano-hybrid modified silicone resin, 22.6 parts of modified titanium dioxide, 20.7 parts of barium sulfate, 3.8 parts of flaky aluminum oxide, 10.0 parts of curing agent, 1.5 parts of silane coupling agent γ-glycidyloxypropyltrimethoxysilane, 4.0 parts of propylene glycol methyl ether acetate, 0.5 parts of diethylene glycol butyl ether, and 0.5 parts of ethylene glycol butyl ether were selected.

[0154] According to the formula, homemade silicone resin, silane coupling agent, leveling agent, high temperature resistant additive, solvent and silicon dioxide were added in sequence, stirred for 1 hour using a high-speed disperser at 3000 rpm, and then a curing agent was added. After mixing evenly using a non-intervention homogenizer, the mixture was ground and dispersed using a three-roller machine for 3-5 times and filtered through a filter to obtain the ink.

[0155] Preparation of reflective coating: The above ink was coated on a glass substrate. The coating thickness was controlled to be 30 μm, and the coating was placed in an oven at 100° C. for curing for 10 min, and then immediately cured at 150° C. for 2 h to obtain a reflective coating.

[0156] Table 1

[0157]

[0158]

[0159] in:

[0160] The reflectivity test refers to HG / T 4915-2016 "Determination method of reflectivity of white reflective film".

[0161] The cross-cut test shall refer to GB / T 9286-2021 "Scratching test for paints and varnishes".

[0162] Reflow resistance test: The prepared reflective coating is placed in an oven at 280°C for 10 minutes. If the reflectivity decreases by no more than 5%, it passes.

[0163] The yellowing resistance test refers to GB11186.3-1989 "Measurement method of paint film color Part 3 Calculation of color difference". The prepared reflective coating is placed in an oven at 280°C for 10 minutes, and it is considered to have passed if ΔE < 1.5.

[0164] Thermal shock resistance test: Place the prepared reflective coating in a thermal shock test chamber, -30 ~ 120 ℃ 30 minutes each, 200 cycles, and it passes if there is no discoloration, falling off, blistering or cracking.

[0165] Conclusion: From the above data, it can be obtained that the reflectivity of the embodiment reaches 85.2-97.5% at a thickness of 30 μm.

[0166] It can be seen from Examples 1-4 that when the molar ratio of diphenyldimethoxysilane to butyl titanate is about 1:0.1, the reflectivity of the reflective coating is optimal; the OH / COOH ratio is about 1.6, the ratio of neopentyl glycol: diethylene glycol: 1,1,1-trimethylolpropane is about 68:20:12; the ratio of terephthalic acid, isophthalic acid, and adipic acid is about 61:21:18; in summary, the pencil hardness and resistance to cold and hot shock of the reflective coating are optimal.

[0167] It can be seen from Examples 4-6 that the best coating performance and reflectivity can be obtained when the resin ratio is 30%.

[0168] It can be seen in Examples 5, 7, 8 and 9 that when the amount of flaky aluminum oxide is increased within a certain range, the ink reflectivity and the pencil hardness of the coating are improved. When the addition amount is 3.5%, the comprehensive performance is optimal.

[0169] It can be seen from Examples 7-9 that the optimal reflectivity is obtained when the ratio of titanium dioxide: barium sulfate: flaky aluminum oxide is approximately 48:44:8.

[0170] Embodiment 9 is the most preferred among all embodiments, and its reflectivity is 97.3%, and the cross-cut test is rated as level 0; the pencil hardness is 4H; the reflow resistance test and the yellowing resistance test are passed, and the specific decrease rate is 1.3%, and ΔE is 1.0; after the cold and hot shock resistance test, there is no discoloration, shedding, blistering, and cracking; the coating has a diffuse reflection effect.

[0171] It can be seen from Comparative Example 1 that the reflective coating prepared by the resin without nano-hybridization has a lower reflectivity than the reflective coating prepared by the resin with nano-hybridization, which proves that the introduction of titanium hybrid segments and titanium nanogel particles significantly improves the reflectivity of the coating; in the reflow resistance test and the yellowing resistance test, the reflectivity decreased by 8.3%, and ΔE was 2.5. Compared with Example 9, the reflective coating prepared by the nano-hybridized resin has a significantly increased reflectivity decrease rate and a color difference value, which does not meet the predetermined requirements. This is because the introduction of the -O-Ti-O- segment has better heat resistance; this shows the necessity of resin hybridization.

[0172] It can be seen from Comparative Example 2 that the pencil hardness and cross-cut test of the reflective coating prepared by the unmodified resin are greatly reduced, which proves that the hardness and adhesion of the resin are greatly improved after being modified by polyester.

[0173] It can be seen from Comparative Example 3 that the reflective coating without adding the high temperature resistant additive has a reflectivity decrease of 10.7% and a ΔE of 3.0 in the reflow resistance test and the yellowing resistance test. Compared with Example 9, the reflective coating with the addition of the high temperature resistant additive has a significantly increased reflectivity decrease rate and a color difference value, which does not meet the predetermined requirements. Compared with Comparative Example 1, the reflectivity decrease rate and the color difference value increase are more obvious, which shows the necessity of adding the high temperature resistant additive.

[0174] It can be seen from Comparative Example 4 that if the resin in the formula is neither nano-hybridized nor added with a high temperature resistant additive, its reflectivity is significantly lower than that of Example 9; the reflectivity of the reflective coating prepared therefrom decreases by 15.4% in the reflow resistance and yellowing resistance tests, and ΔE is 4.0. Compared with Comparative Examples 1 and 3, the decrease rate of reflectivity and the color difference value are more obvious, which shows the necessity of resin hybridization and the addition of high temperature resistant additives.

[0175] It can be seen from Comparative Example 5 that the addition of silica plays a significant role in the thixotropy of the ink. Without the addition of a leveling agent or silica, a diffuse reflection effect cannot be obtained. It should be noted that even if silica and a leveling agent are added, the ratio of the two must be controlled, and the solvent and curing conditions must be coordinated to achieve a diffuse reflection effect.

[0176] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A high temperature resistant and high reflectivity diffuse reflective silicon ink, characterized in that: The invention comprises the following raw material components in parts by weight: 20-40 parts of nano hybrid modified silicone resin, 30-60 parts of reflective filler, 10-20 parts of curing agent, 0.5-5 parts of high temperature resistant additive, 0.3-3 parts of leveling agent, 0.5-5 parts of silane coupling agent, 1-10 parts of solvent and 1-10 parts of silicon dioxide; The nano hybrid modified silicone resin is made of modified resin with Si-O-Si as the main chain, phenyl groups in the side groups and polyester resin grafted at the end through organic hybridization and inorganic hybridization; The nano-hybrid modified silicone resin is prepared by the following process: (A) Diphenyldimethoxysilane and water are put into a reaction kettle, a chelating agent and a dispersant are added, and then butyl titanate, a hydrolysis inhibitor and a catalyst are added dropwise for a preliminary reaction, and hydroxy silicone oil is added continuously, and the temperature is raised for a condensation reaction to obtain an organic / inorganic hybrid terminal hydroxy phenyl silicone resin; (B) putting a dibasic acid, a diol and a polyol into a reaction kettle, heating the reaction kettle under the protection of an inert gas to melt the materials, adding a catalyst butyl titanate, and continuing to heat the reaction kettle to carry out an esterification reaction; (C) After the esterification is completed, the catalyst butyl titanate is added again, the temperature is raised to react, and then the temperature is lowered and the organic / inorganic hybrid terminal hydroxy phenyl silicone resin obtained in step (A) is added, and the reaction is continued to obtain a nano hybrid modified silicone resin; The reflective filler is compounded by 30-60wt% of surface-modified titanium dioxide, 30-60wt% of barium sulfate and 1-10wt% of aluminum oxide, wherein the surface-modified titanium dioxide is selected from any one or a combination of surface aluminum-modified titanium dioxide, surface zirconium-modified titanium dioxide and surface zinc-modified titanium dioxide; The solvent is compounded from one or more of propylene glycol methyl ether acetate, diethylene glycol butyl ether, and ethylene glycol butyl ether; the high temperature resistant additive is selected from one or both of lanthanum oxide and cerium oxide, and the particle size is 500-800nm; The leveling agent is polyether modified silicone oil with a viscosity of 500cp-1000cp; The coupling agent is one of γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane; The curing agent is a trimer of isocyanate, with an NCO mass fraction of 20%-22% and a viscosity of 2000cp-3000cp.

2. The high temperature resistant and high reflectivity diffuse reflective silicon ink according to claim 1, characterized in that: In step (A), the mass ratios of diphenyldimethoxysilane, water, chelating agent, dispersant, hydrolysis inhibitor, catalyst, butyl titanate and hydroxy silicone oil are 25-30:1, 8-10:1, 0.1-0.2:1, 0.1-0.2:1, 5-10:1, 0.5-1.5:1 and 4-15:1 respectively; The chelating agent is selected from one of acetylacetone and polyvinyl alcohol; The dispersant is selected from one of hexadecyltrimethylammonium bromide and sodium dodecylbenzenesulfonate; The hydrolysis inhibitor is selected from one of ethanol and ethylene glycol; The catalyst is selected from hydrochloric acid or acetic acid.

3. The high temperature resistant and high reflectivity diffuse reflective silicon ink according to claim 1, characterized in that: In step (B), the dibasic acid is selected from one or more combinations of adipic acid, isophthalic acid or phthalic acid; The diol is selected from any one of neopentyl glycol and diethylene glycol or a combination of the two; The polyol is 1,1,1-trimethylolpropane; The ratio of the added amount of the dibasic acid to the diol and the polyol satisfies the following molar ratio OH / COOH=1.4-1.

8.

4. The high temperature resistant and high reflectivity diffuse reflective silicon ink according to claim 1, characterized in that: In step (A), the temperature of the initial reaction is 70-80°C for 3-5 hours, and the temperature of the temperature-raising condensation reaction is 90-100°C for 1-2 hours; In step (B), the esterification reaction process is: first react at 160-200°C for 1 hour, then continue to heat up to 220-240°C and react until the acid value is less than 5mgKOH / g; In step (C), the temperature-raising reaction process is: reacting at 220-240° C. for 20-40 min, and the continuing reaction process is: reacting at 160-200° C. for 1-2 h.

5. The method for preparing the high temperature resistant and high reflectivity diffuse reflective silicon ink according to any one of claims 1 to 4, characterized in that: The raw material components are mixed in a non-intrusive homogenizer in turn, dispersed and ground by a three-roll mill, and then filtered through a filter membrane at positive pressure to obtain the target product.

6. The use of the high temperature resistant and high reflectivity diffuse reflective silicon ink according to any one of claims 1 to 4, characterized in that: The silicon-based ink is used in LCD panel backlight modules.

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