TWI882385B - Coating material, coating layer, and light-emitting device - Google Patents

Abstract

A coating material includes a modified particle and a reactive compound. The modified particle includes a core, and a silane coupling agent including an epoxy group (or a double-bond) grafted onto a surface of the core. When the silane coupling agent including the epoxy group is grafted onto the surface of the core, the reactive compound includes a non-silicon multi epoxy compound and a silicon-containing multi epoxy compound. When the silane coupling agent including the double-bond is grafted onto the surface of the core, the reactive compound includes a multi-double bond compound.

Description

Paints, coatings, and light-emitting devices

This disclosure relates to coatings, and more particularly to coating layers formed by coatings and their applications.

Pure organic polymers are difficult to achieve high refractive index. Inorganic coatings have high refractive index, but their low flexibility and high density (>2.5cm ³ ) make subsequent applications difficult in terms of manufacturing process. In summary, there is an urgent need to design new film compositions that combine the advantages of organic and inorganic materials and apply them to high refractive index films.

The coating provided by one embodiment of the present invention comprises: a modified particle, comprising: a core; and a silane coupling agent having an epoxy group or a silane coupling agent having a double bond, grafted to the surface of the core, wherein the core comprises (1) an oxide of zinc and titanium, wherein the weight ratio of zinc to titanium is 1:0.4 to 1:0.9, and (2) an oxide of zirconium and titanium, wherein the weight ratio of zirconium to titanium is 1:0.1 to 1:2. , or (3) oxides of zinc and zirconium, wherein the weight ratio of zinc to zirconium is 1:0.8 to 1:2; and a reactive compound, wherein when a silane coupling agent having an epoxy group is grafted onto the surface of the core, the reactive compound comprises a polyepoxy compound containing no silicon and a polyepoxy compound containing silicon, and when a silane coupling agent having a double bond is grafted onto the surface of the core, the reactive compound comprises a poly-double bond compound.

The coating provided in one embodiment of the present invention is formed by the reaction of the above-mentioned coating material.

The light-emitting device provided in one embodiment of the present invention includes: a substrate; a light-emitting unit located on the substrate; and the above-mentioned coating covering the substrate and the light-emitting unit.

The coating provided in one embodiment of the present disclosure includes modified particles and reactive compounds. The modified particles include a core; and a silane coupling agent having an epoxy group or a silane coupling agent having a double bond, which is grafted to the surface of the core. The core includes (1) an oxide of zinc and titanium, (2) an oxide of zirconium and titanium, or (3) an oxide of zinc and zirconium. When the core includes (1) an oxide of zinc and titanium, the weight ratio of zinc to titanium is 1:0.4 to 1:0.9. If the proportion of zinc is too high, precipitation is likely to occur, and the core is not easy to maintain a crystalline stable state. If the proportion of titanium is too high, the core is likely to gel quickly during the reaction process and cannot be used. When the core includes (2) oxides of zirconium and titanium, the weight ratio of zirconium to titanium is 1:0.1 to 1:2. If the ratio of titanium is too high, the color is dark yellow and cannot maintain high transmittance and low b* value in the visible light band. When the core includes (3) oxides of zinc and zirconium, the weight ratio of zinc to zirconium is 1:0.8 to 1:2. In one embodiment, the weight ratio of zinc to zirconium is 1:0.8 to 1:1.8. If the ratio of zinc is too high, precipitation occurs. If the ratio of zirconium is too high, excessive linkage occurs and gelation occurs.

When a silane coupling agent having an epoxy group is grafted onto the surface of the core, the reactive compound includes a polyepoxy compound that does not contain silicon and a polyepoxy compound that contains silicon. When a silane coupling agent having a double bond is grafted onto the surface of the core, the reactive compound includes a polydouble bond compound.

In one embodiment, the core is formed by hydrolyzing a zinc source to form zinc oxide, which is then condensed with a titanium source to form the core. The core mainly contains titanium, zinc, and oxygen, such as an oxide of titanium and zinc, and has a plurality of hydroxyl and alkoxy groups on its surface. It is worth noting that the core is an oxide of titanium and zinc, rather than a mixture of titanium oxide and zinc oxide (e.g., there is no bond between the titanium of the titanium oxide and the oxygen of the zinc oxide, and there is no bond between the oxygen of the titanium oxide and the zinc of the zinc oxide). Compared with the oxide core of titanium and zinc, the core of the mixture of titanium oxide and zinc oxide is solid precipitated. Then, a silane coupling agent with an epoxy group or a silane coupling agent with a double bond is reacted with the core, so that the Si-O-alkyl group of the silane reacts with the -OR (R=H or alkyl group) on the surface of the core to form a Zn/Ti-O-Si bond, that is, the silane coupling agent is grafted onto the surface of the core. It is worth noting that the above reaction is only one of the methods for forming modified particles, not the only method. Those with general knowledge in this technical field can use appropriate reagents to form the above modified particles.

In one embodiment, the core is formed by condensation reaction of a zirconium source and a titanium source. The core mainly contains titanium, zirconium, and oxygen, such as an oxide of titanium and zirconium, and has a plurality of hydroxyl and alkoxy groups on its surface. It is worth noting that the core is an oxide of titanium and zirconium, rather than a mixture of titanium oxide and zirconium oxide (e.g., there is no bond between the titanium of titanium oxide and the oxygen of zirconium oxide, and there is no bond between the oxygen of titanium oxide and the zirconium of zirconium oxide). Compared with the oxide core of titanium and zirconium, the core of the mixture of titanium oxide and zirconium oxide is solid precipitated. Then, a silane coupling agent with an epoxy group or a silane coupling agent with a double bond is reacted with the core, so that the Si-O-alkyl group of the silane reacts with the -OR (R=H or alkyl group) on the surface of the core to form a Zr/Ti-O-Si bond, that is, the silane coupling agent is grafted onto the surface of the core. It is worth noting that the above reaction is only one of the methods for forming modified particles, not the only method.

In one embodiment, the core is formed by hydrolyzing a zinc source to form zinc oxide, which is then condensed with a zirconium source to form the core. The core mainly contains zinc, zirconium, and oxygen, such as an oxide of zinc and zirconium, and has a plurality of hydroxyl and alkoxy groups on its surface. It is worth noting that the core is an oxide of zinc and zirconium, rather than a mixture of zinc oxide and zirconium oxide (e.g., there is no bond between the zinc of zinc oxide and the oxygen of zirconium oxide, and there is no bond between the oxygen of zinc oxide and the zirconium of zirconium oxide). Compared with the oxide core of zinc and zirconium, the core of the mixture of zinc oxide and zirconium oxide is solid precipitated. Then, a silane coupling agent with an epoxy group or a silane coupling agent with a double bond is reacted with the core, so that the Si-O-alkyl group of the silane reacts with the -OR (R=H or alkyl group) on the surface of the core to form a Zn/Zr-O-Si bond, that is, the silane coupling agent is grafted onto the surface of the core. It is worth noting that the above reaction is only one of the methods for forming modified particles, not the only method. Those with general knowledge in this technical field can use appropriate reagents to form the above modified particles.

In some embodiments, the zinc source may be zinc acetate, zinc perchlorate, or zinc bromide. In some embodiments, the titanium source may be titanium isopropoxide, titanium tetrachloride, or titanium butoxide. In some embodiments, the zirconium source may be zirconium n-propoxide, zirconium isopropoxide, or zirconium tetrachloride.

In some embodiments, the ratio of the total weight of zinc and titanium in the core to the weight of the silane coupling agent having an epoxy group or a silane coupling agent having a double bond is 1:0.1 to 1:3, or 1:0.1 to 1:1.5. In some embodiments, the ratio of the total weight of zirconium and titanium in the core to the weight of the silane coupling agent having an epoxy group or a silane coupling agent having a double bond is 1:0.1 to 1:3, or 1:0.1 to 1:1.5. In some embodiments, the ratio of the total weight of zinc and zirconium in the core to the weight of the silane coupling agent having an epoxy group or a silane coupling agent having a double bond is 1:0.1 to 1:3, or 1:0.1 to 1:1.5. If the proportion of silane coupling agent is too low, film formation will fail. If the proportion of silane coupling agent is too high, the refractive index of the formed coating will be insufficient (e.g., less than 1.7).

In some embodiments, the average particle size of the core is 10nm to 120nm, or 15nm to 55nm. If the average particle size of the core is too small, the coating will not be able to produce a high refractive index effect. If the average particle size of the core is too large, the coating penetration will be lower than 90% and the light collection effect cannot be improved.

In some embodiments, the silane coupling agent having an epoxy group includes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

，其中R為甲基或乙基，且n=1-3。 In some embodiments, the silane coupling agent having a double bond includes 3-trimethoxysilane propyl acrylate, 3-(triethoxysilyl)propyl isocyanate, or

, wherein R is methyl or ethyl, and n=1-3.

In some embodiments, the weight ratio of the core to the reactive compound is 1:0.2 to 1:0.8. If the ratio of the reactive compound is too low, the formed coating is split. If the ratio of the reactive compound is too high, the refractive index of the coating is insufficient.

In some embodiments, the weight ratio of the silicon-free polyepoxide to the silicon-containing polyepoxide is 1:0.4 to 1:1. If the ratio of the silicon-free polyepoxide is too low, the formed coating is split. If the ratio of the silicon-free polyepoxide is too high, the penetration of the coating is insufficient.

、

k=1~6、或上述之組合。 In some embodiments, the silicon-free polyepoxide comprises a long carbon chain, a benzene ring, or a cyclohexane structure, and has a viscosity of <1000 cP at 25°C. For example, the silicon-free polyepoxide comprises

,

k=1~6, or a combination of the above.

，其中m=1~6，n=1~6、

，其中n=1~6、或上述之組合。 In some embodiments, the silicon-containing polyepoxide comprises a long carbon chain, a benzene ring, or a cyclohexane structure, and has a viscosity of <1000 cP at 25°C. For example, the silicon-containing polyepoxide comprises

, where m=1~6, n=1~6,

, where n=1~6, or a combination of the above.

、

，其中a=2~6且b=2~6、或上述之組合。 In some embodiments, the multi-bibond compound comprises a long carbon chain, a benzene ring, or a cyclohexane structure, and has a viscosity of <1000 cP at 25°C. For example, the multi-bibond compound comprises

,

, where a=2~6 and b=2~6, or a combination of the above.

The coating provided in one embodiment of the present invention is formed by the reaction of the above-mentioned coating. For example, if the core surface of the modified particles in the coating is grafted with a silane coupling agent having an epoxy group, and the corresponding reactive compounds include a polyepoxy compound without silicon and a polyepoxy compound containing silicon, the coating may further include a catalytic amount of a crosslinking agent. The crosslinking agent can open the epoxy ring to achieve a crosslinking effect. In some embodiments, the weight ratio of the coating to the crosslinking agent is between 1:0.09 and 1:0.13. If the amount of the crosslinking agent is too low, the coating cannot be crosslinked to form a film during the reaction process. If the amount of the crosslinking agent is too high, the refractive index will be greatly reduced. In some embodiments, the crosslinking agent is a C ₂ -C ₆ amine compound, a C ₂ -C ₆ alcohol compound, or a C ₂ -C ₆ acid compound. In some embodiments, the crosslinking agent is HO-(CH ₂ ) _n -NH ₂ , and n is 2 to 4. For example, if the core surface of the modified particles in the coating is grafted with a silane coupling agent having a double bond, and the corresponding reactive compound includes a multi-double bond compound, the coating may further include a catalytic amount of a free radical initiator. For example, the weight ratio of the coating to the free radical initiator may be 1:0.09 to 1:0.13. The free radical initiator can be a thermal initiator or a photoinitiator, which can generate free radicals after being exposed to light or heated to crosslink the double bonds of the silane coupling agent and the multi-double bond compound.

In some embodiments, the coating can be applied to the substrate by scraper coating or rotation coating, and any active unit or passive unit can be present in and on the substrate. The coating is then cured to form a coating. In some embodiments, the coating has a thickness of 20 microns to 40 microns, a refractive index of 1.70 to 2.4, and a transmittance of 90% to 99.5%. If the thickness of the coating is too small, it cannot effectively protect the active unit or passive unit it covers. If the refractive index is too small, it cannot avoid light loss caused by the difference in refractive index when covering a unit with a high refractive index such as a micro-luminescent diode. If the coating has too low a penetration, it is not suitable as a light-transmitting protective layer (such as a protective layer covering a light-emitting unit).

The light-emitting device provided in one embodiment of the present disclosure includes: a substrate; a light-emitting unit located on the substrate; and the above-mentioned coating covering the light-emitting unit and the substrate. Since the coating of the embodiment of the present disclosure has sufficient thickness, refractive index, and transmittance, the light-emitting unit can be effectively protected. In some embodiments, the light-emitting unit can be a light-emitting diode, such as an organic light-emitting diode, an inorganic light-emitting diode, or other suitable light-emitting diodes. Since the refractive index of the material of the light-emitting unit is generally greater than 2, if the refractive index of the film material covering the light-emitting unit is too small (for example, less than 1.7), the difference in refractive index will cause light loss. It is worth noting that although the coating disclosed herein is mainly used to protect the light-emitting unit in the light-emitting device, it should be understood that the film material can also be used to protect other units other than the light-emitting unit, and is not limited to the light-emitting device.

In summary, the organic-inorganic composite coating disclosed in the present invention can simultaneously include the advantages of light weight, flexibility, high impact resistance, and convenient process of organic molecules, as well as high refractive index, high chemical resistance, and high heat resistance of inorganic materials. Through the design of composite materials, the refractive index can be adjusted and high transmittance can be maintained, and the coating thickness can be further increased. In short, the coating provided by the present disclosure can provide a coating with high transmittance, high refractive index, and high film thickness to achieve the effect of protecting units (such as high refractive index light-emitting diodes).

In order to make the above contents and other purposes, features, and advantages of this disclosure more clearly understood, the following is a detailed description of the preferred embodiments as follows:

[Implementation example]

In the following embodiments, the transmittance of the coating is measured by a UV/visible spectrometer, the band is defined as the value obtained by the reference point of 450nm, and the refractive index is measured by a thin film analyzer (N & K analyze). The particle size of the core particles is measured by a multi-specimen nanoparticle size measurement system (Otsuka nanoSAQLA), the measurement range is 0.6nm~10μm, and the accuracy is within ±2%. In the following embodiments, the viscosity is measured according to ASTM D1084, and the machine model is Brookfield Viscometer DV-III Ultra.

Synthesis example 1

Take 5g of zinc acetate, 20g of isopropanol, and 1.9g of ethanolamine, heat to 80℃ to dissolve and react for 5 minutes. Then add 10g of titanium isopropoxide and 0.25g of isopentanedione, react at 80℃ for 8 hours to form a core containing zinc and titanium oxides, and the weight ratio of zinc to titanium is 1:0.6. Then add 2.2g of 3-glycidyloxypropyltrimethoxysilane for surface modification. The weight ratio of the total weight of zinc and titanium in the core to 3-glycidyloxypropyltrimethoxysilane is 1:0.15, so that Si-O-CH ₃ of silane reacts with -OR (R=H or CH(CH ₃ ) ₂ ) on the surface of the core to form Zn/Ti-O-Si bonds, that is, silane is grafted to the core surface to form a dispersion of modified particles, and the average core particle size is 80nm.

Synthesis example 2

Take 5g of zinc ester, 20g of isopropanol, and 1.9g of ethanolamine, heat to 80℃ to dissolve and react for 5 minutes. Then add 10g of titanium isopropoxide and 0.25g of isopentanedione, react at 80℃ for 8 hours to form a core containing zinc and titanium oxides, and the weight ratio of zinc to titanium is 1:0.6. Then add 2.2g of 3-glycidyloxypropyltrimethoxysilane for surface modification. The weight ratio of the total weight of zinc and titanium in the core to 3-glycidyloxypropyltrimethoxysilane is 1:0.15, so that the Si-O-CH3 of silane reacts with the -OR (R=H or CH(CH ₃ ) ₂ ) on the surface of the core to form a Zn/Ti-O-Si bond, that is, silane is grafted to the core surface to form a dispersion of modified particles, and the average core particle size is 80nm. Finally, the isopropyl alcohol is replaced by toluene.

Synthesis example 3

15g of zirconium n-propoxide, 15g of titanium isopropoxide, 20g of isopropanol, and 0.25g of isopentanedione were reacted at 80°C for 8 hours to form a core containing zirconium and titanium oxides in a weight ratio of 1:0.9. 3g of 3-glycidyloxypropyltrimethoxysilane was then added for surface modification. The weight ratio of the total weight of zirconium and titanium in the core to 3-glycidyloxypropyltrimethoxysilane is 1:0.1, so that Si-O-CH ₃ of silane reacts with -OR (R=H or CH(CH ₃ ) ₂ ) on the surface of the core to form Zr/Ti-O-Si bonds, that is, silane is grafted to the core surface to form a dispersion of modified particles, and the average core particle size is 40nm.

Synthesis example 4

Take 5g of zinc acetate, 20g of isopropyl alcohol, and 1.9g of ethanolamine, heat to 80℃ to dissolve and react for 5 minutes. Then add 10g of titanium isopropyl alcohol and 0.25g of isopentanedione, react at 80℃ for 8 hours to form a core containing zinc and titanium oxides, and the weight ratio of zinc to titanium is 1:0.6. Then add 2.2g of 3-trimethoxysilane propyl acrylate for surface modification. The weight ratio of the total weight of zinc and titanium in the core to 3-trimethoxysilane propyl acrylate is 1:0.15, so that the Si-O-CH ₃ of the silane reacts with the -OR (R=H or CH(CH ₃ ) ₂ ) on the surface of the core to form a Zn/Ti-O-Si bond, that is, the silane is grafted to the surface of the core to form a dispersion of modified particles, and the average core particle size is 75nm.

Synthesis example 5

Take 5g of zinc acetate, 20g of isopropanol, and 3mL of KOH (0.48M), heat to 80℃ to dissolve and react for 5 minutes. Then add 10g of zirconium n-propoxide and react at 80℃ for 8 hours to form a core containing zinc and zirconium oxides, and the weight ratio of zinc to zirconium is 1:1.8. Then add 2.2g of 3-trimethoxysilane propyl acrylate for surface modification. The weight ratio of the total weight of zinc and zirconium in the core to 3-trimethoxysilane propyl acrylate is 1:0.15, so that the Si-O-CH ₃ of the silane reacts with the -OR (R=H or CH(CH ₃ ) ₂ ) on the surface of the core to form a Zn/Zr-O-Si bond, that is, the silane is grafted to the core surface to form a dispersion of modified particles, and the average core particle size is 79nm.

Verification example

，其中m=1~6且n=1~6)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述含矽的環氧化合物GT1250可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，GT1250可作為反應性化合物的選擇之一。 Take 0.25g of silicon-containing polyepoxide GT1250 (purchased from Guangke Industrial, its structure is

, wherein m=1~6 and n=1~6) is mixed with a dispersion containing 1g of the modified particles of Synthesis Example 1 and still maintains a liquid state without phase separation and no precipitation. From the above, it can be seen that the silicon-containing epoxy compound GT1250 is compatible with the modified particles. The above solution can be coated and cured by heat baking (baking at 80℃ for 10 minutes and baking at 120℃ for 10 minutes) to form a dry film with a thickness of 5 microns. In summary, GT1250 can be selected as one of the reactive compounds.

)與含有1g的合成例1的改質粒子的分散液混摻後產生分相或析出，取0.25g的含矽的多環氧化合物ESP-EDTP0204與合成例2的改質粒子1g混摻後產生分相或析出。由上述可知，上述含矽的環氧化合物ESP-EDTP0204與改質粒子不相容。綜上所述，ESP-EDTP0204不可作為反應性化合物。 Take 0.25g of silicon-containing polyepoxide ESP-EDTP0204 (self-synthesized, with the structure

) was mixed with a dispersion containing 1 g of the modified particles of Synthesis Example 1, and phase separation or precipitation occurred. 0.25 g of the silicon-containing polyepoxide ESP-EDTP0204 was mixed with 1 g of the modified particles of Synthesis Example 2, and phase separation or precipitation occurred. As can be seen from the above, the silicon-containing epoxy compound ESP-EDTP0204 is incompatible with the modified particles. In summary, ESP-EDTP0204 cannot be used as a reactive compound.

)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述含矽的環氧化合物SIT8715.6可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，SIT8715.6可作為反應性化合物的選擇之一。 Take 0.25 g of silicon-containing polyepoxide SIT8715.6 (purchased from Gelest, its structure is

) is mixed with the dispersion containing 1g of the modified particles of Synthesis Example 1, and still maintains a liquid state without phase separation and no precipitation. From the above, it can be seen that the silicon-containing epoxy compound SIT8715.6 is compatible with the modified particles. The above solution can be coated and cured by heat baking (baking at 80°C for 10 minutes and baking at 120°C for 10 minutes) to form a dry film with a thickness of 5 microns. In summary, SIT8715.6 can be selected as one of the reactive compounds.

)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出，取0.25g的含矽的多環氧化合物SIT7281.5與含有1g的合成例2的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，含矽的環氧化合物SIT7281.5可與改質粒子相容。但兩種溶液不可塗佈 熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，SIT7281.5不可作為反應性化合物的選擇之一。 Take 0.25 g of silicon-containing polyepoxide SIT7281.5 (purchased from Gelest, its structure is

) was mixed with a dispersion containing 1g of the modified particles of Synthesis Example 1, and it still maintained a liquid state without phase separation and no precipitation. After taking 0.25g of the silicon-containing polyepoxy compound SIT7281.5 and mixing it with a dispersion containing 1g of the modified particles of Synthesis Example 2, it still maintained a liquid state without phase separation and no precipitation. From the above, it can be seen that the silicon-containing epoxy compound SIT7281.5 is compatible with the modified particles. However, the two solutions cannot be applied and cured by heat baking (baking at 80°C for 10 minutes and baking at 120°C for 10 minutes) to form a 5-micron thick dry film. In summary, SIT7281.5 cannot be selected as one of the reactive compounds.

k=1~6)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述不含矽的環氧化合物YX7400可與改質粒子相容。上述合成例1溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，YX7400可作為反應性化合物的選擇之一。 Take 0.25g of silicon-free polyepoxide YX7400 (Mitsubishi Chemical, the structure of which is

k=1~6) is mixed with the dispersion containing 1g of the modified particles of Synthesis Example 1 and still maintains a liquid state without phase separation and no precipitation. From the above, it can be seen that the above silicon-free epoxy compound YX7400 is compatible with the modified particles. The above Synthesis Example 1 solution can be coated and cured by heat baking (baking at 80℃ for 10 minutes and baking at 120℃ for 10 minutes) to form a 5 micron thick dry film. In summary, YX7400 can be selected as one of the reactive compounds.

)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述不含矽的環氧化合物412P可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，412P可作為反應性化合物的選擇之一。 Take 0.25 g of silicon-free polyepoxide 412P (purchased from Double Key Chemicals, with the structure

) is mixed with a dispersion containing 1 g of the modified particles of Synthesis Example 1, and still maintains a liquid state without phase separation and no precipitation. From the above, it can be seen that the above silicon-free epoxy compound 412P is compatible with the modified particles. The above solution can be coated and heat-cured (baked at 80°C for 10 minutes and baked at 120°C for 10 minutes) to form a dry film with a thickness of 5 microns. In summary, 412P can be selected as one of the reactive compounds.

，其中n=1~6)與含 有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出、取0.25g的含矽的多環氧化合物DMS-EC13與含有1g的合成例2的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述含矽的環氧化合物DMS-EC13可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，DMS-EC13可作為反應性化合物的選擇之一。 Take 0.25 g of silicon-containing polyepoxide DMS-EC13 (purchased from Gelest, its structure is

, wherein n=1~6) is mixed with a dispersion containing 1g of the modified particles of Synthesis Example 1 and still maintains a liquid state without phase separation and no precipitation. 0.25g of the silicon-containing polyepoxy compound DMS-EC13 is mixed with a dispersion containing 1g of the modified particles of Synthesis Example 2 and still maintains a liquid state without phase separation and no precipitation. From the above, it can be seen that the silicon-containing epoxy compound DMS-EC13 is compatible with the modified particles. The above solution can be applied and hot-baked (baked at 80°C for 10 minutes, and baked at 120°C for 10 minutes) to form a 5-micron thick dry film. In summary, DMS-EC13 can be selected as one of the reactive compounds.

，其中m=1~6，n=1~6)與含有1g的合成例1的改質粒子的分散液混摻後產生分相或析出。由上述可知，上述含矽的環氧化合物ECMS-924與改質粒子不相容。綜上所述，ECMS-924不可作為反應性化合物的選擇之一。 Take 0.25 g of silicon-containing polyepoxide ECMS-924 (purchased from Gelest, its structure is

, wherein m=1~6, n=1~6) was mixed with a dispersion containing 1g of the modified particles of Synthesis Example 1, resulting in phase separation or precipitation. As can be seen from the above, the silicon-containing epoxy compound ECMS-924 is incompatible with the modified particles. In summary, ECMS-924 cannot be selected as one of the reactive compounds.

)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述含矽的環氧化合物SIB-1110可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘) 成5微米厚的乾膜。綜上所述，SIB-1110可作為反應性化合物的選擇之一。 Take 0.25 g of silicon-containing polyepoxide SIB-1110 (purchased from Gelest, its structure is

) was mixed with the dispersion containing 1g of the modified particles of Synthesis Example 1, and still maintained a liquid state without phase separation and no precipitation. From the above, it can be seen that the silicon-containing epoxy compound SIB-1110 is compatible with the modified particles. The above solution can be coated and cured by heat baking (baking at 80°C for 10 minutes and baking at 120°C for 10 minutes) to form a dry film with a thickness of 5 microns. In summary, SIB-1110 can be selected as one of the reactive compounds.

)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述不含矽的環氧化合物HDGE可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，HDGE可作為反應性化合物的選擇之一。 Take 0.25 g of silicon-free polyepoxide HDGE (1,6-hexanediol diglycidyl ether) (purchased from Aldrich, its structure is

) is mixed with the dispersion containing 1g of the modified particles of Synthesis Example 1, and still maintains a liquid state without phase separation and no precipitation. From the above, it can be seen that the above silicon-free epoxy compound HDGE is compatible with the modified particles. The above solution can be coated and heat-cured (baked at 80°C for 10 minutes and baked at 120°C for 10 minutes) to form a dry film with a thickness of 5 microns. In summary, HDGE can be selected as one of the reactive compounds.

)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述不含矽的環氧化合物YL983U可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，YL983U可作為反應性化合物的選擇之一。 Take 0.25g of silicon-free polyepoxide YL983U (purchased from Mitsubishi Chemical, its structure is

) is mixed with the dispersion containing 1g of the modified particles of Synthesis Example 1 and still maintains a liquid state without phase separation and no precipitation. From the above, it can be seen that the above silicon-free epoxy compound YL983U is compatible with the modified particles. The above solution can be coated and heat-cured (baked at 80℃ for 10 minutes and 120℃ for 10 minutes) to form a dry film with a thickness of 5 microns. In summary, YL983U can be selected as one of the reactive compounds.

)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由 上述可知，上述不含矽的環氧化合物YL980可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，YL 980可作為反應性化合物的選擇之一。 Take 0.25 g of silicon-free polyepoxide YL 980 (purchased from Mitsubishi Chemical, its structure is

) is mixed with the dispersion containing 1g of the modified particles of Synthesis Example 1, and still maintains a liquid state without phase separation and no precipitation. From the above, it can be seen that the above silicon-free epoxy compound YL980 is compatible with the modified particles. The above solution can be coated and heat-cured (baked at 80℃ for 10 minutes and 120℃ for 10 minutes) to form a dry film with a thickness of 5 microns. In summary, YL 980 can be selected as one of the reactive compounds.

)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述多雙鍵化合物SR238可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，SR238可作為反應性化合物的選擇之一。 Take 0.25g of the multi-double bond compound SR238 (purchased from Sartomer AMERICAS, its structure is

) was mixed with the dispersion containing 1 g of the modified particles of Synthesis Example 1, and still maintained a liquid state without phase separation and no precipitation. From the above, it can be seen that the multi-double bond compound SR238 is compatible with the modified particles. The above solution can be coated and cured by heat baking (baking at 80°C for 10 minutes and baking at 120°C for 10 minutes) to form a dry film with a thickness of 5 microns. In summary, SR238 can be selected as one of the reactive compounds.

，其中a=2~6且b=2~6)與含有1g的合成例1的改質粒子的分散液混摻後仍維持無分相之液態以及無析出。由上述可知，上述多雙鍵化合物SR601可與改質粒子相容。上述溶液可塗佈熱烤固化(80℃烘烤10分鐘，以及120℃烘烤10分鐘)成5微米厚的乾膜。綜上所述，SR601可作為反應性化合物的選擇之一。 Take 0.25g of the multi-double bond compound SR601 (purchased from Sartomer AMERICAS, its structure is

, wherein a=2~6 and b=2~6) is mixed with a dispersion containing 1g of the modified particles of Synthesis Example 1 and still maintains a liquid state without phase separation and no precipitation. From the above, it can be seen that the multi-double bond compound SR601 is compatible with the modified particles. The above solution can be coated and cured by heat baking (baking at 80℃ for 10 minutes and baking at 120℃ for 10 minutes) to form a dry film with a thickness of 5 microns. In summary, SR601 can be selected as one of the reactive compounds.

Example 1

Take 8 parts by weight of the dispersion of modified particles of Synthesis Example 1, 1 part by weight of silicon-free polyepoxy HDGE, and 1 part by weight of silicon-containing polyepoxy SIB-1110, and then remove 3 parts by weight of the solvent to form a solution with a viscosity of 30.3 cP at 25°C as a coating. Apply a 50-micron-thick wet film on a glass substrate with a scraper, and heat-bake (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a 20-micron-thick coating. The coating has a transmittance of 96.1%, a Haze of 1.91 (fog-light scattering value), and a refractive index of 2.01 for light with a wavelength of 550nm.

Example 2

After mixing 7 parts by weight of the dispersion of modified particles of Synthesis Example 1, 1.8 parts by weight of the silicon-free polyepoxy compound HDGE, and 1.2 parts by weight of the silicon-containing polyepoxy compound SIB-1110, 3 parts by weight of the solvent was removed to form a solution with a viscosity of 35.6 cP at 25°C as a coating, which was coated with a scraper to form a 50 micron thick wet film on a glass substrate, and then cured by heat baking (baking at 80°C for 10 minutes and 120°C for 10 minutes) to form a 22 micron thick coating. The coating had a transmittance of 97.0%, a Haze of 1.03 (fog-light scattering value), and a refractive index of 1.85 for light with a wavelength of 550 nm. The penetration was then tested at 110°C for 500 hours, and the change rate was ≤1.61%.

Implementation Example 3

Take 7 parts by weight of the dispersion of modified particles of Synthesis Example 1, 1.5 parts by weight of silicon-free polyepoxy HDGE, and 1.5 parts by weight of silicon-containing polyepoxy SIB-1110, and then remove 3 parts by weight of the solvent to form a solution with a viscosity of 32.3 cP at 25°C as a coating. Apply a 50-micron-thick wet film on a glass substrate with a scraper, and heat-bake and cure (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a 21-micron-thick coating. The coating has a transmittance of 96.7%, a Haze of 1.33 (fog-light scattering value), and a refractive index of 1.88 for light with a wavelength of 550nm.

Example 4

Take 6 parts by weight of the dispersion of modified particles of Synthesis Example 1, 2 parts by weight of silicon-free polyepoxy HDGE, and 2 parts by weight of silicon-containing polyepoxy SIB-1110, and then remove 3 parts by weight of the solvent to form a solution with a viscosity of 41.0 cP at 25°C as a coating. Apply a 50-micron-thick wet film on a glass substrate with a scraper, and heat-bake (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a 30-micron-thick coating. The coating has a transmittance of 95.6%, a Haze of 1.10 (fog-light scattering value), and a refractive index of 1.80 for light with a wavelength of 550nm.

Example 5

Take 7 parts by weight of the dispersion of modified particles of Synthesis Example 3, 1.5 parts by weight of silicon-free polyepoxy HDGE, and 1.5 parts by weight of silicon-containing polyepoxy SIB-1110, and then remove 3 parts by weight of the solvent to form a solution with a viscosity of 5.1 cP at 25°C as a coating. Apply a 50-micron-thick wet film on a glass substrate with a scraper, and heat-bake (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a 23-micron-thick coating. The coating has a transmittance of 96.3%, a Haze of 0.71 (fog-light scattering value), and a refractive index of 1.87 for light with a wavelength of 550nm.

Example 6

Take 5 parts by weight of the dispersion of modified particles of Synthesis Example 1, 2.5 parts by weight of silicon-free polyepoxy HDGE, and 2.5 parts by weight of silicon-containing polyepoxy SIB-1110, and then remove 3 parts by weight of the solvent to form a solution with a viscosity of 48 cP at 25°C as a coating. Apply a 50-micron-thick wet film on a glass substrate with a scraper, and heat-bake (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a 36-micron-thick coating. The coating has a transmittance of 98.9%, a Haze of 1.54 (fog-light scattering value), and a refractive index of 1.77 for light with a wavelength of 550nm.

Comparative example 1

After mixing 9 weight parts of the dispersion of modified particles of Synthesis Example 1, 0.5 weight parts of the silicon-free polyepoxy compound HDGE, and 0.5 weight parts of the silicon-containing polyepoxy compound SIB-1110, 3 weight parts of the solvent were removed to form a coating, which was applied with a scraper to form a 50 micron thick wet film on a glass substrate. The coating was cracked during heat curing (baking at 80°C for 10 minutes and 120°C for 10 minutes).

Comparative example 2

After mixing 7 parts by weight of the modified particle dispersion of Synthesis Example 1 with 3 parts by weight of the silicon-free polyepoxy compound HDGE, 3 parts by weight of the solvent was removed to form a coating, which was then applied with a scraper to form a 50 micron thick wet film on a glass substrate, and then cured by heat baking (baking at 80°C for 10 minutes and 120°C for 10 minutes) to form a coating. The penetration of the coating is <80%.

Comparative example 3

Take 7 parts by weight of the dispersion of modified particles of Synthesis Example 1, 2.4 parts by weight of silicon-free polyepoxy HDGE, and 0.6 parts by weight of silicon-containing polyepoxy SIB-1110, and then remove 3 parts by weight of the solvent to form a coating. Apply a 50-micron-thick wet film on a glass substrate with a scraper, and heat-bake (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a coating. The penetration of the coating is <80%.

Comparative example 4

Take 7 parts by weight of the dispersion of modified particles of Synthesis Example 1, 1.2 parts by weight of silicon-free polyepoxy HDGE, and 1.8 parts by weight of silicon-containing polyepoxy SIB-1110, and then remove 3 parts by weight of the solvent to form a coating. Use a scraper to apply a 50 micron thick wet film on a glass substrate, and heat-bake and cure (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a coating. The coating will crack after being placed at room temperature for a period of time.

Comparative example 5

Take 7 parts by weight of the dispersion of modified particles of Synthesis Example 1, 0.6 parts by weight of silicon-free polyepoxy HDGE, and 2.4 parts by weight of silicon-containing polyepoxy SIB-1110, and then remove 3 parts by weight of the solvent to form a coating. Use a scraper to apply a 50 micron thick wet film on a glass substrate, and heat-bake and cure (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a coating. The coating will crack after being placed at room temperature for a period of time.

Comparative example 6

Take 7 parts by weight of the dispersion of modified particles of Synthesis Example 1 and 3 parts by weight of the silicon-containing polyepoxy compound SIB-1110, and then remove 3 parts by weight of the solvent to form a coating. Use a scraper to apply a 50 micron thick wet film on a glass substrate, and heat-bake and cure (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a coating. The coating will crack after being placed at room temperature for a period of time.

Comparative example 7

Take a dispersion containing 7 parts by weight of the core (unmodified) of Synthesis Example 1, 1.5 parts by weight of the silicon-free polyepoxy compound HDGE, and 1.5 parts by weight of the silicon-containing polyepoxy compound SIB-1110, and then remove 3 parts by weight of the solvent to form a coating. Use a scraper to apply a 50-micron-thick wet film on a glass substrate. The coating cracks during thermal curing (baking at 80°C for 10 minutes and 120°C for 10 minutes).

Example 7

After mixing 8 parts by weight of the dispersion of modified particles of Synthesis Example 4, 2 parts by weight of the multi-double bond compound SR238, and 0.01 parts by weight of the initiator azobisisobutyronitrile (AIBN), 3 parts by weight of the solvent was removed to form a solution with a viscosity of 6.8 cP at 25°C as a coating, which was coated with a doctor blade to form a 50 micron thick wet film on a glass substrate, baked at 80°C for 10 minutes, and UV cured (1500 J/cm ² ) for 1 minute to form a 21 micron thick coating. The coating had a transmittance of 95.8%, a Haze of 1.91 (fog-light scattering value), and a refractive index of 1.88 for light with a wavelength of 550 nm.

Example 8

After mixing 7 parts by weight of the dispersion of modified particles of Synthesis Example 4, 3 parts by weight of the multi-double bond compound SR238, and 0.01 parts by weight of the initiator azobisisobutyronitrile (AIBN), 3 parts by weight of the solvent was removed to form a solution with a viscosity of 5.9 cP at 25°C as a coating, which was coated with a doctor blade to form a 50 micron thick wet film on a glass substrate, baked at 80°C for 10 minutes, and UV cured (1500 J/cm ² ) for 1 minute to form a 22 micron thick coating. The coating had a transmittance of 96.3%, a Haze of 1.82 (fog-light scattering value), and a refractive index of 1.82 for light with a wavelength of 550 nm.

Example 9

Take 6 parts by weight of the dispersion of modified particles of Synthesis Example 4, 4 parts by weight of the multi-double bond compound SR238, and 0.01 parts by weight of the initiator azobisisobutyronitrile (AIBN), and remove 3 parts by weight of the solvent to form a solution with a viscosity of 6.5 cP at 25°C as a coating, apply it to a glass substrate with a doctor blade to form a 50 micron thick wet film, bake it at 80°C for 10 minutes, and UV cure (1500 J/cm ² ) for 1 minute to form a 23 micron thick coating. The coating has a transmittance of 96.9%, a Hz of 1.72 (haze-light scattering value), and a refractive index of 1.80 for light with a wavelength of 550 nm.

Example 10

After mixing 5 parts by weight of the dispersion of modified particles of Synthesis Example 4, 5 parts by weight of the multi-double bond compound SR238, and 0.01 parts by weight of the initiator azobisisobutyronitrile (AIBN), 3 parts by weight of the solvent was removed to form a solution with a viscosity of 6.1 cP at 25°C as a coating, which was coated with a doctor blade to form a 50 micron thick wet film on a glass substrate, baked at 80°C for 10 minutes, and UV cured (1500 J/cm ² ) for 1 minute to form a 23 micron thick coating. The coating had a transmittance of 98.2%, a Hz of 1.4 (haze-light scattering value), and a refractive index of 1.75 for light with a wavelength of 550 nm.

Comparative example 8

A dispersion containing 9 parts by weight of the modified particles of Synthesis Example 4, 1 part by weight of the multi-double bond compound SR238, and 0.01 parts by weight of the initiator azobisisobutyronitrile (AIBN) was taken, and 3 parts by weight of the solvent was removed to form a coating. After baking at 80°C for 10 minutes, the coating was UV cured (1500 J/ ^cm2 ) for 1 minute to cleave.

Example 11

Take 8 parts by weight of the dispersion of modified particles of Synthesis Example 5, 1.5 parts by weight of silicon-free polyepoxy HDGE, and 1.5 parts by weight of silicon-containing polyepoxy SIB-1110, and then remove 3 parts by weight of the solvent to form a solution with a viscosity of 46.7 cP at 25°C as a coating. Apply a 50-micron-thick wet film on a glass substrate with a scraper, and heat-bake (bake at 80°C for 10 minutes and 120°C for 10 minutes) to form a 25-micron-thick coating. The coating has a transmittance of 97.1%, a Haze of 0.47 (fog-light scattering value), and a refractive index of 1.82 for light with a wavelength of 550nm.

Although the present disclosure has been disclosed as above with several preferred embodiments, they are not intended to limit the present disclosure. Anyone with ordinary knowledge in the relevant technical field can make any changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be subject to the scope defined by the attached patent application.

without.

Claims (17)

A coating comprises: a modified particle comprising: a core; and a silane coupling agent having an epoxy group or a silane coupling agent having a double bond, grafted to the surface of the core; wherein the core comprises (1) an oxide of zinc and titanium, wherein the weight ratio of zinc to titanium is 1:0.4 to 1:0.9; (2) an oxide of zirconium and titanium, wherein the weight ratio of zirconium to titanium is 1:0.1 to 1:2; or (3) an oxide of zinc and zirconium, wherein the weight ratio of zinc to zirconium is 1:0.8 to 1:2; and a reactive compound; When the silane coupling agent having an epoxy group is grafted onto the surface of the core, the reactive compound includes a silicon-free polyepoxy compound and a silicon-containing polyepoxy compound. When the silane coupling agent having a double bond is grafted onto the surface of the core, the reactive compound includes a polydouble bond compound. A coating as claimed in claim 1, wherein the weight ratio of the total weight of zinc and titanium, the total weight of zirconium and titanium, or the total weight of zinc and zirconium in the core to the silane coupling agent having an epoxy group or the silane coupling agent having a double bond is 1:0.1 to 1:3. A coating as claimed in claim 1, wherein the average particle size of the core is 10 nm to 120 nm. The coating of claim 1, wherein the silane coupling agent having an epoxy group includes 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane. The coating of claim 1, wherein the silane coupling agent having a double bond comprises 3-trimethoxysilane propyl acrylate, 3-(triethoxysilyl)propyl isocyanate, or , wherein R is methyl or ethyl, and n=1-3. The coating of claim 1, wherein the weight ratio of the core to the reactive compound is 1:0.2 to 1:0.8. The coating of claim 1, wherein the weight ratio of the silicon-free polyepoxide to the silicon-containing polyepoxide is 1:0.4 to 1:1. The coating of claim 1, wherein the silicon-free polyepoxide comprises a long carbon chain, a benzene ring, or a cyclohexane structure, and has a viscosity of less than 1000 cP at 25°C. The coating of claim 1, wherein the silicon-free polyepoxide comprises , , , , , k=1~6, or a combination of the above. The coating of claim 1, wherein the silicon-containing polyepoxide comprises a long carbon chain, a benzene ring, or a cyclohexane structure, and has a viscosity of less than 1000 cP at 25°C. The coating of claim 1, wherein the silicon-containing polyepoxide comprises , , where m=1~6 and n=1~6, , , where n=1~6, or a combination of the above. A coating as claimed in claim 1, wherein the multi-double bond compound comprises a long carbon chain, a benzene ring, or a cyclohexane structure, and the viscosity at 25° C. is less than 1000 cP. The coating of claim 1, wherein the multi-double bond compound comprises , , where a=2~6 and b=2~6, or a combination of the above. A coating is formed by reacting the coating material of claim 1. A coating as claimed in claim 14, wherein the coating has a thickness of 20 microns to 40 microns, a refractive index of 1.7 to 2.4, and a transmittance of 90% to 99.5%. A light-emitting device, comprising: a substrate; a light-emitting unit located on the substrate; and a coating as claimed in claim 14, covering the substrate and the light-emitting unit. A light-emitting device as claimed in claim 16, wherein the coating has a thickness of 20 microns to 40 microns, a refractive index of 1.7 to 2.4, and a transmittance of 90% to 99.5%.