Reflection and noctilucence integrated composite PVC (polyvinyl chloride) material and preparation method thereof

Abstract

The invention provides a reflective and noctilucent integrated composite PVC (polyvinyl chloride) material and a preparation method thereof. The composite PVC material is composed of a PVC base material layer and a composite functional layer, the preparation raw materials of the PVC base material layer comprise the following components in parts by weight: 80-120 parts of polyvinyl chloride resin, 40-60 parts of a plasticizer and 2-10 parts of a stabilizer; the composite functional layer is prepared from the following components in parts by weight: 20-40 parts of composite reflective powder, 10-30 parts of long afterglow noctilucent powder, 2-10 parts of a dispersing agent, 40-60 parts of polyvinyl chloride resin, 20-40 parts of a plasticizer and 15-35 parts of a solvent. The prepared composite PVC material has high visible light reflectivity, is good in light reflection effectiveness, high in ageing resistance and weather resistance and long in afterglow time, is high in light energy storage capacity and high in continuous luminous efficiency at night, and can further enhance the reliability and safety of the material in practical application.

Description

Technical Field

[0001] This invention belongs to the field of composite PVC material technology, and particularly relates to a composite PVC material that integrates reflectivity and luminescence and its preparation method. Background Technology

[0002] Due to its low cost, good processing performance, and excellent mechanical properties, PVC material is widely used in clothing, bags, footwear, furniture decoration, traffic safety facilities, and other fields. With the expansion of its applications, the functional requirements for PVC materials are also increasing, especially in areas such as safety protection and nighttime warning systems, where good optical properties are essential.

[0003] Currently, existing technologies have incorporated reflective or luminescent properties into PVC materials. For example, reflective glass fiber films are heat-bonded onto PVC fabrics to impart reflective properties, and rare-earth luminescent powders are added to PVC raw materials to give them luminescent functionality. However, reports on the optical properties of existing technologies often focus on a single function, possessing only reflective or luminescent properties, which is insufficient to meet the stringent requirements of complex and variable environments. There are few reports on materials that simultaneously possess reflective and luminescent properties, mainly because the two functional components are not well-coordinated. This can easily lead to defects such as limited reflective angle, insufficient reflective brightness, or short effective luminescence time in luminescent materials, and can also affect the material's physical and processing properties.

[0004] In view of the problems existing in the prior art, how to provide a composite PVC material that combines reflectivity and luminescence in a coordinated manner without affecting the physical or processing properties of the material itself is the problem that this invention urgently needs to solve. Summary of the Invention

[0005] The purpose of this invention is to provide a composite PVC material that integrates reflectivity and luminescence, and its preparation method, in order to solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides a composite PVC material integrating reflectivity and luminescence, characterized in that it comprises a PVC substrate layer and a composite functional layer; the raw materials for preparing the PVC substrate layer include the following components in parts by weight: 80-120 parts of polyvinyl chloride resin, 40-60 parts of plasticizer, and 2-10 parts of stabilizer; the raw materials for preparing the composite functional layer include the following components in parts by weight: 20-40 parts of composite reflective powder, 10-30 parts of long-afterglow luminescent powder, 2-10 parts of dispersant, 40-60 parts of polyvinyl chloride resin, 20-40 parts of plasticizer, and 15-35 parts of solvent.

[0007] As a further improvement, the composite reflective powder comprises modified silicon-titanium-zirconium microspheres and PMMA microspheres.

[0008] As a further improvement, the synthesis of the modified silicon-titanium-zirconium microspheres includes the following steps: (1) Titanium sol was prepared by stirring and mixing tetrabutyl titanate with anhydrous ethanol, acetylacetone and deionized water; tetraethyl orthosilicate was stirred and mixed with deionized water and the pH of the system was adjusted to 3-5 to prepare silica sol; under stirring, titanium sol was slowly dripped into silica sol to obtain mixed sol one. (2) Zirconium oxychloride and deionized water were stirred to form a mixture, and then the pH of the system was adjusted to 3-5 to obtain zirconium sol. The zirconium sol was slowly dripped into the mixed sol, and then deionized water was added and stirred. When the mixture became viscous, stirring was stopped and then post-processed to obtain silicon titanium zirconium microbeads. (3) Add deionized water and ethanol to the flask, adjust the pH to 4-6 with glacial acetic acid, then slowly add silane coupling agent and stir for 30-60 min, then add silicon titanium zirconium microspheres, heat at 40-70℃ for 1-3 h, after the reaction is completed, post-process to obtain modified silicon titanium zirconium microspheres.

[0009] As a further improvement, the modified silicon-titanium-zirconium microspheres have a particle size of 30-50 μm, and the PMMA microspheres have a particle size of 50-80 μm.

[0010] As a further improvement, the mass ratio of the modified silicon-titanium-zirconium microspheres to PMMA microspheres is 1:1-2.

[0011] As a further improvement, the long afterglow phosphorescent powder is a lanthanide rare earth ion-doped aluminate with a fineness of 300-600 mesh.

[0012] To extend the luminescence duration of the phosphorescent powder, preferably, the long-afterglow phosphorescent powder is a strontium aluminate type long-afterglow phosphorescent powder.

[0013] As a further improvement, the plasticizer is at least one of dioctyl phthalate, dioctyl adipate, and epoxidized soybean oil.

[0014] As a further improvement, the dispersant is a mixture of sodium dodecylbenzenesulfonate and polyethylene glycol.

[0015] Sodium dodecylbenzenesulfonate, as an anionic surfactant, can adsorb onto the surface of modified silicon-titanium-zirconium microspheres to form a negatively charged layer. It achieves dispersion and inhibits sedimentation through charge repulsion. Polyethylene glycol polymer can stabilize PMMA microspheres and prevent agglomeration. The dual dispersion effect of electrostatics and space improves the dispersibility between the various substances.

[0016] As a further improvement, the stabilizer is at least one of zinc-calcium heat stabilizer and barium-zinc stabilizer.

[0017] This invention also provides a method for preparing a composite PVC material that integrates reflectivity and luminescence, comprising the following steps: (1) Raw material pretreatment: S1: Mix polyvinyl chloride resin, plasticizer, and stabilizer at 80-90℃ to obtain a PVC substrate coating. S2: Add the composite reflective powder and part of the dispersant to the solvent and stir to mix evenly. Then add the long afterglow phosphorescent powder and the remaining dispersant and continue to mix. Then add the polyvinyl chloride resin and plasticizer and mix to obtain the composite functional layer coating. (2) Layered coating and curing: S3: Fix the PET release film to the coating machine, then coat a layer of composite functional layer coating, dry at 120-130℃ for 10-15 minutes, then repeat the coating and drying once more to obtain the cured composite functional layer; S4: Apply a layer of PVC substrate coating to the PET release film with the cured composite functional layer, and dry at 140-150℃ for 5-10 minutes to obtain the cured material; (3) Post-processing: After the cured material is cooled to room temperature, the release film is peeled off to obtain a composite PVC material that combines reflectivity and luminescence.

[0018] As a further improvement, the thickness of a single coating of the composite functional layer coating in step (2) is 20-40 μm; the coating thickness of the PVC substrate layer coating is 40-60 μm.

[0019] Compared with the prior art, the beneficial effects of the present invention are: This invention provides a composite PVC material that integrates reflectivity and luminescence, and its preparation method. The resulting composite PVC material has a high visible light reflectivity, and the visible light reflectivity remains high even after aging treatment, indicating good reflectivity and weather resistance. It also has a long afterglow time, indicating that the material has a stronger light energy storage capacity, higher nighttime luminescence efficiency, and better practicality. This application utilizes an emulsion spheroidization method to prepare silicon-titanium-zirconium microspheres with high refractive index (refractive index n=1.9±0.2), good transparency, high hardness, and high sphericity. Surface modification with a silane coupling agent is then performed to obtain modified silicon-titanium-zirconium microspheres, improving their compatibility with organic substrates. Combined with PMMA microspheres as a composite reflective powder, a synergistic mechanism of "light transmission-high-efficiency reflection" is formed. The PMMA microspheres, acting as a light transmission medium, reduce the scattering loss of incident light, guiding the light to the high-refractive-index modified silicon-titanium-zirconium microspheres, thereby achieving a reflective effect. Attached Figure Description

[0020] Figure 1The image shows a normal photograph of the composite PVC material prepared in Example 1. Figure 2 The image shows a reflection of the composite PVC material prepared in Example 1. Figure 3 The image shows the composite PVC material prepared in Example 1, photographed in the dark. Detailed Implementation

[0021] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0022] In the following examples, except for the modified silicon-titanium-zirconium microspheres, all other compound monomers and related reagents used were commercially available. The polyvinyl chloride resin was purchased from Wuhan Xindongyi Chemical Co., Ltd., model SG-8; the PMMA microspheres were purchased from Dongguan Xiuzhisheng Plastics Co., Ltd.; the long afterglow phosphorescent powder was purchased from Shenzhen Longhua District Rendering Technology Pigment Factory, product number 909; the polyethylene glycol was purchased from Nantong Renda Chemical Co., Ltd., model PEG-4000; and the zinc-calcium heat stabilizer and barium-zinc stabilizer were purchased from Guangdong Weilinna New Material Technology Co., Ltd., models BZ-F02 and LBZ-109, respectively.

[0023] The synthesis of modified silicon-titanium-zirconium microspheres includes the following steps: (1) Add 14g of anhydrous ethanol to 68g of tetrabutyl titanate and stir to form a tetrabutyl titanate alcohol solution. Then add 20g of acetylacetone to the tetrabutyl titanate alcohol solution and stir for 30min. Finally, add 29g of deionized water and stir for 2h to obtain titanium sol. Stir 1mol of tetraethyl orthosilicate and 5mol of deionized water and adjust the pH of the system to 3 with 30% hydrochloric acid solution to obtain silica sol. Under stirring, slowly drop 30g of titanium sol into 50g of silica sol to obtain mixed sol one. (2) Add 1 mol of zirconium oxychloride to 5 mol of deionized water and stir to form a mixture. Then slowly add 0.5 mol / L ammonia water to the mixture and adjust the pH of the system to 3 to obtain zirconium sol. Add 20 g of zirconium sol to the mixed sol one that is stirred at a constant speed, and add 3 mol of deionized water and continue stirring. When the mixture becomes viscous, stop stirring. Add the substance after stopping stirring to a mixture of 3 g of Span 60 and 150 g of liquid paraffin. Stir at a constant speed at 50°C. After the gel microspheres are deposited, wash and filter repeatedly with distilled water and anhydrous ethanol. Then place in an 80°C drying oven for 48 hours, keep warm at 150°C for 1 hour, and finally sinter at 600°C for 4 hours at a rate of 5°C / min to obtain silicon titanium zirconium microspheres. (3) Add 15 mL of deionized water and 85 mL of ethanol to a flask, adjust the pH to 5 with glacial acetic acid, then slowly add 1.5 g of KH-570 and stir for 60 min. Then add 100 g of silicon-titanium-zirconium microspheres and heat the reaction at 60 °C for 3 h. After the reaction is complete, filter and wash with anhydrous ethanol. Heat the obtained solid at 100 °C for 2 h and finally cool it to room temperature in a desiccator to obtain modified silicon-titanium-zirconium microspheres.

[0024] The preparation method of Example 1 includes the following steps: (1) Raw material pretreatment: S1: Mix 100 parts of polyvinyl chloride resin, 50 parts of dioctyl phthalate, and 3 parts of zinc-calcium heat stabilizer at 85°C to obtain a PVC base material coating. S2: 13 parts of modified silicon titanium zirconium microspheres, 17 parts of PMMA microspheres, 2 parts of sodium dodecylbenzene sulfonate, and 2 parts of polyethylene glycol are added to 25 parts of acetone and stirred until uniform. Then, 26 parts of long afterglow phosphorescent powder, 1.5 parts of sodium dodecylbenzene sulfonate, and 1.5 parts of polyethylene glycol are added and mixed. Subsequently, 44 parts of polyvinyl chloride resin and 25 parts of dioctyl adipate are added and mixed to obtain a composite functional layer coating. (2) Layered coating and curing: S3: Fix the PET release film to the coating machine, then coat a layer of composite functional layer coating with a coating thickness of 25μm, dry at 120℃ for 12min, then repeat the coating and drying once more with a coating thickness of 25μm, drying temperature of 120℃ and drying time of 12min to obtain the cured composite functional layer. S4: On the PET release film covered with the cured composite functional layer, a layer of PVC substrate coating is applied with a thickness of 50μm, and dried at 150℃ for 8min to obtain the cured composite PVC material. (3) Post-processing: After the cured composite PVC material is cooled to room temperature, the release film is peeled off to obtain a composite PVC material that combines reflectivity and luminescence.

[0025] The preparation method of Example 2 includes the following steps: (1) Raw material pretreatment: S1: Mix 90 parts of polyvinyl chloride resin, 45 parts of dioctyl phthalate, and 4 parts of zinc-calcium heat stabilizer at 90°C to obtain a PVC substrate coating. S2: 12 parts of modified silicon-titanium-zirconium microspheres, 12 parts of PMMA microspheres, 1 part of sodium dodecylbenzenesulfonate, and 1 part of polyethylene glycol are added to 23 parts of acetone and stirred until uniform. Then, 20 parts of long afterglow phosphorescent powder, 1.5 parts of sodium dodecylbenzenesulfonate, and 1.5 parts of polyethylene glycol are added and mixed. Subsequently, 50 parts of polyvinyl chloride resin and 30 parts of epoxidized soybean oil are added and mixed to obtain a composite functional layer coating. (2) Layered coating and curing: S3: Fix the PET release film to the coating machine, then coat a layer of composite functional layer coating with a thickness of 20μm, dry at 120℃ for 10min, then repeat the coating and drying once more with a thickness of 20μm, dry at 120℃ for 10min to obtain the cured composite functional layer. S4: On the PET release film covered with the cured composite functional layer, a layer of PVC substrate coating is applied with a thickness of 40μm, and dried at 150℃ for 8min to obtain the cured composite PVC material. (3) Post-processing: After the cured composite PVC material is cooled to room temperature, the release film is peeled off to obtain a composite PVC material that combines reflectivity and luminescence.

[0026] The preparation method of Example 3 includes the following steps: (1) Raw material pretreatment: S1: Mix 110 parts of polyvinyl chloride resin, 55 parts of dioctyl adipate, and 5 parts of barium zinc stabilizer at 85°C to obtain a PVC substrate coating. S2: Add 15 parts of modified silicon-titanium zirconium microspheres, 20 parts of PMMA microspheres, 2 parts of sodium dodecylbenzene sulfonate, and 2 parts of polyethylene glycol to 30 parts of acetone and stir to mix evenly. Then add 30 parts of long afterglow phosphorescent powder, 1 part of sodium dodecylbenzene sulfonate, and 1 part of polyethylene glycol and continue mixing. Then add 53 parts of polyvinyl chloride resin and 22 parts of epoxidized soybean oil and mix to obtain a composite functional layer coating. (2) Layered coating and curing: S3: Fix the PET release film to the coating machine, then coat a layer of composite functional layer coating with a thickness of 30μm, dry at 130℃ for 10min, then repeat the coating and drying once more with a thickness of 30μm, dry at 130℃ for 10min to obtain the cured composite functional layer. S4: On the PET release film covered with the cured composite functional layer, a layer of PVC substrate coating is applied with a coating thickness of 45μm, and dried at 145℃ for 10min to obtain the cured composite PVC material. (3) Post-processing: After the cured composite PVC material is cooled to room temperature, the release film is peeled off to obtain a composite PVC material that combines reflectivity and luminescence.

[0027] The preparation method of Example 4 includes the following steps: (1) Raw material pretreatment: S1: Mix 100 parts of polyvinyl chloride resin, 50 parts of dioctyl phthalate, and 3 parts of zinc-calcium heat stabilizer at 80°C to obtain a PVC substrate coating. S2: Add 15 parts of modified silicon titanium zirconium microspheres, 15 parts of PMMA microspheres and 4 parts of sodium dodecylbenzene sulfonate to 30 parts of acetone and stir to mix evenly. Then add 26 parts of long afterglow phosphorescent powder and 3 parts of sodium dodecylbenzene sulfonate and continue to mix. Then add 45 parts of polyvinyl chloride resin and 25 parts of dioctyl phthalate and mix to obtain a composite functional layer coating. (2) Layered coating and curing: S3: Fix the PET release film to the coating machine, then coat a layer of composite functional layer coating with a thickness of 25μm, dry at 120℃ for 12min, then repeat the coating and drying once more with a thickness of 25μm, dry at 120℃ for 12min to obtain the cured composite functional layer. S4: On the PET release film covered with the cured composite functional layer, a layer of PVC substrate coating is applied with a thickness of 50μm, and dried at 150℃ for 8min to obtain the cured composite PVC material. (3) Post-processing: After the cured composite PVC material is cooled to room temperature, the release film is peeled off to obtain a composite PVC material that combines reflectivity and luminescence.

[0028] Comparative Example 1: Same as Example 1, except that 13 parts of modified silicon titanium zirconium microspheres in S2 are replaced with 13 parts of silicon titanium zirconium microspheres obtained in step (2) of the synthesis of modified silicon titanium zirconium microspheres, i.e., unmodified silicon titanium zirconium microspheres.

[0029] Comparative Example 2: Same as Example 1, except that 13 parts of modified silicon titanium zirconium microspheres and 17 parts of PMMA microspheres in S2 are replaced with 30 parts of modified silicon titanium zirconium microspheres.

[0030] The composite PVC materials with both reflective and luminescent properties prepared in Examples 1-4 and Comparative Examples 1-2 were tested for visible light reflectivity, weather resistance, and afterglow time. The test methods are as follows: Visible light reflectance: The reflectance was measured using a spectrophotometer in accordance with the HG / T 4915-2016 standard. Weather resistance: According to GB / T 16422.3-2014 standard, the visible light reflectance was tested after aging for 100 hours in an ultraviolet aging chamber (UVB-313 lamp, temperature 60℃, relative humidity 50%). Afterglow time: Irradiated for 10 minutes under a D65 standard light source according to JG / T 446-2014 standard, and then the afterglow time was tested in a dark room.

[0031] The test results are shown in Table 1, and are as follows: Table 1

[0032] As can be seen from the test results of Example 1 and Comparative Examples 1-2 in Table 1, compared with using unmodified silicon-titanium zirconium microspheres and PMMA microspheres as composite reflective powder, or using only modified silicon-titanium zirconium microspheres as reflective powder, the composite PVC material prepared by using the modified silicon-titanium zirconium microspheres and PMMA microspheres of the present invention as composite reflective powder has a higher visible light reflectivity, and the visible light reflectivity is still high after aging treatment, indicating that the reflectivity and weather resistance are better, and the afterglow time is longer, indicating that the material has a stronger light energy storage capacity, higher nighttime continuous luminescence efficiency, and better practicality.

[0033] As can be seen from the test results of Examples 1-4, the composite PVC material prepared by the present invention has a high visible light reflectivity, indicating low light absorption, good reflectivity, and good resistance to ultraviolet aging. It also has a long afterglow time, indicating strong light energy storage capacity and high continuous luminescence efficiency at night. When applied to highway markings, reflective clothing, etc., it further enhances the reliability and safety of the material. Furthermore, the comparison between Examples 1-3 and Example 4 shows that when the dispersant is sodium dodecylbenzenesulfonate and polyethylene glycol, the composite PVC material with both reflectivity and luminescence has better performance.

[0034] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A composite PVC material with integrated light reflection and luminescence, characterized in that, The PVC composite material comprises a PVC base layer and a composite functional layer; the PVC base layer is prepared from the following components in parts by weight: 80-120 parts of polyvinyl chloride resin, 40-60 parts of plasticizer, and 2-10 parts of stabilizer; the composite functional layer is prepared from the following components in parts by weight: 20-40 parts of composite reflective powder, 10-30 parts of long-afterglow luminescent powder, 2-10 parts of dispersing agent, 40-60 parts of polyvinyl chloride resin, 20-40 parts of plasticizer, and 15-35 parts of solvent.

2. The composite PVC material with integrated reflective and luminous properties according to claim 1, characterized in that, The composite reflective powder comprises modified silicon-titanium-zirconium microbeads and PMMA microspheres.

3. The composite PVC material of claim 2, wherein, The modified silicon-titanium-zirconium microbeads are synthesized by the following steps: (1) stirring and mixing tetrabutyl titanate with anhydrous ethanol, acetylacetone and deionized water to obtain a titanium sol; stirring and mixing tetraethyl orthosilicate with deionized water and adjusting the pH of the system to 3-5 to obtain a silicon sol; slowly dropping the titanium sol into the silicon sol under stirring to obtain a mixed sol one; (2) stirring and mixing zirconium oxychloride with deionized water to obtain a mixed solution, then adjusting the pH of the system to 3-5 to obtain a zirconium sol; slowly dropping the zirconium sol into the mixed sol one and continuing to stir with the addition of deionized water; stopping stirring when the mixture is viscous, and then post-processing to obtain silicon-titanium-zirconium microbeads; (3) adding deionized water and ethanol into a flask, adjusting the pH to 4-6 with glacial acetic acid, then slowly adding a silane coupling agent and stirring for 30-60 min, then adding the silicon-titanium-zirconium microbeads, and heating and reacting at 40-70°C for 1-3 h; post-processing after the reaction to obtain modified silicon-titanium-zirconium microbeads.

4. The composite PVC material of claim 2, wherein, The particle size of the modified silicon-titanium-zirconium microbeads is 30-50 μm, and the particle size of the PMMA microspheres is 50-80 μm.

5. The composite PVC material of claim 2, wherein, The mass ratio of the modified silicon-titanium-zirconium microbeads to the PMMA microspheres is 1:1-2.

6. The composite PVC material of claim 1, wherein, The long-afterglow luminescent powder is lanthanide ion doped aluminate with fineness of 300-600 mesh.

7. The composite PVC material of claim 1, wherein the reflective and luminous material is characterized in that, The plasticizer is at least one of dioctyl phthalate, dioctyl adipate and epoxy soybean oil.

8. The composite PVC material of claim 1, wherein, The dispersing agent is a mixture of sodium dodecylbenzenesulfonate and polyethylene glycol.

9. The method of claim 1-8, wherein the method is characterized in that, The method comprises the following steps: (1) raw material pretreatment: S1: stirring and mixing polyvinyl chloride resin, plasticizer and stabilizer at 80-90°C to obtain a PVC base layer coating; S2: stirring and mixing the composite reflective powder with part of the dispersing agent in the solvent until uniform, then adding the long-afterglow luminescent powder and the remaining dispersing agent, and then adding polyvinyl chloride resin and plasticizer to obtain a composite functional layer coating; (2) layered coating and curing: S3: fixing a PET release film on a coating machine, then coating a layer of the composite functional layer coating, drying at 120-130°C for 10-15 min, then repeating the coating and drying once to obtain the cured composite functional layer; S4: coating a layer of the PVC base layer coating on the PET release film with the cured composite functional layer, drying at 140-150°C for 5-10 min to obtain a cured material; (3) post-processing: cooling the cured material to room temperature, peeling off the release film, and obtaining the composite PVC material with reflective and luminescent properties.

10. The method for preparing a composite PVC material integrating reflectivity and luminescence according to claim 9, characterized in that, The single coating thickness of the composite functional layer coating in the step (2) is 20-40 μm; the coating thickness of the PVC substrate layer coating is 40-60 μm. The single coating thickness of the composite functional layer coating in the step (2) is 20-40 μm; the coating thickness of the PVC substrate layer coating is 40-60 μm.

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