Self-repairing optical diffusion plate master batch, preparation method thereof and self-repairing optical diffusion plate

Abstract

The invention provides a self-repairing optical diffusion plate master batch, a preparation method thereof and a self-repairing optical diffusion plate, and particularly relates to the technical field of optical plates. The self-repairing optical diffusion plate master batch comprises 65 to 85 parts of a polystyrene matrix, 5 to 20 parts of a furan functionalized polymer, 5 to 20 parts of a maleimide functionalized polymer, 0.5 to 3 parts of a diffusant and 2.3 to 9.8 parts of an auxiliary agent. A furan functionalized polymer and a maleimide functionalized polymer in a specific proportion are introduced into the master batch, a dynamic reversible covalent cross-linked network based on a Diels-Alder (DA) reaction is constructed in a material system, the network can be subjected to reversible addition and dissociation under the heating condition, and a molecular structure foundation with a self-repairing function is formed; meanwhile, the rigidity and the toughness of the material are effectively balanced through the synergistic effect of the polystyrene matrix and the auxiliaries, and the processing stability, the heat resistance and the long-term use reliability of the master batch are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of optical sheet technology, and in particular to a self-healing optical diffuser masterbatch, its preparation method, and a self-healing optical diffuser. Background Technology

[0002] Optical diffusers are key optical components in devices such as LCD displays, LED lighting, and advertising light boxes. Their main function is to transform point or line light sources into uniform and soft surface light sources to eliminate glare and improve visual comfort.

[0003] Currently, these types of boards mostly use transparent polymers such as polystyrene (PS), polycarbonate (PC), or polymethyl methacrylate (PMMA) as the base material, and achieve light scattering effects by blending with light diffusing agents such as silica and organic microspheres. However, in practical applications, these materials generally suffer from low surface hardness and poor scratch resistance. They are prone to micron-level scratches during production, transportation, and use, leading to uneven light output, scratch marks, and other optical defects, which seriously affect display quality.

[0004] In addition, traditional modification methods, such as adding toughening agents, can improve impact performance, but they are often accompanied by a decrease in strength and heat resistance, making it difficult to achieve a balance between rigidity and toughness.

[0005] In view of this, the present invention is hereby proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a self-healing optical diffusion plate masterbatch, its preparation method, and a self-healing optical diffusion plate, aiming to solve at least one of the above-mentioned technical problems in the prior art.

[0007] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted: A first aspect of the present invention provides a self-healing optical diffuser masterbatch comprising the following components in parts by weight: 65-85 parts of polystyrene matrix, 5-20 parts of furan-functionalized polymer, 5-20 parts of maleimide-functionalized polymer, 0.5-3 parts of diffuser, and 2.3-9.8 parts of additives.

[0008] Furthermore, the furan-functionalized polymer includes furan-functionalized polystyrene and / or furan methacrylate copolymers.

[0009] Preferably, the furan-functionalized polystyrene includes at least one of furan-methanol-terminated polystyrene, furan-methanol-grafted polystyrene, and furan-methanol-terminated and grafted polystyrene.

[0010] Preferably, the furan methacrylate copolymer comprises maleimide-functionalized polystyrene and / or maleimide-modified elastomer.

[0011] Preferably, the maleimide-functionalized polystyrene includes maleimide-terminated polystyrene.

[0012] Furthermore, the dispersant includes at least one of silica, titanium dioxide, polymethyl methacrylate microspheres, cross-linked polystyrene microspheres, and acrylate microspheres.

[0013] Furthermore, the additives include at least one of toughening agents, dispersants, antioxidants, and heat stabilizers.

[0014] Preferably, the toughening agent comprises at least one of styrene-ethylene-butene-styrene block copolymer (SEBS), methyl methacrylate-butadiene-styrene copolymer (MBS), and acrylate core-shell copolymer (ACR).

[0015] Preferably, the toughening agent is present in 2 to 8 parts by weight.

[0016] Preferably, the dispersant comprises a silane coupling agent and / or a titanate coupling agent.

[0017] Preferably, the dispersant is present in a weight fraction of 0.1 to 0.8 parts.

[0018] Preferably, the antioxidant grades include at least one of antioxidant 1010, antioxidant 626, and antioxidant 168.

[0019] Preferably, the antioxidant is present in 0.1 to 0.5 parts by weight.

[0020] Preferably, the heat stabilizer includes dibenzoylmethane and / or hindered amine light stabilizers.

[0021] Preferably, the heat stabilizer is present in 0.1 to 0.5 parts by weight.

[0022] The second aspect of the present invention provides a method for preparing the self-healing optical diffuser masterbatch, wherein a polystyrene matrix, a furan-functionalized polymer, a maleimide-functionalized polymer, a diffuser, and an additive are mixed uniformly to obtain a premix; the premix is ​​melt-blended and granulated using a twin-screw extruder to obtain the self-healing optical diffuser masterbatch.

[0023] Furthermore, the mixing is carried out in a high-speed mixer.

[0024] Preferably, the mixing time is 5 to 15 minutes.

[0025] Preferably, the melt blending temperature is 180~200℃.

[0026] The third aspect of the present invention provides a self-healing optical diffuser plate, which is obtained by hot pressing, annealing and cooling demolding the self-healing optical diffuser plate masterbatch.

[0027] Furthermore, the hot pressing temperature is 170~190℃ and the pressure is 5~15MPa.

[0028] Furthermore, the annealing process is as follows: slowly cool to 60-80°C at a rate of 0.5-2°C / min, and hold at that temperature for 30-60 minutes.

[0029] Furthermore, the notched impact strength of the self-healing optical diffuser plate is 2.7~4.3 kJ / m. 2 The tensile strength is 36~64 MPa, and the Vicat softening point is 92.9~95.4℃.

[0030] Preferably, the self-healing optical diffuser plate can achieve autonomous repair after surface damage through external thermal stimulation.

[0031] Preferably, the depth of the damage is ≤0.3mm.

[0032] Preferably, the temperature of the thermal excitation is 110℃-130℃, and the time is 10min-30min.

[0033] Compared with the prior art, the present invention has at least the following beneficial effects: The self-healing optical diffuser masterbatch provided by this invention introduces a specific ratio of furan-functionalized polymers and maleimide-functionalized polymers to construct a dynamic reversible covalent cross-linked network based on the Diels-Alder (DA) reaction in the material system. This network can undergo reversible addition and dissociation under heating conditions, forming the molecular structural basis for the self-healing function. At the same time, the synergistic effect of the polystyrene matrix and additives effectively balances the rigidity and toughness of the material, significantly improving the processing stability, heat resistance and long-term reliability of the masterbatch.

[0034] The preparation method provided by this invention is simple, efficient, and easy to scale up industrially. It not only achieves the orderly introduction and structural preservation of self-healing functional components, but also takes into account the safety of material processing and batch stability, providing a high-quality raw material basis for the subsequent hot pressing molding preparation of high-performance self-healing optical diffusion plates.

[0035] The self-healing optical diffuser plate provided by this invention has a self-healing function. When scratches or other damage occur on the surface, external thermal stimulation triggers the reverse DA reaction (rDA reaction), enhancing chain segment fluidity and promoting the re-contact and recombination of the crack interface. After cooling, the cross-linked structure recovers, thereby achieving autonomous repair of the scratches. This self-healing optical diffuser plate not only possesses excellent optical diffusion performance but also can repeatedly repair surface micro-damage through thermal stimulation, extending the service life of the optical diffuser plate. It is suitable for high-durability display and lighting devices. Attached Figure Description

[0036] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0037] Figure 1 This is a photograph of the surface with scratches in Test Example 2; Figure 2 This is a photograph of the surface after self-healing in Test Example 2. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0039] In the following, the terms “comprising,” “having,” and their cognates, which may be used in various embodiments of the invention, are intended only to indicate a particular feature, number, step, operation, element, component, or combination thereof, and should not be construed as excluding, firstly, the presence of one or more other features, numbers, steps, operations, elements, components, or combinations thereof, or adding the possibility of one or more features, numbers, steps, operations, elements, components, or combinations thereof.

[0040] A first aspect of the present invention provides a self-healing optical diffuser masterbatch comprising the following components in parts by weight: 65-85 parts of polystyrene matrix, 5-20 parts of furan-functionalized polymer, 5-20 parts of maleimide-functionalized polymer, 0.5-3 parts of diffuser, and 2.3-9.8 parts of additives.

[0041] The self-healing optical diffuser masterbatch provided by this invention introduces a specific ratio of furan-functionalized polymers and maleimide-functionalized polymers to construct a dynamic reversible covalent cross-linked network based on the Diels-Alder (DA) reaction in the material system. This network can undergo reversible addition and dissociation under heating conditions, forming the molecular structural basis for the self-healing function. At the same time, the synergistic effect of the polystyrene matrix and additives effectively balances the rigidity and toughness of the material, significantly improving the processing stability, heat resistance and long-term reliability of the masterbatch.

[0042] Typical, but not limiting, the weight parts of the polystyrene matrix can be, for example, 65 parts, 70 parts, 75 parts, 80 parts, or 85 parts, or any value within the range of 65 to 85 parts; the weight parts of the furan-functionalized polymer can be, for example, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, or 20 parts, or any value within the range of 5 to 20 parts; the weight parts of the maleimide-functionalized polymer can be, for example, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, or 20 parts. The weight percentages of the dispersant can be, for example, 0.5, 1, 1.5, 2, 2.5, or 3 parts, or any value within the range of 0.5 to 3 parts; the weight percentages of the additives can be, for example, 2.3, 3, 4, 5, 6, 7, 8, 9, or 9.8 parts, or any value within the range of 2.3 to 9.8 parts.

[0043] Furan-functionalized polymers refer to a class of functional polymer materials in which furan ring functional groups are introduced into the polymer molecular chain. In this invention, they mainly participate in the construction of dynamic reversible cross-linking networks as dienes in the Diels-Alder (DA) reaction.

[0044] Maleimide-functionalized polymers refer to a class of functional polymer materials in which maleimide functional groups are introduced into the polymer molecular chain. In this invention, they are used as diephiles in the Diels-Alder (DA) reaction and undergo a reversible addition reaction with furan-functionalized polymers to jointly construct a dynamic covalent crosslinking network.

[0045] Furthermore, the furan-functionalized polymer includes furan-functionalized polystyrene and / or furan methacrylate copolymers.

[0046] Preferably, the furan-functionalized polystyrene includes at least one of furan-methanol-terminated polystyrene, furan-methanol-grafted polystyrene, and furan-methanol-terminated and grafted polystyrene.

[0047] Preferably, the furan methacrylate copolymer comprises maleimide-functionalized polystyrene and / or maleimide-modified elastomer.

[0048] Preferably, the maleimide-functionalized polystyrene includes maleimide-terminated polystyrene.

[0049] Furthermore, the dispersant includes at least one of silica, titanium dioxide, polymethyl methacrylate microspheres, cross-linked polystyrene microspheres, and acrylate microspheres.

[0050] Furthermore, the additives include at least one of toughening agents, dispersants, antioxidants, and heat stabilizers.

[0051] Preferably, the toughening agent includes at least one of styrene-ethylene-butene-styrene block copolymer (SEBS), methyl methacrylate-butadiene-styrene copolymer (MBS), and acrylate core-shell copolymer (ACR). The introduction of the toughening agent improves the brittleness of the material, avoids the decrease in toughness caused by excessive crosslinking density, and enables the product to have both good mechanical strength and excellent impact resistance.

[0052] Preferably, the toughening agent is present in 2 to 8 parts by weight.

[0053] Typically, but not limitingly, the toughening agent may be present in parts by weight of, for example, 2, 3, 4, 5, 6, 7, or 8 parts, or any value within the range of 2 to 8 parts.

[0054] Preferably, the dispersant comprises a silane coupling agent and / or a titanate coupling agent.

[0055] Preferably, the dispersant is present in a weight fraction of 0.1 to 0.8 parts.

[0056] Typically, but not limitingly, the weight parts of the dispersant can be, for example, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, or 0.8 parts, or any value in the range of 0.1 to 0.8 parts.

[0057] Preferably, the antioxidant grades include at least one of antioxidant 1010, antioxidant 626, and antioxidant 168.

[0058] Preferably, the antioxidant is present in 0.1 to 0.5 parts by weight.

[0059] Typically, but not limitingly, the antioxidant may be present in parts by weight of, for example, 0.1, 0.2, 0.3, 0.4, or 0.5 parts, or any value within the range of 0.1 to 0.5 parts.

[0060] Preferably, the heat stabilizer includes dibenzoylmethane and / or hindered amine light stabilizers.

[0061] Preferably, the heat stabilizer is present in 0.1 to 0.5 parts by weight.

[0062] Typically, but not limitingly, the heat stabilizer may be present in parts by weight of, for example, 0.1, 0.2, 0.3, 0.4, or 0.5 parts, or any value within the range of 0.1 to 0.5 parts.

[0063] The second aspect of the present invention provides a method for preparing the self-healing optical diffuser masterbatch, wherein a polystyrene matrix, a furan-functionalized polymer, a maleimide-functionalized polymer, a diffuser, and an additive are mixed uniformly to obtain a premix; the premix is ​​melt-blended and granulated using a twin-screw extruder to obtain the self-healing optical diffuser masterbatch.

[0064] The preparation method provided by this invention is simple, efficient, and easy to scale up industrially. It not only achieves the orderly introduction and structural preservation of self-healing functional components, but also takes into account the safety of material processing and batch stability, providing a high-quality raw material basis for the subsequent hot pressing molding preparation of high-performance self-healing optical diffusion plates.

[0065] The strong shearing effect of the twin screw promotes the uniform dispersion of dispersants and additives in the matrix, improves the compatibility and structural uniformity of the material, and ensures the stability of the optical properties and the consistency of the mechanical properties of the final masterbatch.

[0066] Furthermore, the mixing is carried out in a high-speed mixer.

[0067] Preferably, the mixing time is 5 to 15 minutes.

[0068] Typically, but not limitingly, the mixing time can be, for example, 5 min, 7 min, 9 min, 11 min, 13 min, or 15 min, or any value within the range of 5 to 15 min.

[0069] Preferably, the melt blending temperature is 180~200℃. Within this temperature range, the polystyrene matrix is ​​fully plasticized to achieve good flowability, and the Diels-Alder (DA) reaction rate between furan and maleimide can be effectively controlled to prevent excessive crosslinking during processing, which could lead to material gelation or a decrease in processing performance. This achieves the controllable construction of a dynamic reversible crosslinking network.

[0070] Preferably, the melt blending is carried out in five zones: zone one temperature is 180~185℃, zone two temperature is 180~185℃, zone three temperature is 190~195℃, zone four temperature is 198~203℃, zone five temperature is 198~203℃; and the die head temperature is 195℃.

[0071] Typically, but not limitingly, the melt blending temperature can be, for example, 180°C, 185°C, 190°C, 195°C, or 200°C, or any value within the range of 180°C to 200°C.

[0072] Preferably, during the melt blending process, the screw speed is 60~120 rpm.

[0073] Typical, but not limiting, the screw speed can be, for example, 60 rpm, 70 rpm, 80 rpm, 90 rpm, 100 rpm, 110 rpm or 120 rpm, or any value in the range of 60 to 120 rpm.

[0074] The third aspect of the present invention provides a self-healing optical diffuser plate, which is obtained by hot pressing, annealing and cooling demolding the self-healing optical diffuser plate masterbatch.

[0075] The self-healing optical diffuser plate provided by this invention has a self-healing function. When scratches or other damage occur on the surface, external thermal stimulation triggers the reverse DA reaction (rDA reaction), enhancing chain segment fluidity and promoting the re-contact and recombination of the crack interface. After cooling, the cross-linked structure recovers, thereby achieving autonomous repair of the scratches. This self-healing optical diffuser plate not only possesses excellent optical diffusion performance but also can repeatedly repair surface micro-damage through thermal stimulation, extending the service life of the optical diffuser plate. It is suitable for high-durability display and lighting devices.

[0076] Furthermore, the hot pressing temperature is 170~190℃ and the pressure is 5~15MPa.

[0077] Typically, but not limitingly, the temperature of the hot pressing can be, for example, 170°C, 175°C, 180°C, 185°C, or 190°C, or any value within the range of 170°C to 190°C; the pressure can be, for example, 5 MPa, 7 MPa, 9 MPa, 11 MPa, 13 MPa, or 15 MPa, or any value within the range of 5 to 15 MPa.

[0078] Furthermore, the annealing process involves slowly cooling to 60-80°C at a rate of 0.5-2°C / min and holding at that temperature for 30-60 minutes. This programmed cooling annealing process after hot pressing provides sufficient time and suitable temperature conditions for the forward Diels-Alder (DA) reaction between the furan-functionalized polymer and the maleimide-functionalized polymer, thereby promoting full cross-linking between molecular chains and forming a complete and stable dynamic covalent network structure. This structure not only significantly improves the material's mechanical strength, heat resistance (such as Vicat softening point), and dimensional stability, but also ensures the foundation for self-healing functionality. If this step is omitted and rapid quenching is used, the DA reaction cannot proceed effectively, resulting in an incomplete cross-linked network and a significant decrease in material properties, manifested as a severe reduction in impact strength and tensile strength. Therefore, annealing is not a simple cooling process, but a core technological step that determines the final comprehensive performance and self-healing ability of the material.

[0079] Typical, but not limiting, cooling rates can be, for example, 0.5°C / min, 0.8°C / min, 1°C / min, 1.2°C / min, 1.5°C / min, 1.8°C / min, or 2°C / min, or any value within the range of 0.5 to 2°C / min; the target temperature after cooling can be, for example, 60°C, 65°C, 70°C, 75°C, or 80°C, or any value within the range of 60 to 80°C; the holding time can be, for example, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or 60 minutes, or any value within the range of 30 to 60 minutes.

[0080] Furthermore, the notched impact strength of the self-healing optical diffuser plate is 2.7~4.3 kJ / m. 2 The tensile strength is 36~64 MPa, and the Vicat softening point is 92.9~95.4℃.

[0081] Preferably, the self-healing optical diffuser plate can achieve autonomous repair after surface damage through external thermal stimulation.

[0082] Preferably, the depth of the damage is ≤0.3mm.

[0083] Preferably, the temperature of the thermal excitation is 110℃-130℃, and the time is 10-30min.

[0084] The present invention is further illustrated below with specific embodiments and comparative examples. However, it should be understood that these embodiments are merely for illustrative purposes and should not be construed as limiting the invention in any way. Unless otherwise specified, the raw materials used in the embodiments and comparative examples of the present invention were carried out under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0085] Example 1 This embodiment provides a self-healing light diffusion plate masterbatch, and the specific preparation method is as follows: 1. Add 75 parts of polystyrene (PS), 10 parts of furan-grafted polystyrene (4-vinylbenzyl furan ether grafted polystyrene), 10 parts of maleimide-modified polystyrene, 5 parts of ethylene-ethylene-butene-styrene block copolymer (SEBS), 1 part of polymethyl methacrylate (PMMA) microspheres (average particle size 2-5 μm), 0.3 parts of silane coupling agent (KH-570), 0.1 parts each of primary antioxidant (antioxidant 1010) and secondary antioxidant (antioxidant 168), and 0.1 parts of dibenzoylmethane to a high-speed mixer and mix for 5-15 minutes at room temperature to obtain a premix with uniform composition.

[0086] 2. The premixed material is fed into a co-rotating twin-screw extruder through the main feed port. Specific zone control is applied: Zone 1 180℃, Zone 2 180℃, Zone 3 190℃, Zone 4 200℃, Zone 5 200℃, die head 185℃, and screw speed 100 rpm for melt blending. After extrusion, water cooling, and pelletizing, self-healing optical diffuser masterbatch is obtained.

[0087] Example 2 This embodiment provides a self-healing light diffusion plate masterbatch. Unlike Example 1, it contains 55 parts of polystyrene (PS), 20 parts of furan-grafted polystyrene (4-vinylbenzylfuran ether-grafted polystyrene), and 20 parts of maleimide-grafted polystyrene. The remaining raw materials and preparation methods are the same as in Example 1, and will not be repeated here.

[0088] Example 3 This embodiment provides a self-healing light diffusion plate masterbatch. Unlike Example 1, it does not use ethylene-ethylene-butene-styrene block copolymer (SEBS). The other raw materials and preparation methods are the same as in Example 1, and will not be described again here.

[0089] Example 4 This embodiment provides a self-healing light diffusion plate masterbatch. Unlike embodiment 1, it does not use antioxidant 1010 and antioxidant 168. The other raw materials and preparation methods are the same as in embodiment 1, and will not be described again here.

[0090] Example 5 This embodiment provides a self-healing light diffusion plate masterbatch. The difference from Example 1 is that the amount of maleimide-grafted polystyrene is 5 parts. The other raw materials and preparation methods are the same as in Example 1, and will not be repeated here.

[0091] Example 6 This embodiment provides a self-healing light diffusion plate masterbatch. The difference from Example 1 is that the amount of furan-grafted polystyrene (4-vinylbenzylfuran ether-grafted polystyrene) is 5 parts. The other raw materials and preparation methods are the same as in Example 1, and will not be repeated here.

[0092] Example 7 This embodiment provides a self-healing light diffusion plate masterbatch. Unlike Example 1, the amount of maleimide-grafted polystyrene is 5 parts, and the amount of furan-grafted polystyrene (4-vinylbenzylfuran ether-grafted polystyrene) is 20 parts. The remaining raw materials and preparation methods are the same as in Example 1, and will not be repeated here.

[0093] Example 8 This embodiment provides a self-healing light diffusion plate masterbatch. Unlike Example 1, the amount of maleimide-grafted polystyrene is 20 parts, and the amount of furan-grafted polystyrene (4-vinylbenzylfuran ether-grafted polystyrene) is 5 parts. The remaining raw materials and preparation methods are the same as in Example 1, and will not be repeated here.

[0094] Comparative Example 1 This comparative example provides a light diffusion plate masterbatch. Unlike Example 1, it does not use furan-grafted polystyrene and maleimide-grafted polystyrene. The other raw materials and preparation methods are the same as in Example 1, and will not be repeated here.

[0095] Comparative Example 2 This comparative example provides a light diffusion plate masterbatch. Unlike Example 1, it does not use maleimide-grafted polystyrene. The other raw materials and preparation methods are the same as in Example 1, and will not be repeated here.

[0096] Comparative Example 3 This comparative example provides a light diffusion plate masterbatch. Unlike Example 1, it does not use furan-grafted polystyrene. The other raw materials and preparation methods are the same as in Example 1, and will not be repeated here.

[0097] Examples 9-16 These embodiments provide some self-healing optical diffuser plates, corresponding to the self-healing optical diffuser plate masterbatch provided in Embodiments 1-8, which is placed in a hot press flat mold and hot-pressed at 180°C and 12 MPa for 8 minutes to melt and form the plate; then a key process of cooling annealing is performed: the plate is slowly cooled to 70°C at a rate of 1°C / min and held at that temperature for 40 minutes, and finally the self-healing optical diffuser plate is obtained by cooling and demolding.

[0098] Comparative Examples 4-6 These comparative examples provide some optical diffusion plates, corresponding to the optical diffusion plate masterbatch provided in Comparative Examples 1-3, which are placed in a hot press flat mold and hot-pressed at 180°C and 12 MPa for 8 minutes to melt and form the plate. Then, a key process of cooling annealing is performed: the plate is slowly cooled to 70°C at a rate of 1°C / min and held for 40 minutes. Finally, the plate is cooled and demolded to obtain a self-healing optical diffusion plate.

[0099] Comparative Example 7 This comparative example provides an optical diffusion plate, which differs from Example 9 in that it is directly quenched and cooled to room temperature after melt molding, and then demolded after being left for 40 minutes to obtain the optical diffusion plate.

[0100] Test Example 1 The optical diffusion plates obtained in the examples and comparative examples were tested. Tensile strength was tested according to GB / T1040-1992 standard at a tensile rate of 50 mm / min; notched impact strength was tested according to GB / T1043-1993 standard with a notch depth of 2 mm. Vicat softening temperature was tested according to GB / T 1633 standard. The data obtained are shown in Table 1 below.

[0101] Table 1

[0102] As shown in Table 1, Example 9 demonstrates the optimal overall performance under the formulation and process of this invention. Its notched impact strength reaches 3.9 kJ / m. 2 Compared to pure PS or modified PS with only toughening (typically <2kJ / m), 2 This represents a qualitative leap, proving that the material has transformed from brittle to tough. Simultaneously, the tensile strength reaches 59 MPa, superior to conventionally toughened PS, and the Vicat softening point remains at a high level of 95.4℃. These three characteristics demonstrate that the dynamically reversible DA network successfully constructed in this invention acts as a reversible crosslinking point: providing reinforcement and heat resistance similar to chemical crosslinking at room temperature; and upon impact, some dynamic bonds break to dissipate energy, while the toughening agent phase region induces numerous crazes and shear bands, synergistically absorbing impact energy, thus achieving a balance between rigidity and toughness.

[0103] In Comparative Example 4, the PS without DA component was toughened, and the impact strength was 3.1 kJ / m.2 However, it has the lowest strength (42 MPa) and heat resistance (91.0 °C), which is a traditional trade-off between strength and toughness. Comparative Example 5 contains only furan components, and its performance is inferior to that of Example 1 in all aspects, proving that the lack of maleimide functional groups prevents the formation of an effective DA network and results in an incomplete dynamic cross-linking structure.

[0104] Example 10 increased the total content of the DA component. While maintaining high heat resistance, the impact strength decreased slightly, and the tensile strength significantly decreased to 46 MPa. This indicates that excessively high dynamic crosslinking density may restrict molecular chain segment movement, which is detrimental to toughness. Furthermore, excessive functionalized polymers may affect the continuity of the PS matrix. The formulation of Example 9 (10 parts each) represents the optimal balance between strength, toughness, and processability.

[0105] Example 11, without the addition of toughening agent SEBS, has a notched impact strength of 2.8 kJ / m. 2 The ) was the lowest among all embodiments, and the tensile strength also decreased significantly. This directly confirms the concerns mentioned in the background section: a simple DA dynamic network increases brittleness. The introduction of a toughening agent, as an independent energy dissipation phase, is one of the core means to resolve this contradiction and achieve high impact strength.

[0106] Comparative Example 7 used the exact same formula, but the temperature cooling annealing process was omitted, and direct quenching was performed instead. The result was a complete collapse in performance: impact strength (2.2 kJ / m²) was reduced. 2 Both the tensile strength and tensile strength (29 MPa) were the lowest among all samples. This proves that the controlled-temperature annealing treatment after hot pressing is not a normal cooling step, but a key invention that drives the DA forward reaction and reconstructs the complete dynamic network. Without this step, DA groups cannot effectively bind, and the material is equivalent to an uncrosslinked blend with poor performance.

[0107] Test Example 2 The self-healing optical diffuser obtained in Example 9 was tested for its repair capability. The experimenter manually scratched the sample surface with a sharp metal needle, creating visible micro-scratches, and photographed the surface as shown below. Figure 1 As shown; a self-healing optical diffuser plate with scratches was repaired at 120℃ for 20 minutes, and the surface after self-healing was photographed as follows. Figure 2 As shown.

[0108] from Figure 1 and Figure 2As can be seen, after thermal stimulation, the scratches completely disappeared, and the optical surface was restored to its original condition. This intuitive comparison fully demonstrates the self-healing capability of the material endowed by this invention. Once a traditional optical diffuser is damaged, the scratches become permanent defects, directly leading to optical path disruption and visual flaws, severely affecting product yield and lifespan. This invention, through its inherent Diels-Alder dynamic reversible network, enables the material to achieve autonomous repair of micro-damage under mild thermal stimulation. This not only efficiently restores optical uniformity but also fundamentally improves product reliability and durability, achieving a technological leap from passive protection to active repair.

[0109] Finally, it should be noted that the above-described embodiments are merely specific implementations of the present invention, used to illustrate the technical solutions of the present invention, and not to limit it. The scope of protection of the present invention is not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that any person skilled in the art can still modify or easily conceive of changes to the technical solutions described in the foregoing embodiments within the technical scope disclosed in the present invention, or make equivalent substitutions for some of the technical features; and these modifications, changes, or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention, and should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A self-healing optical diffuser masterbatch, characterized in that, It includes the following components by weight: 65-85 parts of polystyrene matrix, 5-20 parts of furan-functionalized polymer, 5-20 parts of maleimide-functionalized polymer, 0.5-3 parts of dispersant, and 2.3-9.8 parts of additives.

2. The self-healing optical diffuser masterbatch according to claim 1, characterized in that, The furan-functionalized polymers include furan-functionalized polystyrene and / or furan methacrylate copolymers; Preferably, the furan-functionalized polystyrene includes at least one of furan-methanol-terminated polystyrene, furan-methanol-grafted polystyrene, and furan-methanol-terminated and grafted polystyrene. Preferably, the furan methacrylate copolymer comprises maleimide-functionalized polystyrene and / or maleimide-modified elastomer; Preferably, the maleimide-functionalized polystyrene includes maleimide-terminated polystyrene.

3. The self-healing optical diffuser masterbatch according to claim 1, characterized in that, The dispersant includes at least one of silica, titanium dioxide, polymethyl methacrylate microspheres, cross-linked polystyrene microspheres, and acrylate microspheres.

4. The self-healing optical diffuser masterbatch according to any one of claims 1 to 3, characterized in that, The additives include at least one of toughening agents, dispersants, antioxidants, and heat stabilizers; Preferably, the toughening agent comprises at least one of styrene-ethylene-butene-styrene block copolymer (SEBS), methyl methacrylate-butadiene-styrene copolymer (MBS), and acrylate core-shell copolymer (ACR); Preferably, the toughening agent is present in 2 to 8 parts by weight; Preferably, the dispersant comprises a silane coupling agent and / or a titanate coupling agent; Preferably, the dispersant is present in an amount of 0.1 to 0.8 parts by weight; Preferably, the antioxidant grade includes at least one of antioxidant 1010, antioxidant 626, and antioxidant 168; Preferably, the antioxidant is present in an amount of 0.1 to 0.5 parts by weight; Preferably, the heat stabilizer comprises dibenzoylmethane and / or hindered amine light stabilizers; Preferably, the heat stabilizer is present in 0.1 to 0.5 parts by weight.

5. A method for preparing a self-healing optical diffuser masterbatch according to any one of claims 1 to 4, characterized in that, A premix is ​​prepared by uniformly mixing polystyrene matrix, furan-functionalized polymer, maleimide-functionalized polymer, dispersant and additives; the premix is ​​then melt-blended and granulated using a twin-screw extruder to obtain a self-healing optical diffuser masterbatch.

6. The preparation method according to claim 5, characterized in that, The mixing is carried out in a high-speed mixer; Preferably, the mixing time is 5-15 minutes; Preferably, the melt blending temperature is 180~200℃.

7. A self-healing optical diffuser plate, characterized in that, The self-healing optical diffuser masterbatch described in any one of claims 1 to 4 is obtained by hot pressing, annealing, and cooling demolding.

8. The self-healing optical diffuser plate according to claim 7, characterized in that, The hot pressing temperature is 170~190℃ and the pressure is 5~15MPa.

9. The self-healing optical diffuser plate according to claim 7, characterized in that, The annealing process is as follows: slowly cool to 60-80°C at a rate of 0.5-2°C / min, and hold at that temperature for 30-60 minutes.

10. The self-healing optical diffuser plate according to any one of claims 7 to 9, characterized in that, The notched impact strength is 2.7~4.3 kJ / m. 2 The tensile strength is 36~64 MPa, and the Vicat softening point is 92.9~95.4℃; Preferably, the self-healing optical diffuser plate can achieve autonomous repair after surface damage through external thermal stimulation; Preferably, the depth of the damage is ≤0.3mm; Preferably, the temperature of the thermal excitation is 110~130℃ and the time is 10~30min.

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