A photoluminescent composition, a light-generating material and its preparation method
By combining specific materials and processes, the problems of long-term light emission in the dark and low-temperature molding in existing technologies have been solved, realizing a light-emitting material with long-term light emission and good outdoor weather resistance on electric vehicles, meeting the requirements of passive position indication.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- BEIJING JU LING YAN PLASTIC CO LTD
- Filing Date
- 2026-05-19
- Publication Date
- 2026-07-31
AI Technical Summary
Existing passive warning materials cannot simultaneously achieve long-lasting luminescence in the dark, low-temperature molding and processing, and long-term reliability for outdoor use, resulting in poor positional warning effects in electric vehicles and low-light environments.
Photoluminescent compositions are prepared by synergistically compounding homopolymer polypropylene with a specific melt index, a specific polyolefin elastomer, and three long-afterglow luminescent powders with different wavelengths, combined with low-temperature melt extrusion and injection molding processes. These compositions form complementary spectra to provide long-lasting luminescence in the dark, and the material properties are enhanced by specific nucleating agents and inorganic fillers.
The photoluminescent material prepared under low-temperature conditions has achieved long-lasting luminescence in the dark, excellent outdoor weather resistance and mechanical strength, meeting the passive position indication requirements of electric vehicle body exterior parts and low-light traffic nodes. It exhibits slow brightness decay, good weather resistance and excellent mechanical properties.
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Abstract
Description
Technical Field
[0001] This application relates to the field of functional polymer materials technology, specifically to a photoluminescent composition, a light-generating material, and a method for preparing the same. Background Technology
[0002] With the increasing prevalence of electric vehicles (including electric passenger cars, electric commercial vehicles, and electric two-wheelers), the demand for passive vehicle location indicators at night and in low-light environments (such as underground parking garages, tunnel entrances and exits, unlit road sections, and charging stations) is becoming increasingly urgent. Ideal vehicle body exterior parts or matching luminous components should possess characteristics such as "no power supply required, maintenance-free, low-temperature molding, and long-lasting visibility in the dark."
[0003] Currently, common passive warning solutions mainly include reflective films, fluorescent coatings, and traditional long-afterglow plastics. Reflective films rely on direct external light sources (such as vehicle headlights) to produce a retroreflective effect, and become completely ineffective in the absence of light or at off-center viewing angles. Fluorescent coatings require continuous ultraviolet excitation and quickly extinguish once the excitation source is removed, leaving no afterglow in the dark. While traditional long-afterglow plastics can maintain a brief period of light emission after excitation stops, their manufacturing process typically requires melt extrusion temperatures above 220°C. High temperatures can cause thermal quenching of the phosphors, resulting in a decrease in afterglow brightness of over 40%; furthermore, the high shear rate during processing can easily damage the phosphor lattice. None of these solutions can simultaneously achieve long-lasting light emission in the dark, low-temperature molding processing, and long-term reliability for outdoor use.
[0004] Therefore, developing a photoluminescent material that can be prepared under low-temperature processing conditions, has a long duration of light emission in the dark, and also possesses excellent weather resistance and mechanical properties has significant engineering application value. Summary of the Invention
[0005] In order to overcome the problems of existing passive warning materials that cannot simultaneously achieve long-term luminescence in the dark, low-temperature molding and processing, and long-term reliability for outdoor use, this application provides a photoluminescent composition, a light-storing material, and a method for preparing the same.
[0006] In a first aspect, this application provides a photoluminescent composition, which adopts the following technical solution: A photoluminescent composition comprising the following components in parts by weight: 20-30 parts of homopolymer polypropylene with a melt index of 80-150 g / 10 min, 30-40 parts of homopolymer polypropylene with a melt index of 18-22 g / 10 min, 15-20 parts of polyolefin elastomer, 15-20 parts of composite luminescent powder, 0.4-1 part of nucleating agent, and 8-15 parts of inorganic filler; The polyolefin elastomer is TAFMER A-4090S; The composite luminescent powder is a SrAl2O4:Eu compound with a weight ratio of 1:(0.25-0.45):(0.05-0.2). 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ Zn 2+ A mixture.
[0007] This application provides a photoluminescent composition, which, through the synergistic compounding of homopolymer polypropylene with a specific melt index, a specific polyolefin elastomer, and three long-afterglow luminescent powders with different wavelengths, achieves comprehensive and excellent effects in terms of long-lasting luminescence in the dark, low-temperature processing adaptability, outdoor weather resistance, and mechanical strength. It can meet the passive location indication requirements of electric vehicle body exterior parts, charging facility markings, and low-light traffic nodes.
[0008] In this application, by using a blend of high melt index and low melt index homopolymer polypropylene, combined with a specific polyolefin elastomer, the composition can be melt extruded and injection molded within a low-temperature range of 180-200°C. Compared with traditional long-afterglow plastics that require processing temperatures above 220°C, the temperature of this application can effectively avoid thermal quenching of the luminescent powder and lattice damage caused by high temperatures, ensuring the performance of the photoluminescent material.
[0009] In this application, the composite luminescent powder is SrAl2O4:Eu 2+ ,Dy 3+ (Yellow-green emission, peak at approximately 520 nm), Sr2MgSi2O7:Eu 2+ ,Dy 3+ (Blue-green emission, peak at approximately 490 nm, excellent water resistance) and CaTiO3:Pr 3+ Zn 2+ (Red emission, peak at approximately 610 nm, high warning visibility) These three luminescent powders are blended in a weight ratio of 1:(0.25-0.45):(0.05-0.2). Their emission spectra complement each other in the visible light region, producing a near-warm white or orange-yellow warning light in the dark. Furthermore, the SrAl2O4 system provides a deeper trap to ensure a long afterglow; the Sr2MgSi2O7 system exhibits high chemical stability and maintains luminescence even in humid environments; and the CaTiO3:Pr... 3+ Zn 2+ The system is treated with Zn 2+ After doping, the initial brightness of the material can be significantly improved. The three luminescent materials mentioned above can form a "deep and shallow trap relay" effect in the same matrix, making the afterglow brightness decay curve smoother.
[0010] Optionally, the SrAl2O4:Eu 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ Zn 2+ The weight ratio is 1:(0.3-0.4):(0.1-0.2).
[0011] Optionally, the SrAl2O4:Eu 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ Zn 2+ The weight ratio is 1:0.35:0.15.
[0012] In some embodiments, the SrAl2O4:Eu 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ Zn 2+ The weight ratio can be 1:(0.25-0.3):0.15, 1:(0.25-0.35):0.15, 1:(0.25-0.4):0.15, 1:(0.25-0.45):0.15, 1:(0.3-0.35):0.15, 1:(0.3-0.4):0.15, 1:(0.3-0.45):0.15, or 1:(0.35-0.4):0. .15、1:(0.35-0.45):0.15、1:(0.4-0.45):0.15、1:0.35:(0.05-0.1)、1:0.35:(0.05-0.15)、1:0.35:(0.05-0.2)、1:0.35:(0.1-0.15)、1:0.35:(0.1-0.2) or 1:0.35:(0.15-0.2).
[0013] In one specific implementation, the SrAl2O4:Eu 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ Zn 2+The weight ratio can also be 1:0.25:0.15, 1:0.3:0.15, 1:0.35:0.15, 1:0.4:0.15, 1:0.45:0.15, 1:0.35:0.05, 1:0.35:0.1 or 1:0.35:0.2.
[0014] Optionally, the inorganic filler is selected from one or more of magnesium sulfate whiskers, hollow glass microspheres, and silicon dioxide.
[0015] Optionally, the nucleating agent is selected from sorbitols, phosphate salts, or organosilicones.
[0016] Optionally, the nucleating agent is NX8000K.
[0017] Optionally, the photoluminescent composition further comprises one or more of antioxidants, lubricants, ultraviolet absorbers, and anti-hydrolysis agents.
[0018] Secondly, this application provides a light-emitting material prepared using the aforementioned photoluminescent composition.
[0019] The photoluminescent material provided in this application can be used to manufacture door panel decorations or various automotive parts, such as automotive interior components (door panel handles, etc.). Figure 3-4 As shown), automotive exterior parts (rearview mirror housings), bumper upper edge trim strips, etc.
[0020] Optionally, the preparation method includes the following steps: mixing the components other than the composite luminescent powder evenly to obtain a main mixture; using the composite luminescent powder as a secondary mixture; adding the main mixture to the extruder through the main feed port and the secondary mixture to the extruder through the side feed port; then melt-extruding and granulating at 160-190℃ and injection molding to obtain a photoluminescent material.
[0021] In this application, when inorganic fillers are used in the material, and these fillers are magnesium sulfate whiskers and / or hollow glass microspheres, the composite luminescent powder, magnesium sulfate whiskers, and hollow glass microspheres are fed into the extruder via side feeding; the remaining components are fed into the extruder through the main feed port.
[0022] In summary, this application has the following beneficial effects: 1. This application utilizes a homopolymer polypropylene with a specific melt index, a specific polyolefin elastomer, and three different wavelength long afterglow luminescent powders to synergistically combine them, thereby obtaining a photoluminescent material with good low-temperature processing adaptability, excellent long-lasting luminescence in the dark, and superior outdoor weather resistance and mechanical strength. This material can meet the passive location indication requirements for exterior parts of electric vehicle bodies, charging facility markings, and low-illuminance traffic nodes.
[0023] 2. The photoluminescent material provided in this application exhibits slow brightness decay and excellent outdoor weather resistance, with an effective visibility time of ≥11h and a retention rate of ≥85% of afterglow brightness after 10 minutes of xenon lamp aging after 2000h, which can meet the usage requirements of outdoor traffic warning components.
[0024] 3. The processing temperature of the photoluminescent material of this application can be controlled within the range of 200℃, which can avoid the problem of thermal quenching of luminescent powder caused by high-temperature processing of traditional long-afterglow plastics, thus significantly improving the brightness retention rate of the material. Attached Figure Description
[0025] Figure 1 This is a normal physical image of a sample injection molded using the preparation method provided in Example 3; Figure 2 This is a photograph of the luminescent sample made by injection molding using the preparation method provided in Example 3; Figure 3 This is a normal physical image of the door panel top handle injection molded using the preparation method provided in Example 3; Figure 4 This is a photograph of the luminescent state of the handle above the door panel, which was injection molded using the preparation method provided in Example 3. Detailed Implementation
[0026] This application provides a photoluminescent composition comprising the following components in parts by weight: 20-30 parts of homopolymer polypropylene with a melt index of 80-150 g / 10 min, 30-40 parts of homopolymer polypropylene with a melt index of 18-22 g / 10 min, 15-20 parts of polyolefin elastomer, 15-20 parts of composite luminescent powder, 0.4-1 part of nucleating agent, 0.4-0.8 parts of antioxidant, and 8-15 parts of inorganic filler; wherein the composite luminescent powder is SrAl2O4:Eu in a weight ratio of 1:(0.25-0.45):(0.05-0.2). 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ Zn 2+ A mixture.
[0027] The method for preparing the photoluminescent composition provided in this application includes the following steps: (1) Add the components other than the composite luminescent powder into the mixer and mix at a speed of 300-500 rpm for 8-10 min to obtain the main mixture; add magnesium sulfate whiskers, hollow glass microspheres and composite luminescent powder into the mixer and mix at a speed of 80-120 rpm for 3-5 min to obtain the secondary mixture.
[0028] (2) Start the twin-screw extruder, add the main mixture into the extruder through the main feed port, and add the secondary mixture into the extruder through the side feed port; set the temperatures of each section of the extruder as follows: Zone 1 160-165℃, Zone 2 170-180℃, Zone 3 180-185℃, Zone 4 185-190℃, and the die head 180-185℃; the main screw speed is 250 rpm, and the side feed screw speed is 80 rpm; the extrudate is water-cooled, stretched, granulated, and dried to obtain photoluminescent material granules; (3) Add the photoluminescent material particles to the injection molding machine and injection mold them at 180-190℃ to obtain the photoluminescent material.
[0029] The raw materials, reagents, solvents, etc. used in this application can all be obtained commercially.
[0030] The present application will be further described in detail below with reference to embodiments, performance testing tests and accompanying drawings. Examples 1-8
[0031] Examples 1-8 each provide a light-gathering material.
[0032] The difference in the above embodiments is that: the composite luminescent powder (SrAl2O4:Eu) 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3 + and CaTiO3:Pr 3+ Zn 2+ The weight ratios of ) are shown in Table 1 below.
[0033] The method for preparing the photoluminescent material provided in Examples 1-8 includes the following steps: (1) Weigh 2.5 kg of homopolymer polypropylene with a melt index of 100 g / 10 min, 3.5 kg of homopolymer polypropylene with a melt index of 20 g / 10 min, 2 kg of polyolefin elastomer TAFMER A-4090S, 60 g of sorbitol nucleating agent NX8000K, 40 g of antioxidant 1010 and 20 g of antioxidant 168 respectively, put them into a mixer, mix at 400 rpm for 8 min to obtain the main mixture; put 0.3 kg of magnesium sulfate whiskers NP-YW2, 0.7 kg of hollow glass microspheres (D50 of 40 μm) and 2 kg of composite luminescent powder into a mixer, mix at 100 rpm for 3 min to obtain the secondary mixture.
[0034] (2) Start the twin-screw extruder, add the main mixture into the extruder through the main feed port, and add the secondary mixture into the extruder through the side feed port; set the temperatures of each section of the extruder as follows: Zone 1 165℃, Zone 2 175℃, Zone 3 180℃, Zone 4 190℃, and the die head 185℃; the main screw speed is 250 rpm, and the side feed screw speed is 80 rpm; the extrudate is water-cooled, stretched, granulated, and dried to obtain photoluminescent material granules; (3) Add the photoluminescent material particles to the injection molding machine and injection mold at 185°C to obtain the photoluminescent material.
[0035] Table 1. Types and proportions of composite luminescent powders in Examples 1-8 Example 9
[0036] Example 9 provides a light-gathering material.
[0037] The difference between the above embodiment and Embodiment 3 is that the sorbitol nucleating agent NX8000K is replaced with the sorbitol nucleating agent HX-3. Example 10
[0038] Example 10 provides a light-gathering material.
[0039] The difference between the above embodiment and Embodiment 3 is that the sorbitol nucleating agent NX8000K is replaced with the phosphate salt nucleating agent NA-11. Example 11
[0040] Example 11 provides a light-gathering material.
[0041] The difference between the above embodiment and Embodiment 3 is that the sorbitol nucleating agent NX8000K is replaced with KH550 modified silica sol nucleating agent. Comparative Example 1
[0042] Comparative Example 1 provides a light-gathering material.
[0043] The difference between the above comparative example and Example 3 is that the homopolymer polypropylene with a melt index of 20 g / 10 min was replaced with an equal amount of homopolymer polypropylene with a melt index of 100 g / 10 min. Comparative Example 2
[0044] Comparative Example 2 provides a light-gathering material.
[0045] The difference between the above comparative example and Example 3 is that the homopolymer polypropylene with a melt index of 100 g / 10 min was replaced with an equal amount of homopolymer polypropylene with a melt index of 20 g / 10 min. Comparative Example 3
[0046] Comparative Example 3 provides a light-gathering material.
[0047] The difference between the above comparative example and Example 3 is that the polyolefin elastomer TAFMER A-4090S was replaced with a low-temperature resistant rubber (ethylene octene copolymer, CAS number 26221-73-8). Comparative Example 4
[0048] Comparative Example 4 provides a light-gathering material.
[0049] The difference between the comparative example and Example 3 is that the composite luminescent powder is SrAl2O4:Eu in a weight ratio of 1:1:1. 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ Zn 2+ A mixture. Comparative Example 5
[0050] Comparative Example 5 provides a light-gathering material.
[0051] The difference between the above comparative example and Example 3 is that the composite luminescent powder is replaced with SrAl2O4:Eu. 2+ ,Dy 3+ Luminescent powder. Performance testing
[0052] Photoluminescent materials were prepared according to the methods of Examples 1-11 and Comparative Examples 1-5, and various performance tests were performed on the samples. The results are shown in Table 2 below.
[0053] (1) Initial brightness and afterglow decay test: The photoluminescent material was cut into circular strips with a diameter of 40 mm. According to GB / T24972-2010 "Elastic Traffic Posts" and GB / T 26443-2010 "Safety Color Fluorescent and Photoluminescent Materials" standards, the strips were excited at 1000 lx illuminance for 15 min under a D65 standard light source, and then quickly transferred to a dark room. The brightness values were measured at 1 min, 10 min, 60 min and 10 h after the excitation was stopped using a luminance meter (LS-110, Konica Minolta). In addition, the lowest luminance that the human eye can recognize in the dark is about 0.32 mcd / m². The time it takes for the brightness to decay to below this value is recorded as the "effective visible time".
[0054] (2) Weather resistance test: The photoluminescent material was cut into test strips of 80mm in length × 10mm in width × 4mm in thickness; in accordance with ISO17398 and GB / T 26443 standards: a xenon lamp aging test chamber was used, with an irradiance of 0.51W / m² (at a wavelength of 340nm), a blackboard temperature of 65℃, and a relative humidity of 65%, for a 2000-hour accelerated aging test. The afterglow brightness of the aged strips after 10 minutes was tested, and the retention rate of the afterglow brightness after 10 minutes relative to the unaged strips was calculated.
[0055] (3) Impact strength: The phosphorescent material was cut into test strips with a length of 80mm, a width of 10mm, a thickness of 4mm and an A-type notch milled. The impact strength of the notch was tested using a cantilever beam impact tester in accordance with GB / T 1843-2008 "Determination of Impact Strength of Plastic Cantilever Beam".
[0056] Table 2 Performance test results of the photoluminescent material samples obtained in Examples 1-11 and Comparative Examples 1-5
[0057] According to the test results in Table 2, the light-gathering materials obtained in Examples 1-11 exhibit slow brightness decay, with an effective visibility time of 11.9-17.7 hours. After 2000 hours of xenon lamp aging, the afterglow brightness retention rate after 10 minutes is 85.3-94.9%, and the impact resistance is 15.4-18.8 KJ / m². 2 This application describes the use of homopolymer polypropylene with a melt index of 80-150 g / 10 min and homopolymer polypropylene with a melt index of 18-22 g / 10 min, blended in a weight ratio of 1:(0.25-0.45):(0.05-0.2) of SrAl2O4:Eu 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ Zn 2+ The mixture of the two components, with TAFMER A-4090S as the polyolefin elastomer, is used as a composite luminescent powder. This results in a light-emitting material with excellent overall performance, including long-lasting luminescence in the dark, good low-temperature processing adaptability, excellent outdoor weather resistance, and good mechanical strength, which can meet the needs of passive warning throughout the night.
[0058] Comparative Example 1 used only high melt index homopolymer polypropylene as the main component, and the resulting photoluminescent material had slightly poor afterglow performance and extremely poor mechanical properties.
[0059] Comparative Example 2 uses only low melt index homopolymer polypropylene as the main component. The dispersion of the luminescent powder in the material is poor, resulting in extremely poor afterglow performance and slightly poor mechanical properties of the phosphorescent material.
[0060] Comparative Example 3 used low-temperature resistant rubber to replace polyolefin elastomer, and the resulting photoluminescent material had poor toughness.
[0061] Comparative Example 4 used SrAl2O4:Eu in a weight ratio of 1:1:1. 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ Zn 2+ When the mixture of the three components is used as a composite luminescent powder, the spectral complementarity between them fails, the synergistic effect is poor, and the afterglow performance of the resulting luminescent material is extremely poor.
[0062] Comparative Example 5 uses only SrAl2O4:Eu 2+ ,Dy 3+ As a luminescent powder, the resulting phosphorescent material exhibits the fastest afterglow decay and poor weather resistance.
[0063] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.
Claims
1. A photoluminescent composition, characterized in that, The product comprises the following components in parts by weight: 20-30 parts of homopolymer polypropylene with a melt index of 80-150 g / 10 min, 30-40 parts of homopolymer polypropylene with a melt index of 18-22 g / 10 min, 15-20 parts of polyolefin elastomer, 15-20 parts of composite luminescent powder, 0.4-1 part of nucleating agent, and 8-15 parts of inorganic filler; The polyolefin elastomer is TAFMER A-4090S; The composite luminescent powder is a SrAl2O4:Eu compound with a weight ratio of 1:(0.25-0.45):(0.05-0.2). 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ ,Zn 2+ A mixture.
2. The photoluminescent composition according to claim 1, characterized in that, The SrAl2O4:Eu 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ ,Zn 2+ The weight ratio is 1:(0.3-0.4):(0.1-0.2).
3. The photoluminescent composition according to claim 1, characterized in that, The SrAl2O4:Eu 2+ ,Dy 3+ Sr2MgSi2O7:Eu 2+ ,Dy 3+ and CaTiO3:Pr 3+ ,Zn 2+ The weight ratio is 1:0.35:0.
15.
4. The photoluminescent composition according to claim 1, characterized in that, The inorganic filler is selected from one or more of magnesium sulfate whiskers, hollow glass microspheres, and silicon dioxide.
5. The photoluminescent composition according to claim 1, characterized in that, The nucleating agent is selected from sorbitols, phosphate salts, or organosilicones.
6. The photoluminescent composition according to claim 5, characterized in that, The nucleating agent is NX8000K.
7. The photoluminescent composition according to any one of claims 1-6, characterized in that, The photoluminescent composition further comprises one or more of antioxidants, lubricants, ultraviolet absorbers, and anti-hydrolysis agents.
8. A light-gathering material, characterized in that, It is prepared using the photoluminescent composition according to any one of claims 1-7.
9. The method for preparing the photoluminescent material as described in claim 8, characterized in that, The process includes the following steps: mixing all components except the composite luminescent powder evenly to obtain a main mixture; using the composite luminescent powder as a secondary mixture; adding the main mixture to the extruder through the main feed port and the secondary mixture to the extruder through the side feed port; then melting and extruding the mixture at 160-190℃ and injection molding to obtain a photoluminescent material.