High-efficiency long-afterglow noctilucent flow line color master batch and preparation method thereof

Abstract

The invention relates to the field of color master batches, and discloses a high-efficiency long-afterglow noctilucent flow line color master batch which comprises the following components in percentage by mass: 10-25% of a noctilucent matrix which adopts a nitride system, and a wide-band gap in a crystal structure of the noctilucent matrix can provide a deeper electron trap depth; 2-8% of a flow line pigment; 0.5-1% of a coupling agent; 75-90% of carrier resin; the carrier resin is a maleic anhydride grafted ethylene-vinyl acetate copolymer, the grafting rate is 1-3%, and the melt index is 15-25 g / 10 min; 0.5-2% of an auxiliary agent, wherein the auxiliary agent comprises an antioxidant and a lubricant; and the coupling agent is isopropyl trititanate. According to the technical scheme of directionally modifying hydroxyl on the surface of the flow-line pigment by adopting the titanate coupling agent, chemical bonding and physical winding dual anchoring of a pigment-resin interface are realized, and the problems of sudden mechanical property drop caused by interface defects and light transmittance fluctuation caused by pigment agglomeration are solved.

Description

Technical Field

[0001] The invention relates to the technical field of masterbatches, in particular to a high-efficiency, long-lasting luminous rhyolite masterbatch and a preparation method thereof. Background Art

[0002] High-efficiency, long-lasting luminous rhyme color masterbatches are widely used in safety signs, decorations, toys, automotive accessories, smart home applications, and other fields. The core requirement is to simultaneously achieve long-lasting luminous performance, resistance to complex environments, and high surface decorative effects. Existing technologies primarily focus on inorganic-organic composite systems, including silane coupling agent modification, vapor deposition coating, and UV curing processes. Typical preparation methods involve high-energy ball milling dispersion, multi-layer coating protection, and high-temperature injection molding.

[0003] In existing processes, insufficient interfacial bonding leads to pigment agglomeration and a sharp drop in mechanical properties. A single protective layer is inadequate to withstand the combined effects of heat, humidity, and UV radiation. A mismatch between the photocuring process and the material response leads to surface embrittlement or adhesion defects. Furthermore, high rare earth content and complex coating steps drive up costs and limit large-scale production. Poor flow pattern stability, weak environmental adaptability, and unbalanced economics are key bottlenecks hindering the efficient application of luminescent materials. Summary of the Invention

[0004] In response to the shortcomings of the existing technology, the present invention provides a high-efficiency long-afterglow luminous rhyolite masterbatch and a preparation method thereof, which solves the problems in the existing technology such as weak interface bonding causing pigment agglomeration and mechanical failure, insufficient resistance to environmental erosion of a single protective structure, mismatch between the photocuring process and the dynamic response of the material, and high rare earth usage and complex process leading to cost out of control.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions: a high-efficiency long-lasting luminous rhyolite masterbatch, comprising the following components by mass percentage: Luminous matrix: 10-25%; Rhythm pigment: 2-8%; Coupling agent: 0.5-1%; Carrier resin: 75-90%; Additives: 0.5-2%, including antioxidants and lubricants.

[0006] The luminous matrix adopts nitride system (CaAlSiN3:Eu 2+ ,Nd 3+ ,Dy 3+ ), whose wide band gap (~2.5eV) in the crystal structure can provide a deeper electron trap depth, compared with traditional aluminates (SrAl2O4:Eu 2+ ,Dy 3+) has a narrow band gap (~1.8eV), which significantly slows down the electron release rate and extends the afterglow time to more than 15 hours.

[0007] By introducing Nd 3+ With Dy 3+ Double doping, construction of multi-level trap energy chain (Eu 2+ →Nd 3+ →Dy 3+ ). Among them, Nd 3+ As a shallow trap (0.6-0.8eV) providing short afterglow, Dy 3+ As a deep trap (1.0-1.2eV) to maintain long-lasting luminescence, the two work together to achieve an optimal balance between afterglow time and brightness decay rate.

[0008] Using a gradient coating technique, the material is sequentially coated with SiO2 (5-10nm), a UV absorbing layer (2-5nm), and a fluorosilane layer (3-5nm). The SiO2 layer isolates non-radiative recombination caused by surface oxygen vacancies, the UV absorbing layer blocks 300-400nm ultraviolet radiation from damaging the luminescent center, and the fluorosilane layer reduces humidity sensitivity (contact angle ≥120°). These three factors work together to reduce the material's brightness decay to <10% at 85% humidity.

[0009] The rhyolite pigment (metal oxide or organic phthalocyanine dye) is chemically bonded to the luminescent particles and resin via a titanate coupling agent (isopropyl tri(dioctyl pyrophosphate) titanate). The phosphate groups of the coupling agent react with the hydroxyl groups on the pigment surface, and the long-chain alkyl groups are grafted onto the maleic anhydride groups of the EVA resin, forming a three-dimensional "pigment-coupling agent-resin" network.

[0010] In traditional masterbatches, the pigment and luminous material are prone to phase separation due to their polarity differences. However, the present invention uses the interfacial bonding effect of the coupling agent to evenly disperse the rhyolite pigment around the luminous particles. After a 1000-hour aging test, the color difference ΔE is less than 1.5, and there is no agglomeration or stratification.

[0011] The carrier resin is maleic anhydride-grafted ethylene-vinyl acetate copolymer (EVA-g-MAH, grafting ratio 1-3%). The grafted maleic anhydride groups react with the coupling agent to lower the resin's melting temperature to below 160°C (melt index 15-25g / 10min), while also improving the interfacial bonding strength with the luminous particles.

[0012] Conventional EVA processing temperature (180-200℃) easily leads to thermal degradation of luminous materials (deactivation rate>15%), while low melting point EVA and shear rate control (200-250s -1 ) work synergistically, so that the thermal degradation rate of the luminous particles during processing is less than 3%, and the melt fluidity (MFI ≥ 15g / 10min) meets the needs of complex injection molding.

[0013] The additives include antioxidant (1010) and lubricant (zinc stearate), which act at different stages: Antioxidant: Captures free radicals generated during processing, blocks the thermal oxidation degradation chain reaction of EVA resin, and reduces the thermal weight loss rate of masterbatch to less than 0.5% / h at 160°C; Lubricant: Reduce melt viscosity, reduce shear heat generation during extrusion and injection molding, and avoid local temperature rise that causes inactivation of luminous materials.

[0014] Preferably, the carrier resin is maleic anhydride grafted ethylene-vinyl acetate copolymer, with a grafting rate of 1-3% and a melt index of 15-25 g / 10 min.

[0015] The grafting modification of maleic anhydride introduces polar carboxylic acid groups into the EVA molecular chain. On the one hand, these groups react chemically with the phosphate groups of the titanate coupling agent to form a stable "resin-coupling agent-luminescent particle" chemical bonding network, preventing interfacial debonding caused by shear forces during processing. On the other hand, the introduction of polar groups improves the compatibility between the resin and the luminescent powder (containing hydroxyl groups on the surface), reducing the dispersion uniformity (D90 / D10) of the luminescent particles in the molten resin from ≥5 in conventional systems to ≤3. When the grafting rate is less than 1%, insufficient polar groups lead to weak interfacial bonding. When it is higher than 3%, the resin rigidity increases excessively, the melt fluidity decreases, and it is not conducive to low-temperature processing.

[0016] The melt index characterizes the flowability of the resin at a specific temperature. In this invention, the melt index of EVA-g-MAH is controlled to 15-25g / 10min, so that it can achieve full flow at a low temperature of 155-160℃. This characteristic strictly matches the thermal stability of the luminous material (degradation temperature ≤ 180℃): when the processing temperature exceeds 160℃, the Eu of the luminous particles 2+ The luminescent centers will be deactivated due to the increase in lattice oxygen vacancies, resulting in a reduction of afterglow time by more than 30%. Resins with too low a melt index (<15g / 10min) require higher processing temperatures (≥170°C), increasing the risk of thermal damage. In addition, a moderate melt index ensures a stable shear field in the melt during twin-screw extrusion, allowing for uniform dispersion of the luminescent particles and rhyolite pigments, avoiding localized agglomeration.

[0017] Preferably, the coupling agent is isopropyl trititanate.

[0018] The phosphate group (-PO4 -) undergoes a dehydration condensation reaction with the hydroxyl groups (-OH) on the surface of the rhyolite pigment (TiO2, Fe2O3 metal oxide) to form a stable Ti-OP covalent bond. Compared with traditional silane coupling agents (which rely on Si-O bonding), the bonding ability of the phosphate group to the metal oxide surface can be increased by about 30%, and the reaction can be completed under low temperature conditions of 50-70°C, avoiding high temperature (>80°C) that causes lattice distortion of the luminous material. Experiments show that the dispersion uniformity (D90 / D10) of the rhyolite pigment treated by this coupling treatment in EVA resin is reduced from ≥5 for the untreated one to ≤2.5, and there is no phase separation after 1000 hours of wet heat aging (85°C / 85% RH).

[0019] The coupling agent's long dioctylpyrophosphate acyloxy chains (C8H17-OPO-) are embedded in the resin matrix (EVA-g-MAH). They entangle with the maleic anhydride grafted segments of the resin through van der Waals forces, forming a three-in-one interface structure: rhyotropic pigment-coupling agent-resin. This structure effectively buffers shear stress during processing, preventing the luminescent particles from being mechanically separated from the resin. Furthermore, the hydrophobic nature of the long-chain alkyl groups reduces polarity differences at the resin-pigment interface, increasing the melt flow index (MFI) by 15-20%, ensuring the dispersion integrity of the luminescent particles during low-temperature extrusion (≤160°C).

[0020] A preparation method based on the above masterbatch comprises the following steps: (1) Synthesis and gradient coating of luminescent matrix; Multi-ion cooperative doping: Eu 2+ As the luminescence center, its 4f-5d transition produces the main luminescence peak (620-630nm); Nd 3 + The shallow trap level (0.6-0.8eV) provides a short afterglow, Dy 3+ The deep trap energy level (1.0-1.2eV) of the three extends the afterglow time, and the electron capture-release chain transfer is formed, which prolongs the afterglow time by more than 50% compared with the single-doping system.

[0021] SiO2 layer (5-10nm): reduces non-radiative recombination caused by surface defects through physical isolation, increasing the luminous efficiency to over 85% (about 70% for the uncoated system); UV absorption layer (benzotriazole): selectively absorbs 300-400nm ultraviolet rays and blocks the ultraviolet photons from reaching Eu 2+ The lattice perturbation of the luminescence center, the brightness decay rate after 1000 hours of UV irradiation is less than 8%; Fluorosilane layer (3-5nm): reduces surface energy (contact angle ≥ 120°), inhibits lattice hydrolysis caused by water molecule penetration, and maintains the afterglow time of the material at 85% humidity to > 90%.

[0022] (2) Coupling treatment of rhyolite pigments; Phosphate directional bonding: The phosphate group of the coupling agent undergoes dehydration condensation with the hydroxyl group (-OH) on the pigment surface to form a Ti-OP covalent bond with a bond energy of 450kJ / mol (the Si-O bond of a traditional silane coupling agent is about 370kJ / mol), which increases the pigment-resin interface bonding strength by 40%; Dynamic stress buffering: The long-chain alkyl group (C8H17-) of the coupling agent is physically entangled with the maleic anhydride grafted chain segment of the resin. Under the action of processing shear force, the chain segment slips to absorb energy, preventing the pigment and the luminous particles from peeling off due to mechanical stress, and the elongation at break of the masterbatch is increased to more than 250%.

[0023] (3) Blending and extrusion granulation of masterbatch; Low temperature shear dispersion: by screw speed (corresponding to shear rate 200-250s -1 ) and melt viscosity are matched to achieve uniform dispersion of luminous particles (D90 / D10≤3) at ≤160℃, avoiding the degradation of Eu caused by high temperature (>170℃) 2+ Deactivation caused by the increase of lattice oxygen vacancies (thermal degradation rate <3%); Melt pressure control: melt pressure of 3-5MPa ensures that the resin is fully plasticized and wraps the particles, while avoiding excessive pressure (>6MPa) that causes the fluorosilane coating to rupture, and the interface integrity retention rate is >95%.

[0024] (4) Injection molding and UV curing; Low temperature injection molding protection: The mold temperature is 40-60℃, which allows the melt to cool and shape quickly, reducing the high temperature exposure time of the luminous particles in the melt (<30 seconds), and controlling the lattice oxygen vacancy density to ≤10 16 / cm 3 (Conventional injection molding>10 17 / cm 3 ); Surface cross-linking strengthening: UV-induced maleic anhydride groups on the resin surface react with the photoinitiator (TPO) to form a cross-linked network (cross-linking degree ≥ 80%), increasing the surface hardness to 2H (uncured system < H), and improving the wear resistance by more than 3 times.

[0025] Preferably, step (1) comprises: A. Mix CaCO3, Al2O3, Si3N4 with Eu2O3, Nd2O3 and Dy2O3 according to mass percentage, sinter at 1450-1550℃ for 6-8 hours in N2 / H2 mixed gas with a volume ratio of 95:5 to obtain CaAlSiN3:Eu 2+ ,Nd 3+ ,Dy 3+powder; B. The powder is coated with SiO2 layer, UV absorption layer and fluorosilane hydrophobic treatment in sequence. The coating order is SiO2 layer → UV absorption layer → fluorosilane layer.

[0026] Mix CaCO3, Al2O3, Si3N3 with Eu2O3, Nd2O3, and Dy2O3 in proportion and sinter at 1450-1550℃ for 6-8 hours in N2 / H2 (volume ratio 95:5). During this process, N2 / H2 mixture inhibits the formation of oxygen vacancies and oxidation of rare earth ions (Eu 3+ →Eu 2+ Restore), ensure Eu 2+ As luminescent centers, high concentrations (1.2-1.8%) are embedded in the CaAlSiN3 lattice. 3+ With Dy 3+ The synergistic doping forms deep and shallow composite trap levels: Nd 3+ (Shallow trap 0.6-0.8eV) Rapid release of electrons maintains initial high brightness, Dy 3+ The slow release of electrons (deep traps 1.0-1.2eV) prolongs the afterglow time. These factors transform the afterglow decay curve from a single exponential mode (traditional systems) to a bi-exponential mode, increasing the afterglow duration to over 18 hours (traditional aluminate systems are approximately 8-10 hours). Sintering temperatures below 1450°C result in incomplete lattice development, while temperatures above 1550°C lead to >5% rare earth ion volatilization losses.

[0027] The powder is coated with a SiO2 layer, a UV absorbing layer and a fluorosilane hydrophobic treatment in sequence, and the order is irreversible.

[0028] SiO2 inner layer coating (5-10nm): A dense SiO2 layer is formed on the powder surface through the sol-gel method. Its high chemical inertness can isolate the penetration of external H2O and O2 molecules, block the non-radiative recombination caused by lattice surface defects, and increase the luminous efficiency from 70% to more than 85%.

[0029] UV absorption layer coating (benzotriazole, 2-5nm): The UV absorption layer formed by the dipping method selectively blocks 300-400nm ultraviolet rays, reducing the damage of high-energy photons to Eu 2+ The excited state of the luminescence center is quenched, and the brightness retention rate after 1000 hours of UV aging is greater than 92% (uncoated system is less than 80%).

[0030] Fluorosilane hydrophobic layer (3-5nm): Vapor-deposited heptadecafluorodecyltrimethoxysilane forms a low surface energy hydrophobic layer (contact angle ≥120°), inhibiting the adsorption and capillary penetration of water molecules on the powder surface, reducing the afterglow time decay rate of the material at 85% humidity to <5% (untreated system >20%).

[0031] Preferably, the doping ratio of the rare earth oxide in step A is: Eu2O3: 1.2-1.8%; Nd2O3: 0.8-1.2%; Dy2O3: 0.3-0.5%.

[0032] Eu 2+ As the luminescence center, its 4f-5d electron transition dominates the main luminescence peak (620-630nm). When the Eu2O3 doping amount is lower than 1.2%, the density of the luminescence center is insufficient and the initial brightness of the material (afterglow intensity for 10 minutes) is lower than 3000mcd / m 2 ; When it exceeds 1.8%, Eu 2+ The small ion spacing causes concentration quenching, which shortens the afterglow time (T50) from 18 hours to less than 12 hours. The 1.2-1.8% range of the present invention balances the luminescent center density and the quenching effect, so that the initial brightness reaches 4000-4500mcd / m 2 , while the afterglow time T50 ≥ 18 hours (test conditions: D65 light source excitation for 10 minutes).

[0033] Innovation mechanism: By controlling Eu 2+ The solid solubility in the CaAlSiN3 lattice (≤1.8%) avoids non-radiative recombination caused by lattice distortion, and increases the luminous efficiency (QE) to more than 82% (about 65% for traditional aluminate systems).

[0034] Nd 3+ The introduction of Nd2O3 forms shallow trap levels (0.6-0.8eV) in the lattice, with an electron capture-release time constant (τ1) of 10-30 seconds, which is responsible for maintaining the high brightness in the initial afterglow period (0-2 hours). When the Nd2O3 content is lower than 0.8%, the shallow trap density is insufficient, and the brightness decay rate (ΔB / Δt) in the initial afterglow period exceeds 20mcd / m 2 When the value exceeds 1.2%, the shallow traps over-capture electrons, inhibiting the release of electrons from the deep traps, causing the brightness to drop sharply to 500mcd / m in the middle and late stages of the afterglow (>6 hours). 2 The present invention optimizes the shallow trap density by 0.8-1.2% so that the initial decay rate of afterglow ΔB / Δt≤10mcd / m 2 ·min, and the brightness transitions smoothly in the middle and late stages.

[0035] Innovation mechanism: Through Nd 3+ Shallow trap and Eu 2+ The energy level matching of the luminescence center (ΔE≤0.2eV) enables rapid electron release and efficient energy transfer, reducing energy loss during electron capture.

[0036] Dy 3+ Deep trap energy levels (1.0-1.2eV) are formed in the lattice, and their electron capture-release time constant (τ2) is 5-8 hours, which dominates the long-lasting luminescence in the middle and late stages of afterglow (>2 hours). When the Dy2O3 content is less than 0.3%, the deep trap density is insufficient and the afterglow time T50 is less than 15 hours; when it exceeds 0.5%, the strong electron confinement of the deep traps leads to the suppression of the brightness of the initial afterglow (<3000mcd / m 2 The 0.3-0.5% ratio of the present invention balances the deep trap density and the electron binding energy, so that the afterglow time T50 is ≥ 18 hours, and the initial brightness is not significantly affected.

[0037] Innovation mechanism: Through Dy 3+ The "electron reservoir" effect of the deep trap, combined with the rapid release of the shallow trap, forms a double exponential decay kinetic model, and the afterglow brightness decay function satisfies: The B1 / B2 ratio is given by Nd 3+ / Dy 3+ Proportional control to achieve a smooth transition of the brightness attenuation curve (goodness of fit R 2 ≥0.99).

[0038] Preferably, in step B: The thickness of the SiO2 layer is 5-10nm, the thickness of the UV absorbing layer is 2-5nm, and the thickness of the fluorosilane layer is 3-5nm; The UV absorption layer is a benzotriazole compound, and the fluorosilane is heptadecafluorodecyltrimethoxysilane.

[0039] Preferably, in step (2): The mass ratio of rhyolite pigment to titanate coupling agent is 1:0.05; The coupling reaction temperature is 50-70°C, and the reaction time is 20-40 minutes.

[0040] A mass ratio of 1:0.05 ensures that the coupling agent molecules form a monolayer covering the pigment surface (coverage ≥ 90%). When the ratio is less than 1:0.05, insufficient coupling agent results in coverage ≤ 70%, and the interfacial bonding strength decreases by > 30%. When the ratio is greater than 1:0.05, excess coupling agent self-aggregates to form micelles (particle size > 50 nm), hindering the resin-pigment interface. By optimizing the 1:0.05 ratio, the interfacial shear strength is increased to ≥ 25 MPa (≤ 15 MPa for the untreated system).

[0041] Reaction temperature 50-70°C: When the temperature is less than 50°C, the coupling agent hydrolysis rate is low (less than 0.1 mol / (L·min)), resulting in incomplete reaction (bonding rate ≤ 75%). When the temperature is greater than 70°C, the coupling agent thermal decomposition rate is greater than 5%, and a phase transition of the rhyolitic pigment (rutile TiO2 to anatase) is initiated. The present invention utilizes kinetic control in the 50-70°C range to match the coupling agent hydrolysis rate with the condensation rate, achieving a bonding rate of ≥ 95%.

[0042] Reaction time 20-40 minutes: When the reaction time is less than 20 minutes, the condensation reaction has not reached equilibrium (bonding rate ≤ 80%); when it is greater than 40 minutes, the bonded coupling agent undergoes a partial hydrolysis reverse reaction (reverse reaction rate > 10%). The 20-40 minute reaction window allows the system to reach dynamic equilibrium, resulting in optimal bonding rate and stability.

[0043] Preferably, in step (3): The temperature zones of the twin-screw extruder are: feeding section 140-150°C, melting section 155-160°C, mixing section 160-165°C, and die head 150-155°C; Temperature gradient innovation: A dynamic balance between resin plasticization, melt mixing and low-temperature discharging is achieved through four-stage temperature control.

[0044] Feeding section (140-150℃): low temperature pre-plasticization reduces local overheating of luminous particles at the feeding port (surface temperature ≤ 145℃), avoiding Eu 2+ The lattice oxygen vacancy density increases (controlled to ≤10 16 / cm 3 , conventional process ≥10 17 / cm 3 ); Melting stage (155-160°C): slightly higher than the resin melting point (EVA-g-MAH melting temperature is about 150°C), ensuring that the resin is fully melted and wraps the luminous particles, and the melt viscosity drops to 800-1200 Pa·s (suitable for shear dispersion); Mixing section (160-165℃): briefly increase the temperature (ΔT≤5℃) to improve the melt fluidity, so that the rhytoid pigment and the luminous particles are mixed in the high shear zone of the screw (shear rate 200-250s -1 ) uniform dispersion (D90 / D10 ≤ 3), while avoiding heat accumulation through time control (residence time ≤ 30 seconds); Die section (150-155°C): Cool down to near the melting point of the resin, reduce the melt outlet expansion rate (≤5%), and prevent the fluorosilane coating from rupturing due to expansion stress (rupture rate <2%).

[0045] The total temperature rise is controlled within 25°C (the temperature rise of conventional process is ≥40°C), so that the thermal degradation rate of the luminous material is less than 3%, which is significantly lower than the traditional process (>15%).

[0046] Dispersion mechanism: Screw speed and resin melt index (MFI15-25g / 10min) coordinately regulate shear rate (200-250s -1 ).

[0047] Low speed zone (<300rpm): Insufficient shearing results in pigment agglomerate size ≥5μm and uneven flow effect (color difference ΔE ≥2.5); High-speed zone (>400 rpm): Excessive shear heat generation causes the local melt temperature to be >170°C, initiating thermal decomposition of the fluorosilane layer (weight loss rate >5%). Optimization range (300-400rpm): By matching the shear rate and melt viscosity, the luminous particles are broken to D50 = 2-3μm (original particles D50 = 5-10μm), while the rhyolite pigment dispersion uniformity D90 / D10 ≤ 2.5, and the color difference ΔE < 1.5 (CIELab standard).

[0048] Achieve low-temperature high-shear dispersion, breaking the contradiction between "high-temperature dispersion" and "thermal protection" in traditional processes.

[0049] Pressure balance design: melt pressure of 3-5MPa ensures that the resin fully penetrates into the gap between the luminous particles and the pigment (penetration depth ≥50nm), forming a dense coating structure.

[0050] Low pressure area (<3MPa): The resin filling is incomplete, and there are micropores (pore diameter>100nm) between the particles, resulting in a masterbatch tensile strength of <25MPa; High pressure area (>5MPa): Excessive extrusion pressure causes the fluorosilane coating to rupture (rupture rate>10%), and the water and oxygen permeability increases to ≥10-3g / (m 2 h); Optimize pressure (3-5MPa): Through pressure-viscosity matching, the resin coating integrity of the particles is ≥98%, the interface bonding strength is ≥20MPa, and the fluorosilane layer rupture rate is <2%.

[0051] Under the premise of protecting the integrity of the coating layer, the mechanical properties (tensile strength ≥ 30MPa) and weather resistance of the masterbatch are both improved.

[0052] Preferably, in step (4): The barrel temperature of the injection molding process is 155-160°C, and the mold temperature is 40-60°C; UV curing conditions: wavelength 365nm, irradiation intensity 50-60mW / cm 2 , time 30-60 seconds, photoinitiator TPO addition amount 0.1-0.3%.

[0053] Barrel temperature 155-160℃: This temperature is slightly higher than the melting temperature of the carrier resin (EVA-g-MAH) (about 150°C), ensuring sufficient melt flow (melt flow index ≥ 15g / 10min), and strictly lower than the thermal degradation threshold of the luminous material (180°C). When the temperature is greater than 160°C, Eu 2+ The lattice oxygen vacancy density of the luminescence center increases sharply (>10 17 / cm 3 ), resulting in a shortening of the afterglow time by more than 30%; at temperatures below 155°C, the resin is not fully plasticized, the melt fluidity is insufficient (MFI < 10g / 10min), and flow marks appear on the product surface (roughness Ra > 1.5μm). The present invention achieves a balance between melt fluidity and thermal protection in the 155-160°C range, resulting in a thermal degradation rate of less than 3% and a surface finish of Ra ≤ 0.8μm.

[0054] Mold temperature 40-60℃: The low-temperature design of the mold allows the melt to cool and solidify quickly (cooling rate ≥ 20℃ / s), reducing the high-temperature exposure time of the luminous particles in the melt (<30 seconds). When the mold temperature is greater than 60℃, the cooling rate decreases (<10℃ / s), and the lattice oxygen vacancy density of the luminous particles increases to ≥10 16 / cm 3 At temperatures below 40°C, the temperature difference between the melt and the mold is too large, leading to internal stress accumulation (residual stress ≥ 15 MPa) and product warpage > 5%. The present invention utilizes dynamic thermal management in the 40-60°C range to simultaneously optimize product dimensional stability (warpage < 0.5%) and luminous performance (afterglow time ≥ 18 hours).

[0055] UV curing condition design (wavelength 365nm, intensity 50-60mW / cm 2 , time 30-60 seconds, TPO addition amount 0.1-0.3%) Wavelength 365nm and TPO initiator synergistically: The photoinitiator TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) has a maximum absorption peak at a wavelength of 365 nm (ε=1200 L / mol·cm), and its excited state lifetime (τ≈10 -6 s) matches the reactivity of the maleic anhydride groups in the resin. When the TPO addition is less than 0.1%, the free radical generation rate is insufficient and the crosslinking degree is less than 60%. When it is greater than 0.3%, residual initiator causes yellowing of the product (Δb* > 2.5). The 0.1-0.3% addition of the present invention achieves a surface crosslinking degree of ≥ 80% and a color difference ΔE of < 1.5 (CIELab standard).

[0056] Irradiation intensity 50-60mW / cm2 With time control: This intensity range enables the UV photon flux (1.5-1.8×10 18 photons / cm 2 ·s) matches the initiation efficiency of TPO to ensure that the cross-linking reaction depth is controlled within 50-100μm (the surface layer is strengthened while the internal resin is not affected). When the irradiation time is less than 30 seconds, the cross-linking network is incomplete (hardness < H); when it is greater than 60 seconds, over-irradiation causes thermal aging of the resin (surface crack density ≥ 5 / mm 2 Through precise control within 30-60 seconds, the surface hardness of the product is increased to 2H (pencil hardness), and the wear resistance (Taber abrasion) is less than 10mg / 1000 times.

[0057] The present invention provides a high-efficiency, long-lasting luminous rhyolite masterbatch and its preparation method. It has the following beneficial effects: 1. This invention utilizes a titanate coupling agent to modify the surface hydroxyl groups of rhyochrome pigments, achieving dual anchoring at the pigment-resin interface through chemical bonding and physical entanglement. This increases tensile strength to ≥25 MPa and achieves pigment dispersion uniformity (D90 / D10) ≤2.5. Compared to existing solutions that rely on single physical mixing or general-purpose silane coupling agents, this solution addresses the issues of sudden drop in mechanical properties due to interface defects (existing solutions have tensile strength ≤15 MPa) and transmittance fluctuations caused by pigment agglomeration.

[0058] 2. The present invention adopts the sandwich coating design of SiO2 dense layer (5-10nm) - benzotriazole ultraviolet absorption layer - fluorosilane hydrophobic layer, and the water and oxygen permeability is less than 10 -5 g / (m 2 h) Afterglow retention after damp heat aging is >90%. Compared to existing protection solutions using a single SiO2 or organic coating, this overcomes interfacial peeling under UV irradiation (brightness decay >20% after aging in existing solutions) and the runaway lattice oxygen vacancy defects caused by water vapor penetration.

[0059] 3. This invention achieves a surface crosslinking degree of 80-85% and internal toughness retention (elongation at break ≥ 200%) through the synergistic optimization of UV initiator concentration (0.05-0.1%) and curing time (30-60s). Compared to the existing crude strategies of blindly extending curing time or increasing initiator dosage, it solves the problems of brittle cracking caused by excessive crosslinking (existing solutions have a wear value of ≥ 25mg / 1000 times) and surface adhesion caused by insufficient curing.

[0060] 4. The present invention combines low content rare earth doping (Eu 2+1.2-1.5%) and thin layer coating (SiO2 thickness 5nm) components are simplified, the raw material cost is reduced by 30-40%, and the yield rate is stabilized at ≥92% through low temperature injection molding (mold temperature 40-60℃). Compared with the existing technology that relies on high rare earth loading (existing solution Eu 2+ ≥2%) or complex multi-layer coating solutions, breaking through the bottleneck of large-scale application of luminous materials due to high cost constraints. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 Schematic diagram of the method of the present invention. DETAILED DESCRIPTION

[0062] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the present specification. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0063] Example 1: High-brightness masterbatch for outdoor signage Raw material ratio (mass percentage): Luminous matrix (CaAlSiN3:Eu 2+ 1.5%,Nd 3+ 1.0%,Dy 3+ 0.4%): 22% Rhyolite pigment (rutile TiO2): 6% Titanate coupling agent (isopropyl trititanate): 0.8% Carrier resin (EVA-g-MAH, grafting rate 2.5%): 70% Additives (antioxidant 1010: 0.5% + zinc stearate: 0.7%): 1.2% Preparation process: Luminous matrix synthesis: Mix CaCO3:Al2O3:Si3N4=35:40:25, add Eu2O3 (1.5%), Nd2O3 (1.0%), Dy2O3 (0.4%), and sinter at 1500℃ for 7 hours in N2 / H2 (95:5); Gradient coating: SiO2 layer (8 nm) → benzotriazole layer (3 nm) → heptafluorodecylsilane layer (4 nm).

[0064] Flow pigment treatment: The rhyolite pigment and the coupling agent were mixed at a ratio of 1:0.05 and reacted at 60°C for 30 minutes.

[0065] Blending extrusion: Twin-screw extruder parameters: feeding section 145℃ → melting section 158℃ → mixing section 162℃ → die head 153℃; The screw speed is 350 rpm and the melt pressure is 4 MPa.

[0066] Injection molding and curing: Injection molding: barrel temperature 158°C, mold temperature 50°C; UV curing: 365nm / 55mW / cm 2 / 40 seconds, TPO addition amount 0.2%.

[0067] Example 2: Masterbatch for highly weather-resistant automotive parts Raw material ratio (mass percentage): Luminous matrix (CaAlSiN3:Eu 2+ 1.8%,Nd 3+ 0.8%,Dy 3+ 0.5%): 18% Rhythm pigment (iron oxide red Fe2O3): 5% Titanate coupling agent: 0.6% Carrier resin (EVA-g-MAH, grafting rate 1.8%): 75% Additives (antioxidant 168: 0.3% + erucamide: 0.3%): 0.6% Preparation process: Luminous matrix synthesis: Sintering: 1520℃ / 6.5 hours, coating layer: SiO2 (10nm)→benzotriazole (5nm)→fluorosilane (5nm).

[0068] Flow pigment treatment: Coupling reaction: 55°C / 25 minutes.

[0069] Blending extrusion: Temperature zones: feeding section 148°C → melting section 160°C → mixing section 165°C → die head 155°C; The screw speed is 380 rpm and the melt pressure is 3.5 MPa.

[0070] Injection molding and curing: Injection molding: barrel 160℃, mold 60℃; UV curing: 365nm / 60mW / cm 2 / 60 seconds, TPO added 0.3%.

[0071] Example 3: Low-cost masterbatch for smart home Raw material ratio (mass percentage): Luminous matrix (CaAlSiN3: Eu 2+ 1.2%,Nd 3+ 1.2%,Dy 3+ 0.3%): 16% Rhythm pigment (phthalocyanine blue): 3% Titanate coupling agent: 0.5% Carrier resin (EVA-g-MAH, grafting rate 1.0%): 80% Additives (antioxidant 1076: 0.2% + PE wax: 0.3%): 0.5% Preparation process: Luminous matrix synthesis: Sintering: 1450℃ / 8 hours, coating layer: SiO2 (5nm)→benzotriazole (2nm)→fluorosilane (3nm).

[0072] Flow pigment treatment: Coupling reaction: 70°C / 20 minutes.

[0073] Blending extrusion: Temperature zones: feeding section 140°C → melting section 155°C → mixing section 160°C → die head 150°C; The screw speed was 300 rpm and the melt pressure was 5 MPa.

[0074] Injection molding and curing: Injection molding: barrel 155℃, mold 40℃; UV curing: 365nm / 50mW / cm 2 / 30 seconds, TPO added 0.1%.

[0075] Comparative Example 1: Compared with Example 1, the difference is that the rhyolite pigment is not treated with a titanate coupling agent, and the rest are the same.

[0076] Comparative Example 2: Compared with Example 1, the difference is that the thickness of the SiO2 coating layer is adjusted to 15nm (outside the range of 5-10nm), and the rest are the same.

[0077] Comparative Example 3: Compared with Example 2, the difference is that the ultraviolet absorption layer is replaced by ordinary carbon black (non-benzotriazole), and the rest are the same.

[0078] Comparative Example 4: Compared with Example 2, the difference is that the temperature of the injection mold is adjusted to 80° C. (outside the range of 40-60° C.), and the rest are the same.

[0079] Comparative Example 5: Compared with Example 3, the difference is that the fluorosilane hydrophobic layer coating is eliminated, and the rest are the same.

[0080] Comparative Example 6: Compared with Example 3, the difference is that the UV curing time is extended to 90 seconds (outside the range of 30-60 seconds), and the rest are the same.

[0081] Experiment 1: Luminous Performance and Afterglow Stability Test Instructions Experimental procedures Sample preparation: The masterbatches of Examples 1-3 and Comparative Examples 1, 2, and 5 were injection molded into standard samples of 50 mm×50 mm×2 mm, and the surfaces were polished (Ra≤0.5 μm).

[0082] Initial brightness test: Use D65 standard light source (1000 lux) to excite the sample for 10 minutes. After turning off the light source, immediately use ST-86LA luminance meter to measure the initial brightness (test points: center and four corners of the sample, take the average value).

[0083] Afterglow time test: The time (T50) for the brightness to decay to 50% of the initial value was recorded in a dark room, and data were recorded every 30 minutes for 24 hours.

[0084] Wet heat aging treatment: The sample was placed in a constant temperature and humidity chamber (85°C / 85% RH) for 1000 hours, and then taken out and steps 2-3 were repeated to test the afterglow retention rate.

[0085] The experimental data are shown in Table 1 below: Table 1 - Luminous performance and afterglow stability test data The experimental data show that the embodiment group has 2+ -Nd 3+ -Dy 3+ The energy level collaborative design significantly improves the initial brightness and afterglow time. 2+ The doping amount (1.5%) is in the optimized range, which not only avoids concentration quenching but also ensures the density of luminescent centers. Its initial brightness reaches 4285mcd / m 2 , far exceeding the 3520mcd / m of comparative example 1 (uneven dispersion due to no coupling agent) 2In addition, the protective effect of the gradient coating structure (SiO2-UV absorption layer-fluorosilane) is particularly critical in Comparative Example 2 (the SiO2 layer is too thick) and Comparative Example 5 (no fluorosilane layer): the overly thick SiO2 layer induces microcracks due to internal stress, and the water and oxygen permeability increases, resulting in the afterglow time decreasing from 18.3h (Example 1) to 14.7h; while the afterglow retention rate of Comparative Example 5 without a fluorosilane layer after wet heat aging is only 53.8%, significantly lower than the 93.7% of Example 1, confirming the inhibitory effect of the hydrophobic layer on lattice oxygen vacancies.

[0086] Nd 3+ Shallow trap and Dy 3+ The synergistic effect of deep traps is further demonstrated in the afterglow decay curves: T50 for the Example groups is consistently greater than 16 hours, while the Comparative Example group experiences a sudden drop in brightness due to a break in the energy level chain (interface defects in Comparative Example 1 hinder electron transfer). This bi-exponential decay pattern is consistent with the staged electron release mechanism of deep and shallow traps, confirming the importance of multi-ion doping energy level design for long-lasting luminescence.

[0087] In summary, Experiment 1 systematically demonstrated the innovativeness of the component optimization and structural design of the present invention from the three dimensions of luminescence performance, environmental stability, and energy level synergy, providing a reliable basis for the efficient application of luminous materials.

[0088] Experiment 2: Weathering Resistance and Environmental Stability Test Instructions Experimental procedures Sample preparation: The masterbatches of Examples 1-3 and Comparative Examples 2, 3, and 5 were injection molded into 100 mm×100 mm×1 mm sheets, and the surfaces were cleaned and then sprayed with a transparent epoxy resin protective layer (50 μm thick).

[0089] UV aging treatment: The samples were placed in a QUV accelerated aging chamber (UVA-340 lamp, irradiation intensity 0.76W / m 2 @340nm), continuous irradiation for 1000 hours, pause every 200 hours to test brightness.

[0090] Water and oxygen permeability test: The water vapor transmission rate (WVTR) and oxygen transmission rate (OTR) were measured at 25°C / 50% RH using the differential pressure method (ASTM F1249).

[0091] Contact angle test: Using a contact angle meter (5 μL deionized water droplet), 5 points were randomly selected on the sample surface to measure the static contact angle and the average value was taken.

[0092] The experimental data are shown in Table 2 below: Table 2- Weather resistance and environmental stability test data The design of the gradient coating structure (SiO2-benzotriazole-fluorosilane) showed significant environmental protection advantages in this experiment. The water and oxygen permeability of Examples 1-3 were all lower than 1.5×10 -5 g / (m 2 h), while the permeability of comparative example 2 (SiO2 layer is too thick) soared to 86.7×10 -5 g / (m 2 h), verifying the necessity of a 5-10 nm thickness for balancing compactness and mechanical stability. The selective shielding effect of the benzotriazole UV absorbing layer is particularly prominent in Comparative Example 3 (replaced with carbon black): although carbon black can absorb some ultraviolet light, its broad spectrum absorption leads to a decrease in visible light transmittance, causing an increase in color difference ΔE (1.2 in Example 2 and 3.5 in Comparative Example 3). At the same time, due to the inability to quickly dissipate ultraviolet energy (benzotriazole excited state lifetime is 10 -9 s), resulting in increased photodegradation of the material, with the brightness decay rate increasing from 3.8% in Example 2 to 23.9% in Comparative Example 3.

[0093] The hydrophobic protection mechanism of the fluorosilane layer is further confirmed by contact angle data. The contact angles of the Example group are all >119°. However, due to the enhanced surface hydrophilicity of Comparative Example 5 (no fluorosilane layer) (contact angle 61.7°), water molecules more easily penetrate into the luminous matrix, causing an increase in the lattice oxygen vacancy density and a brightness decay rate of up to 31.4% after wet heat aging. This synergistic effect of hydrophobicity and chemical shielding enables the Example group to maintain stable luminous performance even in harsh environments.

[0094] Comprehensive experimental data demonstrates that the gradient coating design and optimized components of the present invention overcome the weather resistance bottleneck of traditional materials through multi-level protection, including physical isolation, UV energy dissipation, and a hydrophobic barrier. The performance degradation observed in the control group demonstrates the essential importance of each functional layer, providing key technical support for the long-term outdoor application of luminous products.

[0095] Experiment 3: Interface bonding and mechanical properties test description Experimental procedures Sample preparation: The masterbatches of Examples 1-3 and Comparative Examples 1, 4, and 6 were injection molded into dumbbell-shaped specimens (thickness 2 mm, gauge length 50 mm) according to ASTM D638, and the surfaces had no scratches.

[0096] Tensile strength test: The tensile strength was measured using a universal material testing machine (speed 5 mm / min), the maximum load before fracture was recorded, and the stress (load / cross-sectional area) was calculated.

[0097] Elongation at break test: During the stretching process, the elongation of the gauge section was recorded synchronously, and the elongation was calculated based on the elongation at the moment of fracture (ΔL / L0×100%).

[0098] Surface hardness test: Use a pencil hardness tester (Mitsubishi UNI standard) to scratch the surface from 6H to 6B, and take the highest hardness that does not produce permanent scratches as the test value.

[0099] The experimental data are shown in Table 3 below: Table 3 - Interface bonding and mechanical properties test data Experimental data reveals the central role of titanate coupling agents in interfacial strengthening. The tensile strength of the Example group (26.8-31.7 MPa) was significantly higher than that of Comparative Example 1 (14.6 MPa), demonstrating that the coupling agent effectively enhances the interfacial adhesion between the rhyochrome pigment and the resin through a dual mechanism of chemical bonding (—Ti—O—pigment surface hydroxyl groups) and physical entanglement (interpenetration of long resin chains). Because Comparative Example 1 lacked a coupling agent, pigment agglomeration led to stress concentration, resulting in an elongation at break of only 83%, less than one-third that of Example 1, confirming the crucial influence of the coupling agent on dispersion uniformity.

[0100] The impact of molding temperature on lattice integrity is particularly pronounced in Comparative Example 4. Increasing the mold temperature to 80°C slows the cooling rate, increasing the oxygen vacancy density within the luminescent particles and weakening the plastic deformation capacity of the matrix resin. Although the tensile strength of Comparative Example 4 (18.9 MPa) is slightly higher than that of Comparative Example 1, its elongation at break (105%) is still significantly lower than that of Example 2 (218%), indicating that high-temperature-induced lattice defects irreversibly reduce the material's toughness.

[0101] Precise control of UV curing parameters directly affects the formation of surface cross-linked networks. Although the surface hardness of Comparative Example 6 (curing time 90 seconds) reaches 3H due to excessive cross-linking, the excessively high cross-linking density causes the resin to become brittle, and the elongation at break drops sharply to 68%. In contrast, Example 3 forms a moderately cross-linked network (cross-linking degree ≈ 75%) by curing for 30 seconds, which maintains an elongation at break of more than 200% while maintaining the hardness (H grade), verifying the balanced design logic of "time-strength-toughness". From the dimension of mechanical properties, this experiment systematically demonstrates the necessity of the synergy between component optimization and process control.

[0102] Experiment 4: Processing Thermal Stability and Dispersion Uniformity Test Description Experimental procedures Sample preparation: The masterbatches of Examples 1-3 and Comparative Examples 2, 4, and 6 were extruded by a twin-screw extruder and then injection-molded into 50 mm × 50 mm × 2 mm samples. The surfaces were ultrasonically cleaned with alcohol and dried.

[0103] Thermal degradation rate test: The weight loss curve of the sample from 50°C to 400°C was recorded using a thermogravimetric analyzer (TGA, nitrogen atmosphere, heating rate 10°C / min), and the weight loss rate at 250°C was calculated (excluding the effect of water volatilization).

[0104] Dispersion uniformity analysis: The sample was fractured in liquid nitrogen and the cross section was observed using SEM after gold spraying. Ten viewing fields (×5000 times) were randomly selected to calculate the D90 / D10 ratio of the luminous particles.

[0105] Surface roughness test: A white light interferometer profilometer (Zygo New View 9000) was used to scan along the diagonal line of the sample to calculate the surface roughness Ra value.

[0106] The experimental data are shown in Table 4 below: Table 4 - Processing thermal stability and dispersion uniformity test data The thermal stability of the gradient coating was fully verified in this experiment. The thermal degradation rates of Examples 1-3 were all lower than 3.8%, while in Comparative Example 2 (the SiO2 layer was too thick), the thermal degradation rate rose to 8.5% due to microcracks causing local thermal oxidation of the resin. SEM analysis showed that the D90 / D10 of the luminous particles in Comparative Example 2 reached 5.7, indicating that the overly thick coating broke during the shearing process and the released SiO2 fragments triggered secondary agglomeration of the particles. In contrast, the D90 / D10 of Example 1 was only 2.3, proving that a coating thickness of 5-10 nm can both buffer shear stress and avoid dispersion degradation caused by its own brittleness.

[0107] Mold temperature's regulation of melt cooling dynamics directly impacts surface quality. In Comparative Example 4 (mold temperature 80°C), insufficient cooling rate (<5°C / s) resulted in slow crystallization of the melt, leading to migration and aggregation of luminescent particles. The surface roughness Ra increased from 0.57 μm in Example 2 to 1.95 μm. Furthermore, high temperature prolonged the relaxation time of the resin molecular chains, resulting in a significantly higher thermal degradation rate (6.3%) than in the Example group, confirming the necessity of low-temperature molding for thermal-mechanical coupling stability.

[0108] The nonlinear effect of UV curing time on the surface cross-linking degree is particularly evident in Comparative Example 6. Although extending the curing time (90 seconds) increases the surface cross-linking degree to 95%, excessive cross-linking leads to uneven resin shrinkage stress, the surface roughness Ra reaches 2.14μm, and the thermal stability of the internal uncured resin decreases (thermal degradation rate 9.7%). In Example 3, a gradient cross-linked structure (80% surface / 60% interior) is formed by 30 seconds of curing, while maintaining a thermal degradation rate of ≤3.8% at Ra=0.82μm, verifying the precise balance logic of time-energy input. The experimental data reveals the strong correlation between process parameters and material properties from three aspects: heat, dispersion, and morphology.

[0109] Experiment 5: Surface wear resistance and anti-aging test instructions Experimental procedures Sample preparation: The masterbatches of Examples 1-3 and Comparative Examples 3, 5, and 6 were injection molded into 100 mm×100 mm×3 mm flat plate samples, and the surface was polished to Ra≤0.3 μm.

[0110] Taber abrasion test: The mass loss of the test piece after 1000 rotations was measured using a CS-10 grinding wheel (load 1 kg, rotation speed 60 rpm) (accuracy 0.1 mg).

[0111] UV aging treatment: The samples were placed in a QUV aging box (UVA-340 lamp, 0.76W / m 2 @340nm) for 500 hours, and pause every 100 hours to test the color difference.

[0112] Surface crack observation: Five fields of view (1 mm × 1 mm) were randomly selected using a laser confocal microscope (×200 times) to count the crack density per unit area.

[0113] The experimental data are shown in Table 5 below: Table 5 - Surface wear resistance and anti-aging test data The energy dissipation mechanism of the benzotriazole UV absorption layer plays a key role in this experiment. The Taber abrasion values ​​of Examples 1-2 are all lower than 12 mg / 1000 times, while the comparative example 3 (carbon black replaces the UV layer) lacks selective UV shielding, and the photodegradation of the resin surface is aggravated, the abrasion value rises to 26.9 mg, and the color difference ΔE reaches 3.8. Although the broad spectrum absorption of carbon black can block some ultraviolet light, its light absorption and heating effect (local temperature rise> 15 ° C) causes the surface resin chain to break, and the crack density (7 / mm 2 ) was significantly higher than that of the embodiment group (0-1 / mm 2), verifying the rapid relaxation of the benzotriazole excited state (lifetime 10 -9 s) Inhibitory effect on heat accumulation.

[0114] The hydrophobic protection of the fluorosilane layer and the surface cross-linking synergistically improve the wear resistance. In comparative example 5 (without fluorosilane layer), due to the enhanced surface hydrophilicity (contact angle 61.7°), water molecules penetrated and caused the resin to swell, the wear value soared to 34.5 mg, and the crack density reached 12 / mm. 2 In Example 1, the hydrophobic barrier (contact angle 124.3°) of fluorosilane and the surface cross-linked network (cross-linking degree ≥80%) synergistically maintained an abrasion value of ≤8.3 mg even in a high humidity environment, confirming the necessity of the "hydrophobic-cross-linking" dual mechanism for interface stability.

[0115] The precise control of UV curing time directly affects the mechanical properties of the surface layer. In Comparative Example 6 (curing time 90 seconds), the resin became brittle due to over-crosslinking. Although the surface hardness was increased to 3H, the internal stress release was insufficient, causing micro cracks (density 9 / mm 2 ), the wear value (18.7 mg) is higher than that of Example 3 (11.6 mg). Example 2 achieves a balance between hardness (3H) and toughness (elongation at break 218%) through moderate crosslinking (crosslinking degree ≈ 85%) during a 60-second cure, demonstrating that the dynamic matching of energy input and material response is the core logic of durability design. Comprehensive experimental data shows that the multi-level protection and process synergy strategy of the present invention effectively overcomes the surface degradation problem of traditional luminous materials.

[0116] Experiment 6: Economic and processing efficiency test instructions Experimental procedures Raw material cost accounting: The raw material purchase prices of Examples 1-3 and Comparative Examples 1, 5, and 6 (based on the market quotation in 2025) were counted to calculate the raw material cost per kilogram of masterbatch.

[0117] Machining cycle measurement: The total time of injection molding (including demoulding) and UV curing was recorded, and the average value was obtained by repeating 10 times (equipment: Haitian MA2500II injection molding machine + UV curing tunnel).

[0118] Yield rate statistics: Continuously produce 1000 standard samples (50mm×50mm×2mm), remove defective parts such as surface bubbles, cracks, deformation, etc., and calculate the yield rate.

[0119] The experimental data are shown in Table 6 below: Table 6 - Economic and processing efficiency test data Sample Group Raw material cost (yuan / kg) Processing cycle (seconds) Comprehensive yield rate (%) Example 1 182.5 58 96.3 Example 2 168.9 63 94.8 Example 3 127.4 42 92.1 Comparative Example 1 175.2 55 68.7 Comparative Example 5 122.8 39 71.5 Comparative Example 6 134.6 89 83.2 Experimental data reveals the dual impact of component optimization and process synergy on economic efficiency. In Example 3, by reducing the content of the luminous matrix (15%) and simplifying the coating layer (SiO2 thickness 5nm), the raw material cost (127.4 yuan / kg) is reduced by 30% compared with Example 1 (182.5 yuan / kg). At the same time, the processing cycle (42 seconds) is significantly shortened due to low-temperature molding and short-time curing. However, although the cost of Comparative Example 5 (fluorine-free silane layer) is further reduced to 122.8 yuan / kg, the yield rate drops sharply to 71.5% due to wet heat aging, which confirms the irreducibility of functional components (such as fluorosilane) - although its hydrophobic protection increases the cost by about 5%, it increases the yield rate from 70% to more than 90%, and the overall cost performance is better.

[0120] Precise control of process parameters directly impacts processing efficiency and quality balance. In Comparative Example 6 (90-second curing time), excessive crosslinking extended the processing cycle to 89 seconds, and internal stress-induced warping resulted in a yield of only 83.2%, far below the 92.1% in Example 3. In contrast, the 30-second curing in Example 3, achieved by optimizing the photoinitiator (TPO) concentration (0.1%), ensured a crosslinking degree (≥75%) while avoiding energy waste, achieving the optimal "speed-quality" balance.

[0121] The hidden costs associated with component substitution are particularly prominent in Comparative Example 1. While omitting the titanate coupling agent reduces raw material costs by 4%, insufficient interfacial bonding leads to a significant drop in yield (68.7%), resulting in actual production costs exceeding those of Example 1. This demonstrates that the present invention's technical solution is not simply a stacking of high-cost components, but rather achieves an optimal balance between performance, cost, and efficiency through scientific formulation and process innovation. The experimental data validates the commercial feasibility of the present invention's technical approach from an industrial perspective.

[0122] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A high-efficiency long afterglow luminous rhyolite masterbatch, characterized in that: The following components are included by mass percentage: Luminous matrix: 10-25%; Rhythm pigment: 2-8%; Coupling agent: 0.5-1%; Carrier resin: 75-90%; Additives: 0.5-2%, including antioxidants and lubricants.

2. The high-efficiency long afterglow luminous rhyolite masterbatch according to claim 1, characterized in that: The carrier resin is maleic anhydride grafted ethylene-vinyl acetate copolymer, with a grafting rate of 1-3% and a melt index of 15-25 g / 10 min.

3. The high-efficiency long afterglow luminous rhyolite masterbatch according to claim 1, characterized in that: The coupling agent is isopropyl trititanate.

4. A method for preparing the masterbatch according to claim 1, characterized in that: The following steps are involved: (1) Synthesis and gradient coating of luminescent matrix; (2) Coupling treatment of rhyolite pigments; (3) Blending and extrusion granulation of masterbatch; (4) Injection molding and UV curing.

5. The method for preparing a masterbatch according to claim 4, characterized in that: Step (1) includes: A. Mix CaCO3, Al2O3, Si3N4 with Eu2O3, Nd2O3 and Dy2O3 according to mass percentage, sinter at 1450-1550℃ for 6-8 hours in N2 / H2 mixed gas with a volume ratio of 95:5 to obtain CaAlSiN3:Eu 2+ ,Nd 3+ ,Dy 3+ powder; B. The powder is coated with SiO2 layer, UV absorption layer and fluorosilane hydrophobic treatment in sequence. The coating order is SiO2 layer → UV absorption layer → fluorosilane layer.

6. The method for preparing a masterbatch according to claim 5, characterized in that: The doping ratio of rare earth oxide in step A is: Eu2O3: 1.2-1.8%; Nd2O3: 0.8-1.2%; Dy2O3: 0.3-0.5%.

7. The method for preparing a masterbatch according to claim 5, characterized in that: In step B: The thickness of the SiO2 layer is 5-10nm, the thickness of the UV absorbing layer is 2-5nm, and the thickness of the fluorosilane layer is 3-5nm; The UV absorption layer is a benzotriazole compound, and the fluorosilane is heptadecafluorodecyltrimethoxysilane.

8. The method for preparing a masterbatch according to claim 4, wherein: In step (2): The mass ratio of rhyolite pigment to titanate coupling agent is 1:0.05; The coupling reaction temperature is 50-70°C, and the reaction time is 20-40 minutes.

9. The method for preparing a masterbatch according to claim 4, wherein: In step (3): The temperature zones of the twin-screw extruder are: feeding section 140-150°C, melting section 155-160°C, mixing section 160-165°C, and die head 150-155°C; The screw speed is 300-400 rpm and the melt pressure is 3-5 MPa.

10. The method for preparing a masterbatch according to claim 4, characterized in that: In step (4): The barrel temperature of the injection molding process is 155-160°C, and the mold temperature is 40-60°C; UV curing conditions: wavelength 365nm, irradiation intensity 50-60mW / cm 2 , time 30-60 seconds, photoinitiator TPO addition amount 0.1-0.3%.

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