High-luminous-flux high-color-rendering three-primary-color fluorescent powder composition and preparation method thereof

Abstract

The invention discloses a high-luminous-flux high-color-rendering three-primary-color fluorescent powder composition and a preparation method thereof, and relates to the technical field of fluorescent powder materials. The composition comprises the following components in parts by mass: 100 parts of addition type organic silicon resin, 5-10 parts of hydrogen-containing silicone oil, 50-90 parts of three-primary-color fluorescent powder containing specific rare earth and 2-8 parts of modified porous nano silicon dioxide, a fluorine-containing silane coupling agent is grafted on the surface of the modified porous nano silicon dioxide. According to the composition, the compatibility and dispersity of a resin matrix are improved through fluorine-containing modified silicon dioxide, and a three-dimensional physical barrier network is constructed in a gel system in combination with a stepped cross-linking curing process, so that the gravity settling and migration of large-particle-size fluorescent powder particles are effectively inhibited, the phenomena of color temperature drift and non-uniform space chromaticity are improved, and the service life of the fluorescent powder is prolonged. Therefore, the product has excellent high luminous flux and high color rendering performance.

Description

Technical Field

[0001] This invention relates to the field of phosphor materials technology, specifically to a high luminous flux and high color rendering three-primary-color phosphor composition and its preparation method. Background Technology

[0002] In the field of fluorescent tube lighting technology, phosphors, as the core light conversion material, directly determine the luminous efficiency and final color quality of the lamp. To meet the demand for high color rendering white light lighting, a three-primary-color phosphor combination scheme, mixing blue, green, and red rare-earth materials, is commonly used in production. Phosphors with different physicochemical structures exhibit inherent differences in compatibility and dispersion in a matrix medium represented by silicone resin. Due to the varying surface characteristics of the powder particles, interfacial defects easily arise between the material and the resin matrix, leading to internal light scattering phenomena that cause a significant loss in the overall luminous flux of the lamp.

[0003] Phosphors of different colors exhibit significant differences in particle size and density. During the preparation of the fluorescent tube coating slurry and subsequent cross-linking and curing stages, gravity easily causes powder particles to settle and agglomerate within the gel system. This imbalance in the spatial distribution of powder directly leads to color temperature drift and spatial color inhomogeneity during lamp illumination, affecting the product's color consistency and reliability. Traditional phosphor colloidal curing processes often rely on one-step cross-linking at a constant temperature. The cross-linking process cannot effectively intervene in the dynamic rheological behavior of the phosphor, making it difficult to establish a spatial network structure to lock the particles in advance. Consequently, powder settling is difficult to fundamentally suppress in the early stages of curing. Insufficient refractive index matching between the matrix material and the phosphor, as well as the attenuation of the light transmittance of the encapsulation medium under long-term service conditions, further weaken the lamp's luminous flux maintenance and color rendering stability. How to achieve uniform dispersion of multi-color phosphors in the matrix and effectively suppress curing settling while ensuring high color rendering has become a crucial technical challenge to overcome in improving the overall color quality of fluorescent tubes. Summary of the Invention

[0004] The purpose of this invention is to address the problems existing in the prior art, such as poor dispersibility of multicolor phosphors in organosilicon resin matrices, easy occurrence of specific gravity sedimentation leading to color temperature drift and spatial color inhomogeneity, and the difficulty of effectively suppressing phosphor agglomeration by traditional curing processes. The invention provides a high luminous flux and high color rendering tricolor phosphor composition and its preparation method, which has uniform phosphor dispersion, good sedimentation suppression effect, high luminous flux and color rendering, and excellent encapsulation stability.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is: a high luminous flux and high color rendering tri-color phosphor composition and its preparation method, characterized in that the composition is composed of the following raw materials in parts by weight: 100 parts of addition-type organosilicon resin, 5-10 parts of hydrogen-containing silicone oil, 50-90 parts of tri-color phosphor containing specific rare earth elements, and 2-8 parts of modified porous nano-silica. The tri-color phosphor is composed of a mixture of three rare-earth phosphors that emit blue, green, and red light; The modified porous nano-silica surface is grafted with a fluorinated silane coupling agent. Furthermore, the fluorinated silane coupling agent is... .

[0006] Furthermore, the tri-color phosphor containing specific rare earth elements is composed of the following components in parts by weight: 15-25 parts by weight of divalent europium-activated barium magnesium aluminate (BaMgAl). 10 O 17 Eu 2+ Blue phosphor, 30-50 parts by weight of cerium trivalent activated yttrium aluminum garnet (Y3Al5O3). 12 :Ce 3+ Green phosphor, 5-15 parts by weight of divalent europium-activated calcium aluminum silicon nitride (CaAlSiN3:Eu) 2+ Red fluorescent powder.

[0007] Furthermore, the addition-type silicone resin is a vinylphenyl silicone resin with a phenyl mass fraction of 40%-50% and a vinyl mass fraction of 1%-3%; the hydrogen-containing silicone oil is a phenyl hydrogen-containing silicone oil with an active hydrogen mass fraction of 0.5%-1.5%.

[0008] Furthermore, the porous nano-silica has an average particle size of 50-150 nm and a specific surface area of ​​300-600 m². 2 / g, with a pore size of 10-20nm.

[0009] Furthermore, the method for preparing the modified porous nano-silica includes: (1) Surface activation treatment: 100 parts of porous nano silica are dispersed in 150-250 parts of anhydrous ethanol, 2-8 parts of deionized water are added, and ultrasonic treatment is carried out at 40-50℃ for 20-40 minutes to obtain activated silica dispersion. (2) Coordination grafting reaction: Add 10-25 parts of fluorinated phosphonate compound to the activated silica dispersion obtained in step (1), and add anhydrous ethanol to adjust the silica dispersion concentration in the reaction system to 12-25 wt%. Stir and reflux at 60-70℃ for 6-10 hours. (3) Post-processing: After the reaction is completed, the reaction solution is centrifuged and separated. The obtained solid product is washed with anhydrous ethanol 3-5 times, then vacuum dried at 50-70℃ for 12-20 hours, and then ground and sieved to obtain modified porous nano silica.

[0010] Modified porous nano-silica functions as a functional rheology modifier and refractive index adjusting medium in the system. Its mechanism of action lies in the surface grafting of fluorinated phosphonate compounds, achieving a transformation from simple physical filling to interface regulation and structural stabilization. Unmodified porous nano-silica is rich in hydroxyl groups, easily agglomerates, and has poor compatibility with organosilicon resins, only able to be passively dispersed. However, after grafting with fluorinated phosphonates, it forms coordination bonds with surface hydroxyl groups through PO bonds, introducing a fluorinated long-chain structure, significantly reducing surface energy, and improving its wettability and dispersion stability in the resin matrix. In the pre-curing stage, this modified material constructs a three-dimensional physical barrier network through the interfacial interaction between rigid fluorinated segments and the resin matrix, effectively inhibiting the migration and sedimentation of phosphor particles, and solving the problems of color temperature drift and spatial colorimetric inhomogeneity caused by specific gravity differences. At the same time, the introduction of fluorinated groups helps to regulate interfacial refractive index matching, reduce light scattering loss, and indirectly improve luminous flux. Therefore, through the synergistic effect of interface engineering and network barrier, this modified material transforms from a passive filler to an active structural stabilizing medium, improving the dispersion uniformity and sedimentation inhibition effect of phosphor in resin, and playing a good role in improving problems such as poor dispersion, severe sedimentation and light scattering loss.

[0011] A method for preparing a high luminous flux and high color rendering tri-color phosphor composition according to any one of claims 1-5, comprising the following preparation steps: S1. Matrix pre-dispersion: The modified porous nano silica is mixed with the addition-type silicone resin and subjected to high-shear milling to uniformly disperse the low-refractive-index modified material in the resin matrix, thereby obtaining a modified matrix adhesive. S2. Mixing and degassing: After the three primary color phosphors are mixed evenly, they are added to the modified matrix adhesive obtained in step S1. Hydrogen-containing silicone oil is added, and planetary stirring combining revolution and rotation is carried out under vacuum conditions to obtain a bubble-free mixed slurry. S3. Stepwise crosslinking and curing: After the mixed slurry obtained in step S2 is filled, it is first pre-cured at a first temperature, and then heated to a second temperature for complete crosslinking and curing of the resin phase.

[0012] Furthermore, in step S1, the high-shear grinding is performed using a three-roll mill, with the gap between the grinding rollers set to 10-20 μm and the grinding cycle being 3-5 times.

[0013] Furthermore, in step S2, the vacuum degree of the planetary stirrer under vacuum conditions is controlled to be -0.09MPa to -0.1MPa, the revolution speed is 800-1000r / min, and the rotation speed is 1200-1500r / min.

[0014] Furthermore, in step S3, the first temperature is set to 60-80℃, and the pre-curing time is 1-2 hours; the second temperature is set to 120-150℃, and the curing time is 2-4 hours.

[0015] Furthermore, the first temperature is lower than the rapid crosslinking threshold temperature of the addition-type silicone resin; In step S3, the mixed slurry after filling is placed in a temperature-controlled oven for step cross-linking and curing, and after the pre-curing is completed, the temperature is directly raised to the second temperature.

[0016] This invention achieves high luminous flux and high color rendering through the synergistic formulation of its components. The addition-type silicone resin and hydrogen-containing silicone oil form a crosslinkable matrix, providing an encapsulation environment for the tri-color phosphors. The tri-color phosphors containing specific rare earth elements emit tri-color light under blue light excitation, which mixes to form highly color-rendered white light. The key lies in the introduction of modified porous nano-silica, whose surface-grafted fluorinated phosphonate compounds alter the interfacial properties between the inorganic filler and the organic matrix. This fluorinated coupling agent is firmly grafted onto the silica surface via PO bonds, introducing low surface energy fluorinated segments. On one hand, this enhances the dispersibility of the modified material in the resin, preventing self-aggregation. On the other hand, during curing, the rigid fluorinated molecular chains form physical entanglements with the resin matrix, constructing a three-dimensional barrier network that effectively inhibits the migration and sedimentation of phosphor particles with different densities, solving the problems of color temperature drift and spatial chromaticity inhomogeneity caused by specific gravity differences in the prior art. Simultaneously, the fluorinated groups can adjust the interfacial refractive index, reducing light scattering loss and increasing luminous flux. Furthermore, the stepped crosslinking process utilizes the network formed during the pre-curing stage to further fix the phosphor, enhancing the sedimentation inhibition effect. Therefore, this invention achieves highly uniform dispersion and stability of the phosphor through the synergistic effect of interface engineering and network barrier, thereby obtaining high luminous flux and high color rendering.

[0017] Compared with the prior art, the beneficial effects of the present invention are: 1. Higher overall luminous flux: This invention introduces fluorine-modified porous nano-silica, which improves the compatibility between the inorganic filler and the resin matrix, promoting more uniform phosphor dispersion. The fluorine-containing groups help regulate the interfacial refractive index, reduce light scattering loss, and result in a significant increase in the overall luminous flux of the device.

[0018] 2. More uniform spatial color: To address the issue of easy sedimentation of multicolor phosphors, modified silica utilizes fluorine-containing segments to form a physical barrier network with the matrix, effectively suppressing particle migration. This mechanism significantly improves color temperature drift and spatial color uniformity, resulting in a more uniform light emission from the device.

[0019] 3. More stable encapsulation structure: The stepped curing process utilizes a pre-cured network to lock the phosphor in advance, further enhancing the anti-settling effect. This approach effectively controls the curing rheological behavior, resulting in a composition exhibiting superior structural stability and long-term anti-aging properties. Attached Figure Description

[0020] Figure 1 The image shows a comparison of the infrared spectra of modified porous nano-silica and unmodified porous nano-silica. Detailed Implementation

[0021] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example 1

[0022] Preparation of a high luminous flux and high color rendering tri-color phosphor composition: 1) Preparation of fluorinated silane coupling agents: ; The CAS number for raw material 1 is 882853-72-7, and its Chinese name is 4-(perfluorooctylbenzoyl)benzyl bromide. The CAS number for raw material 2 is 122-52-1, and its Chinese name is triethyl phosphite. The CAS number for raw material 3 is 2857-97-8, and its Chinese name is trimethylbromosilane.

[0023] First, under nitrogen protection, 2.95 g of raw material 1 was added to a 25 mL double-necked round-bottom flask. 1.71 mL of raw material 2 was then injected into the reaction flask using an anhydrous syringe. The reaction was carried out in an oil bath at 140 °C. The mixture was stirred continuously under reflux at 140 °C for 4 hours. After the reaction was complete, the reaction flask was removed from the oil bath and allowed to cool naturally to room temperature. The reaction mixture was transferred to a 100 mL separatory funnel, and 30 mL of dichloromethane (DCM) was added to dilute the system. 20 mL of deionized water was slowly added to quench any remaining water-soluble impurities and a first extraction was performed. After thorough shaking and allowing the layers to separate, the lower organic phase was collected. The aqueous phase was extracted twice more with DCM (2 × 15 mL). All organic layers were combined and washed successively with 20 mL of deionized water and 20 mL of saturated brine to remove residual phosphites. The washed organic phase was transferred to an Erlenmeyer flask, and an appropriate amount of anhydrous sodium sulfate (Na₂SO₄) was added for drying for 30 minutes. The desiccant was then filtered out through a glass funnel lined with absorbent cotton, and the filter cake was washed with a small amount of DCM. The filtrate was transferred to a single-necked flask, and most of the solvent was evaporated under reduced pressure. Finally, the crude product was placed under a high-vacuum oil pump for 2 hours to remove residual excess triethyl phosphite and trace amounts of solvent, yielding the crude product. The crude product was purified by silica gel column chromatography (200-300 mesh silica gel) using petroleum ether / ethyl acetate as eluent. Initially, the leading impurities were eluted with PE / EA = 10:1, and then the polarity was gradually increased to PE / EA = 2:1 to elute the target product. The fraction containing the pure product was collected, concentrated, and dried under high vacuum to finally obtain 2.07 g of the intermediate.

[0024] In the second step, under argon protection, 2.07 g of the intermediate was added to a 50 mL double-necked round-bottom flask. Then, 15.0 mL of anhydrous dichloromethane was injected using a glass syringe, and magnetic stirring was started to completely dissolve the substrate. The reaction flask was placed in an ice-water bath, and after the system temperature dropped to 0°C, 1.27 mL of the starting material 3 was slowly added dropwise through a constant-pressure dropping funnel. The dropwise addition process was maintained for 15 minutes. After the addition was complete, the ice-water bath was removed. The reaction system was slowly raised to room temperature and stirred continuously for 14 hours under an argon atmosphere. After the reaction was complete, the reaction solution was transferred to a single-necked flask and concentrated under reduced pressure using a rotary evaporator (water bath 30°C) in a fume hood. The oily intermediate was then redissolved in methanol (10.0 mL), and 5 drops of deionized water were added. Hydrolysis was carried out by stirring at room temperature for 2 hours. After hydrolysis, methanol and volatiles were removed again by rotary evaporation under reduced pressure. Ethyl acetate (40.0 mL) was added to the residue to dissolve it, and the solution was transferred to a separatory funnel. The residue was washed successively with deionized water (20.0 mL) and saturated saline solution (20.0 mL). The separated organic layer was collected in an Erlenmeyer flask and dried for 30 minutes with anhydrous sodium sulfate. The desiccant was then removed by vacuum filtration through a Buchner funnel. The filtrate was concentrated to dryness under reduced pressure using a rotary evaporator to obtain the crude product. A small amount of dichloromethane (3 mL) was added to the crude product to dissolve it by gentle heating. Then, n-hexane (15.0 mL) was slowly added dropwise under vigorous stirring, resulting in the precipitation of a large amount of solid. After further slurrying at 0 °C for 1 hour, the mixture was filtered. The filter cake was washed with cold n-hexane (5 mL) and dried in a vacuum drying oven (40 °C, high vacuum with oil pump) for 4 hours to obtain 1.17 g of fluorinated silane coupling agent.

[0025] Structural assessment: NMR of intermediates 1 HNMR(400MHz, CDCl3):7.58(d,2H),7.42(dd,2H),4.08-3.96(m,4H),3.22(d,2H),1.26(t,6H); ¹H NMR (400 MHz, DMSO-d6) of the fluorosilane coupling agent: 7.62 (d, 2H), 7.48 (d, 2H), 3.08 (d, 2H). (Note: The active proton -OH did not elute).

[0026] 2) Modified porous nano-silica: Step 1: Surface activation treatment. Accurately weigh 100g of porous nano-silica with an average particle size of 100nm, a specific surface area of ​​450m² / g, and a pore size of 15nm. Disperse it in 200g of anhydrous ethanol, and then add 5g of deionized water. Place the above mixed dispersion in an ultrasonic device and sonicate it at a constant temperature of 45℃ for 30 minutes to obtain the activated silica dispersion. Step 2: Coordination grafting reaction. 1g of the fluorinated silane coupling agent synthesized in the preparation of the above-mentioned fluorinated silane coupling agent was added to the activated silica dispersion obtained in Step 1. Then, an appropriate amount of anhydrous ethanol was added to the system to adjust the silica dispersion concentration to 15wt%. The reaction system was placed in a constant temperature water bath and stirred and refluxed at 65°C for 8 hours. Step 3: Post-processing. After the reaction is complete, stop heating and allow the reaction solution to cool naturally to room temperature. Transfer the reaction solution to a centrifuge for centrifugation and discard the supernatant. Add an appropriate amount of anhydrous ethanol to the obtained solid product, redisperse it, and centrifuge again. Repeat the washing process three times. After washing, place the solid product in a vacuum drying oven and vacuum dry it at 60°C for 16 hours. Finally, remove the dried agglomerated material, grind it thoroughly, and sieve it to obtain well-dispersed modified porous nano-silica powder.

[0027] like Figure 1 The image shows a comparison of the Fourier transform infrared (FT-IR) spectra of unmodified porous nano-silica and fluorinated phosphonate-modified silica. Compared with the unmodified sample, the modified spectrum exhibits several key changes: First, at 3400 cm⁻¹... -1 The -OH stretching vibration peak near the 960 cm⁻¹ was significantly weakened, and the peak at 960 cm⁻¹ was also significantly weakened. -1 The Si-OH bending vibration absorption peak at 1100 cm⁻¹ almost disappeared. This indicates that a large number of silanol groups on the silica surface were consumed, and they successfully coordinated with the phosphate groups of the coupling agent. Secondly, at 1100 cm⁻¹... -1 Up to 1300cm -1 A significantly broadened, complex, and strong absorption band appeared in the region, which is a direct reflection of the superposition of newly introduced numerous CF bonds and P=O bonds with the existing strong Si-O-Si peaks. Furthermore, at 2800 cm⁻¹... -1 Up to 3000cm -1 The vicinity shows a double peak of the CH stretching vibration of the methylene group, and at 1500 cm⁻¹ -1 A C=C vibration peak representing the benzene ring skeleton was observed nearby. The rise and fall of these characteristic peaks fully confirm that the fluorine-containing long chain and aromatic ring structure have been firmly attached to the porous nano-silica surface through chemical bonds, successfully achieving the expected interface modification goal.

[0028] 3) Raw material components by weight: Addition-type silicone resin: 100 parts (specifically, vinylphenyl silicone resin with 45% phenyl mass fraction and 2% vinyl mass fraction); Supplier: (Hubei Langbowan Biomedical Co., Ltd., vinyl content 2% / 5%, industrial grade); Hydrogen-containing silicone oil: 8 parts (specifically, phenyl hydrogen-containing silicone oil with an active hydrogen mass fraction of 1.0%); Supplier: (Wuhan Lanabai Pharmaceutical Chemical Co., Ltd., purity: 1kg2500, refractive index 1.46, packaging information: 1kg25kg); Modified porous nano-silica: 5 parts (i.e., the product obtained in "2. Preparation of modified porous nano-silica" above); Three-color phosphors containing specific rare earth elements: 70 parts. Specifically, they include: Divalent europium-activated barium magnesium aluminate (BaMgAl) 10 O 17 Eu 2+ Blue fluorescent powder: 20 parts; Cerium trivalent activated yttrium aluminum garnet Y3Al5O 12 :Ce 3+ Green fluorescent powder: 40 parts; Divalent europium-activated calcium aluminum silicon nitride (CaAlSiN3:Eu) 2+ Red fluorescent powder: 10 parts.

[0029] The divalent europium-activated barium magnesium aluminate (BaMgAl) 10 O 17 Eu 2+ The preparation method is referenced from "Wang Xiaojuan, Zhang Yingtang, Ma Baoke. Effect of sintering time on BaMgAl". 10 O 17 Eu 2+ Influence of blue luminescent materials [J]. China Powder Technology, 2008, (04): 10-12. DOI: 10.13732 / j.issn.1008-5548.2008.04.016. The paper discusses BaMgAl. 10 O 17 Eu 2+ The preparation method involves sintering for 7 hours to obtain the desired product; The trivalent cerium-activated yttrium aluminum garnet Y3Al5O 12 :Ce 3+ Refer to "Mu Zhongfei, Hu Yihua. YAG:Ce 3+ High-Temperature Solid-State Preparation of Yellow Phosphor [J]. Guangzhou Chemical Industry, 2011, 39(08): 1-2. (The paper mentions Y3Al5O...) 12 :Ce 3+ The preparation method involves solid-state sintering at 1550℃ for 4 hours to obtain the product. The divalent europium-activated calcium aluminum silicon nitride CaAlSiN3:Eu 2+Referring to the paper "Zhang Hong, Wang Le, Luo Dong, et al. Study on Eu2+ doped CaAlSiN3-based nitride red phosphor and its luminescence properties [J]. Spectroscopy and Spectral Analysis, 2020, 40(01):59-64.", CaAlSiN3:Eu 2+ The preparation method involves sintering at 1800℃ and 1MPa pressure for 4 hours.

[0030] 4) Preparation method: S1. Matrix Pre-dispersion: The weighed 5 parts of modified porous nano-silica and 100 parts of addition-type silicone resin were mixed evenly, and then the mixture was poured into a three-roll mill for high-shear milling. The gap between the milling rollers was set to 15 μm, and milling was performed 4 times consecutively. Through high-shear action, a uniform and transparent modified matrix adhesive was obtained.

[0031] S2. Mixed Flow Degassing: 20 parts blue phosphor, 40 parts green phosphor, and 10 parts red phosphor are pre-mixed evenly in a powder mixer. Then, the mixed tri-color phosphors are added to the modified matrix adhesive obtained in step S1, along with 8 parts of hydrogen-containing silicone oil. The container containing the mixture is placed in a planetary vacuum mixer, and a combined revolution and rotation stirring operation is performed under a vacuum of -0.095 MPa. The revolution speed is set to 900 r / min, and the rotation speed to 1350 r / min, and stirring is continued for 15 minutes to obtain a bubble-free slurry.

[0032] S3. Stepwise Crosslinking and Curing: The mixed slurry obtained in step S2 is dispensed or filled into the LED bracket / mold, and then placed in a programmable temperature-controlled oven for stepwise curing: First, pre-curing is performed at a first temperature of 70°C for 1.5 hours. After pre-curing, the temperature is directly raised to a second temperature of 135°C and held for 3 hours to promote complete crosslinking and curing of the silicone resin bulk phase, ultimately obtaining a high luminous flux, high color rendering, and highly uniform phosphor spatial distribution encapsulated cured body. Example 2

[0033] Preparation of a high luminous flux and high color rendering tri-color phosphor composition: 1. Raw material components by weight: Addition-type silicone resin: 100 parts (specifically, vinylphenyl silicone resin with a phenyl mass fraction of 40% and a vinyl mass fraction of 1%); Hydrogen-containing silicone oil: 5 parts (specifically, phenyl hydrogen-containing silicone oil with an active hydrogen mass fraction of 0.5%); Modified porous nano-silica: 2 parts (i.e., the product obtained from the above preparation); Three-color phosphors containing specific rare earth elements: 50 parts. Specifically, they include: Divalent europium activated barium magnesium aluminate BaMgAl10O17:Eu2+ blue phosphor: 15 parts (same as Example 1); Trivalent cerium-activated yttrium aluminum garnet Y3Al5O12:Ce3+ green phosphor: 30 parts (same as Example 1); Divalent europium activated calcium aluminum nitride (CaAlSiN3:Eu2+) red phosphor: 5 parts (same as Example 1).

[0034] 2. The rest remains the same as in Example 1. Example 3

[0035] Preparation of a high luminous flux and high color rendering tri-color phosphor composition: 1. Raw material components by weight: Addition-type silicone resin: 100 parts (specifically, vinylphenyl silicone resin with 50% phenyl mass fraction and 3% vinyl mass fraction); Hydrogen-containing silicone oil: 10 parts (specifically, phenyl hydrogen-containing silicone oil with an active hydrogen mass fraction of 1.5%); Modified porous nano-silica: 8 parts (i.e., the product obtained from the above preparation); Three-color phosphors containing specific rare earth elements: 90 parts. Specifically, they include: Divalent europium activated barium magnesium aluminate BaMgAl10O17:Eu2+ blue phosphor: 25 parts (same as Example 1); Trivalent cerium-activated yttrium aluminum garnet Y3Al5O12:Ce3+ green phosphor: 50 parts (same as Example 1); Divalent europium activated calcium aluminum nitride (CaAlSiN3:Eu2+) red phosphor: 15 parts (same as Example 1).

[0036] 2. The rest remains the same as in Example 1.

[0037] Comparative Example 1 The preparation of a high luminous flux and high color rendering tri-color phosphor composition is carried out by referring to the preparation method of Example 1, except that the modified porous nano silica is replaced with an equal amount of ordinary porous nano silica that has not been grafted with a fluorinated silane coupling agent, and the rest is the same as in Example 1.

[0038] Comparative Example 2 The preparation of a high luminous flux and high color rendering tri-color phosphor composition is carried out according to the preparation method of Example 1. No porous nano-silica is added when preparing the composition. Only addition-type organosilicon resin, hydrogen-containing silicone oil and tri-color phosphor are mixed and cured. The rest is the same as in Example 1.

[0039] Comparative Example 3 The preparation of a high luminous flux and high color rendering tri-color phosphor composition is carried out according to the preparation method of Example 1. In the preparation process, the pre-prepared modified porous nano-silica is not used. Instead, an equal amount of unmodified porous nano-silica and a corresponding equivalent ratio of fluorinated silane coupling agent are directly added to addition-type organosilicon resin by physical mixing and high-shear grinding dispersion. The remaining process steps and parameters are the same as in Example 1.

[0040] Comparative Example 4 The preparation of a high luminous flux and high color rendering tri-color phosphor composition is carried out by referring to the preparation method of Example 1, except that the "S3. step cross-linking curing" process is replaced by the traditional constant temperature one-step cross-linking curing process, that is: the mixed slurry after filling is directly placed in a constant temperature oven at 135°C for complete cross-linking curing for 4.5 hours, and the remaining raw material ratios and previous processes are the same as in Example 1.

[0041] Performance testing 1. Testing Method A1. Initial Luminous Flux and Color Rendering Index (Ra): Referring to the national standard GB / T24824-2009 "Test Methods for LED Modules for General Lighting", at an ambient temperature of 25℃, a rated forward current of 350mA was applied, and the initial luminous flux and color rendering index after the device stabilized were measured using an integrating sphere spectroradiometer system (equipped with a standard DC power supply). The data are shown in Table 1.

[0042] A2. Spatial Chromaticity Inhomogeneity (Δu'v'): Using a goniophotometer, spectral chromaticity data were measured at different angles within an observation angle range of -90° to +90° (with a step angle set in 10° increments). The maximum chromaticity difference Δu'v' in the CIE1976 (u',v') uniform chromaticity space at different angles was calculated. This index directly reflects whether the phosphor undergoes gravitational sedimentation and aggregation within the colloid; a smaller value indicates higher spatial color uniformity. The data are shown in Table 1.

[0043] A3. High Temperature and High Humidity Aging Color Temperature Drift (ΔCCT): Referring to the national standard GB / T33720-2017 "Test Method for Luminous Flux Maintenance of LED Lighting Products", the device was placed in a dual 85℃ / 85%RH aging test chamber and continuously lit for 1000 hours. The correlated color temperature (CCT) before and after aging was measured, and the color temperature drift ΔCCT was calculated to characterize the long-term structural stability and anti-yellowing aging ability of the packaging system. The data are shown in Table 1.

[0044] Table 1. The test results show that the overall optical performance and long-term reliability of each embodiment are significantly better than those of the comparative examples, strongly demonstrating the synergistic advantages of the modification mechanism and the step-curing process of this invention. In the comparative examples, whether no porous silica was added or only unmodified or physically blended silica was used, the poor matrix compatibility and lack of effective interfacial crosslinking led to severe specific gravity sedimentation of large-particle phosphors during the curing stage, resulting in extreme spatial color uniformity (yellow circle phenomenon) and a decrease in color rendering index. At the same time, the isothermal one-step curing (comparative example 4) also exacerbated powder migration because the crosslinking was too fast and network locking could not be formed. In contrast, the embodiments of the present invention significantly improve the dispersibility of silica in the resin and regulate the interfacial refractive index through the coordination grafting of fluorinated coupling agents, effectively reducing light scattering loss and thus increasing luminous flux. More importantly, its unique rigid fluorinated segments form a stable three-dimensional physical barrier network with the resin matrix during the stepped pre-curing stage, firmly locking the three primary color phosphors of different densities in situ, fundamentally overcoming the color temperature drift caused by gravity sedimentation, and endowing the device with excellent spatial color uniformity and extremely high anti-aging stability.

[0045] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A high luminous flux and high color rendering tri-color phosphor composition, characterized in that, The composition consists of the following raw materials in parts by weight: 100 parts addition-type silicone resin, 5-10 parts hydrogen-containing silicone oil, 50-90 parts tri-color phosphor containing specific rare earth elements, and 2-8 parts modified porous nano-silica. The tri-color phosphor containing specific rare earth elements is composed of a mixture of three rare earth phosphors that emit blue, green, and red light. The modified porous nano-silica surface is grafted with a fluorinated silane coupling agent. The fluorinated silane coupling agent is .

2. The high luminous flux and high color rendering tri-color phosphor composition according to claim 1, characterized in that, The tri-color phosphor containing specific rare earth elements is composed of the following components in parts by weight: 15-25 parts by weight of divalent europium-activated barium magnesium aluminate (BaMgAl). 10 O 17 Eu 2+ Blue phosphor, 30-50 parts by weight of cerium trivalent activated yttrium aluminum garnet (Y3Al5O3). 12 :Ce 3+ Green phosphor, 5-15 parts by weight of divalent europium-activated calcium aluminum silicon nitride (CaAlSiN3:Eu) 2+ Red fluorescent powder.

3. The high luminous flux and high color rendering tri-color phosphor composition according to claim 1, characterized in that, The addition-type silicone resin is a vinylphenyl silicone resin with a phenyl mass fraction of 40%-50% and a vinyl mass fraction of 1%-3%; the hydrogen-containing silicone oil is a phenyl hydrogen-containing silicone oil with an active hydrogen mass fraction of 0.5%-1.5%.

4. The high luminous flux and high color rendering tri-color phosphor combination according to claim 1, characterized in that, The porous nano-silica has an average particle size of 50-150 nm and a specific surface area of ​​300-600 m². 2 / g, with a pore size of 10-20nm.

5. The high luminous flux and high color rendering tri-color phosphor composition according to claim 1, characterized in that, The method for preparing the modified porous nano-silica includes: (1) Surface activation treatment: 100 parts of porous nano silica are dispersed in 150-250 parts of anhydrous ethanol, 2-8 parts of deionized water are added, and ultrasonic treatment is carried out at 40-50℃ for 20-40 minutes to obtain activated silica dispersion. (2) Coordination grafting reaction: Add 10-25 parts of fluorinated phosphonate compound to the activated silica dispersion obtained in step (1), and add anhydrous ethanol to adjust the silica dispersion concentration in the reaction system to 12-25 wt%. Stir and reflux at 60-70℃ for 6-10 hours. (3) Post-processing: After the reaction is completed, the reaction solution is centrifuged and separated. The obtained solid product is washed with anhydrous ethanol 3-5 times, then vacuum dried at 50-70℃ for 12-20 hours, and then ground and sieved to obtain modified porous nano silica.

6. A method for preparing a high luminous flux and high color rendering tri-color phosphor composition according to any one of claims 1-5, characterized in that, The preparation steps include the following: S1. Matrix pre-dispersion: The modified porous nano silica is mixed with the addition-type organosilicon resin and sheared and ground to uniformly disperse it in the resin matrix, thereby obtaining the modified matrix adhesive. S2. Mixing and degassing: After the three primary color phosphors are mixed evenly, they are added to the modified matrix adhesive obtained in step S1. Hydrogen-containing silicone oil is added, and planetary stirring combining revolution and rotation is carried out under vacuum conditions to obtain a bubble-free mixed slurry. S3. Stepwise crosslinking and curing: After the mixed slurry obtained in step S2 is filled, it is first pre-cured at a first temperature; The temperature is then raised to a second temperature to allow for complete cross-linking and curing of the resin phase.

7. The method for preparing a high luminous flux and high color rendering tri-color phosphor composition according to claim 6, characterized in that, In step S1, the high-shear grinding is performed using a three-roll mill with the gap between the grinding rollers set to 10-20 μm and the grinding cycle being 3-5 times.

8. The method for preparing a high luminous flux and high color rendering tri-color phosphor composition according to claim 6, characterized in that, In step S2, the vacuum degree of the planetary stirrer under vacuum conditions is controlled to be -0.09MPa to -0.1MPa, the revolution speed is 800-1000r / min, and the rotation speed is 1200-1500r / min.

9. The method for preparing a high luminous flux and high color rendering tri-color phosphor composition according to claim 6, characterized in that, In step S3, the first temperature is set to 60-80℃ and the pre-curing time is 1-2 hours; the second temperature is set to 120-150℃ and the curing time is 2-4 hours.

10. The method for preparing a high luminous flux and high color rendering tri-color phosphor composition according to claim 9, characterized in that, The first temperature is lower than the rapid crosslinking threshold temperature of the addition-type silicone resin; In step S3, the mixed slurry after filling is placed in a temperature-controlled oven for step cross-linking and curing, and after the pre-curing is completed, the temperature is directly raised to the second temperature.

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