High-light-transmittance weather-resistant impact-resistant color stripe plate and manufacturing method thereof

Abstract

The invention relates to the technical field of multi-layer structures, in particular to a high-light-transmittance weather-proof impact-resistant color stripe plate and a manufacturing method. The problem that in the prior art, the mechanical property and the optical property of a color stripe plate cannot be considered at the same time is solved. A multi-layer structure is adopted, the weather-proof layer, the base body layer and the weather-proof layer are sequentially arranged from top to bottom, and the stripe layer penetrates through the interface of the weather-proof layer and the base body layer; the matrix layer is obtained by melt copolymerization of polycarbonate, PBAT and MBS; the weather-proof layer is obtained by melting polymethyl methacrylate, polycarbonate, maleic anhydride grafted polycarbonate and an ultraviolet absorbent; the stripe layer is prepared by mixing weather-resistant PC, modified nano titanium dioxide and composite inorganic pigment step by step, and fine stripes are formed by using a multi-runner distributor. Through the synergistic effect of the material components and the multi-layer co-extrusion process, the problem that the mechanical property and the light transmittance performance of a traditional plate are difficult to consider at the same time is effectively solved, and the light-transmitting plate is suitable for building decoration with the high-performance requirement.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of multi-layer structure, in particular to a high-transmittance weather-resistant impact-resistant color stripe plate and a manufacturing method. BACKGROUND

[0002] The polycarbonate plate is a new type of material with high transmittance, impact resistance and anti-aging, which is widely used in industrial safety partition protection and municipal traffic partition safety protection. Because of its excellent permeability, it is not easy to be observed by pedestrians when applied in industrial and municipal safety partitions, which may easily cause personnel collision, scratches and injuries caused by falling debris due to impact, etc., without fundamentally reducing the safety hazards.

[0003] The existing color stripe plate, especially the plate used in the fields of building and decoration, usually faces the challenge of difficult to balance the mechanical properties and optical properties. In order to obtain the color stripe effect, the traditional single-layer blending plate needs to directly mix the pigment with the polymer matrix; however, this blending method easily leads to uneven dispersion of the pigment, forming agglomerates, which not only affects the clarity and aesthetics of the stripes, but also significantly reduces the light transmittance of the plate due to the enhanced light scattering. In addition, the pigment agglomerates form stress concentration points in the material, making the material have poor toughness and low impact strength when impacted.

[0004] In addition, in order to improve the mechanical properties, especially the impact strength, it is usually necessary to add a toughening agent in the prior art, but this may sacrifice the rigidity or transparency of the material, leading to unbalanced performance. Therefore, how to design the material system and processing technology to balance the comprehensive mechanical properties of the plate while maintaining the high light transmittance and optical properties of the clear stripes is the main problem limiting the application range of the color stripe plate.

[0005] Therefore, a high-transmittance weather-resistant impact-resistant color stripe plate and a manufacturing method are provided. SUMMARY

[0006] The present application aims to provide a high-transmittance weather-resistant impact-resistant color stripe plate and a manufacturing method. The present application adopts a multi-layer structure, from top to bottom, a weather-resistant layer, a matrix layer and a weather-resistant layer, and a stripe layer penetrating the interface between the weather-resistant layer and the matrix layer; the matrix layer is obtained by melt copolymerization of polycarbonate, PBAT and MBS; the weather-resistant layer is obtained by melt of polymethyl methacrylate, polycarbonate, maleic anhydride grafted polycarbonate and ultraviolet absorber; the stripe layer is prepared by stepwise mixing of weather-resistant PC, modified nano-titanium dioxide and composite inorganic pigment, and fine stripes are formed by using a multi-channel distributor. The present application effectively solves the problem of difficult to balance the mechanical properties and light transmittance of the traditional plate through the synergistic effect of the material components and the multi-layer co-extrusion process, and is suitable for high requirement decoration and functional application.

[0007] To achieve the above object, the present application provides the following technical solutions.

[0008] The present application provides a manufacturing method of high-transparency weather-resistant impact-resistant color stripe plate, comprising the following manufacturing steps:

[0009] The weather-resistant layer, the base layer and the weather-resistant layer are sequentially arranged from top to bottom, the base layer is added into a main extruder to obtain a base layer melt by melting extrusion, the weather-resistant layer is added into a satellite extruder to obtain a weather-resistant layer melt by melting extrusion, the stripe layer is added into a small extruder to obtain a stripe layer melt by melting extrusion, at the end of the homogenization section of the main extruder, precise injection of dicumyl peroxide as an initiator is carried out by a metering pump, the amount of the initiator is 0.15% of the total mass of the base layer, the weather-resistant layer melt, the base layer melt and the weather-resistant layer melt are introduced into a multi-channel distributor to form a three-layer structure, at the same time, the stripe layer melt is divided into multiple streams by the distribution channels in the distributor and is injected into the weather-resistant layer melt and the base layer melt to obtain a composite melt, the composite melt is introduced into a die, the temperature is controlled to be 250-260 DEG C to obtain a multi-layer melt, the multi-layer melt is introduced into a three-roll calender, the three-roll temperature is controlled to be 110 DEG C, 125 DEG C and 130 DEG C respectively, the thickness of the plate is accurately controlled by the gap between the rollers, the plate precursor is obtained by preliminary shaping and cooling, the plate precursor is heated to 125-130 DEG C by an online annealing furnace, the temperature is maintained for 20-30 min, the cooling rate is 1-2 DEG C / min, the temperature is slowly cooled to below 60 DEG C, and the color stripe plate is obtained by air cooling to room temperature.

[0010] The base layer is obtained by melting copolymerization of polycarbonate and polybutylene adipate terephthalate, and melting extrusion of MBS and an auxiliary agent;

[0011] The weather-resistant layer is obtained by melting extrusion of polymethyl methacrylate and polycarbonate;

[0012] The stripe layer is obtained by melting extrusion of weather-resistant PC, modified nano titanium dioxide and composite inorganic pigment.

[0013] Preferably, the layered structure is a symmetric three-layer design of weather-resistant layer / base layer / weather-resistant layer, the stripe layer is embedded in the upper and lower weather-resistant layers in the form of 8-12 streams, and the embedding depth is 1 / 3 of the thickness of the weather-resistant layer, wherein the width of the stripe is accurately controlled to be 1-3 mm and the interval is 5-10 mm by the design of the micro-channel and the nozzle of the distributor to ensure uniform decoration effect, and the thickness of the weather-resistant layer is 0.5-1.0 mm and the thickness of the base layer is 2-3 mm.

[0014] Preferably, the stripe layer melt is divided into multiple streams by 8-12 micro-channels of the flow distributor, and the flow rate is accurately controlled to be 0.5-1.0 kg / h by the metering pump; each stream is injected into the interface between the weather-resistant layer and the base layer by the nozzle of the distribution channel at an angle of 15-30 DEG.

[0015] Preferably, the manufacturing of the base layer comprises the following steps:

[0016] Polycarbonate 70-80 parts and polybutylene adipate terephthalate 15-25 parts are placed in a vacuum drying oven, dried at 80°C for 4h to obtain dry raw materials; the dry raw materials are added into a twin-screw extruder, 0.3-0.5 parts of tetrabutyl titanate is added, the melt temperature is 250-260°C, the screw rotation speed is 200-300 rpm, and the melt copolymerization is carried out for 10-20 min to obtain a copolymer; 5-10 parts of MBS, 0.3 parts of antioxidant 1010, and 0.5 parts of zinc stearate are added into the copolymer, the feeding section temperature is 180-220°C, the compression section temperature is 240-260°C, the metering section temperature is 245-255°C, the die temperature is 240-250°C, and the screw rotation speed is maintained at 300-450 rpm to obtain the base layer, and the melt index of the base layer is 8-10 g / min;

[0017] Preferably, the manufacturing of the weather-resistant layer comprises the following steps:

[0018] Polymethyl methacrylate 50-60 parts and polycarbonate 35-45 parts are placed in a vacuum drying oven, dried at 90°C for 4h to obtain dry materials; the dry materials are added into a twin-screw extruder, 3-5 parts of maleic anhydride grafted polycarbonate, 0.5 parts of ultraviolet absorber-326, 0.5 parts of ultraviolet absorber 1600, 0.8 parts of HALS, and 0.5 parts of zinc stearate are added, the feeding section temperature is 180-210°C, the compression section temperature is 230-250°C, the metering section temperature is 230-240°C, the die temperature is 220-230°C, and the screw rotation speed is maintained at 300-400 rpm to obtain the weather-resistant layer, and the melt index is 6-8 g / min;

[0019] Preferably, the manufacturing of the weather-resistant layer comprises the following steps:

[0020] Place 80-90 parts of weather-resistant PC in a vacuum drying oven and dry at 80℃ for 4 hours to obtain a dried system. Add the dried system to a high-speed mixer, add 5-8 parts of modified nano-titanium dioxide, and stir for 5 minutes at a speed of 500-600 rpm to obtain a mixture. Add 8-12 parts of composite inorganic pigment to the mixture, and stir for 10 minutes at a speed of 300-400 rpm to obtain a mixed system. Add 0.6 parts of polyether dispersant, 0.5 parts of zinc stearate, and 0.3 parts of antioxidant 1010 to the mixed system, and then add it to a twin-screw extruder. During the discharge process, the temperature of the feeding section is maintained at 190-220℃, the temperature of the compression section at 250-270℃, the temperature of the metering section at 250-260℃, and the temperature of the die head at 245-255℃. The screw speed is maintained at 200-400 rpm to obtain the striped layer. The composite inorganic pigment is obtained by mixing titanium dioxide and iron oxide red in a certain mass ratio. The specific mass ratio can be adjusted according to the specific color requirements. During the mixing process, the ball-to-material ratio is maintained at 10:1 in a ball mill, the ball mill speed is 300-500 rpm, and the ball milling time is 2-4 hours.

[0021] Preferably, the stepwise blending includes the following steps:

[0022] Place 80-90 parts of weather-resistant PC in a vacuum drying oven and dry at 80℃ for 4 hours to obtain a dried system; add the dried system to a high-speed mixer, add 5-8 parts of modified nano titanium dioxide, maintain the speed at 500-600 rpm, and stir for 5 minutes to obtain a mixture; add 8-12 parts of composite inorganic pigment to the mixture, maintain the speed at 300-400 rpm, and stir for 10 minutes to obtain a mixed system.

[0023] Preferably, the preparation of modified nano-titanium dioxide includes the following steps:

[0024] By mass, 10 parts of nano-titanium dioxide were dispersed in 50 parts of 95% ethanol aqueous solution, the pH of the system was adjusted to 5 with acetic acid, and the mixture was stirred in a magnetic stirrer at 50°C for 3 hours to obtain an inorganic dispersion; 1 part of KH-570 was slowly added to the inorganic dispersion, and the mixture was reacted at 80°C for 2 hours to obtain a modified system; the modified system was dried and ground to obtain modified nano-titanium dioxide;

[0025] The present invention also provides a high light transmittance, weather-resistant and impact-resistant colored striped plate, which consists of a weather-resistant layer, a substrate layer and a weather-resistant layer from top to bottom. The striped layer is injected between the weather-resistant layer and the substrate layer to form a uniform and parallel striped pattern that runs through the interface between the weather-resistant layer and the substrate layer, giving the plate a visual effect of colored stripes.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] 1、The application significantly improves the rigidity of the substrate layer by blending PC and PBAT, promoting interfacial compatibility with tetrabutyl titanate to form a chemically bonded copolymer; the micro-crosslinking of the initiator during the melting process further enhances the interlayer bonding force; compared with the prior art, the application avoids the defect of insufficient toughness of rigid materials through MBS and multi-layer structure design, releases internal stress in the subsequent process, improves molecular chain arrangement, reduces micro-cracks, ensures that the material still maintains excellent rigidity under high load, and is suitable for high-strength application scenarios such as building decoration and automotive interior.

[0028] 2、The application avoids stress concentration by using MBS as a toughening agent, the synergistic effect of the flexibility of PBAT and the rigidity of PC, and the improvement of interfacial compatibility by tetrabutyl titanate; compared with the prior art, the application enhances energy absorption and dispersion ability through multi-layer structure and interlayer crosslinking induced by DCP, and further optimizes molecular chain arrangement through online annealing and slow cooling process, so that the plate exhibits excellent toughness under impact load.

[0029] 3、The application significantly improves the light transmittance of the traditional color stripe plate through the design of the composite weather-resistant layer of PMMA and PC, and the stripe layer of modified nano titanium dioxide and composite inorganic pigment; the multi-channel distributor forms uniform and delicate stripe patterns, reducing light scattering; the step-by-step mixing process ensures uniform dispersion of nano fillers and avoids agglomeration; maleic anhydride grafted PC improves compatibility and reduces micro-phase separation; through the synergistic effect of components and process, high light transmittance and visual effect of color stripes are considered, and the application is suitable for transparent decorative plate field.

[0030] 4、The application covers a wide ultraviolet band through the synergistic effect of UV-326, UV-1600 and HALS in the weather-resistant layer, inhibits photooxidation reaction, and has better weather resistance than traditional PC plates; in addition, the composite substrate of PMMA and PC provides high transparency and weather resistance, protects the stripe layer and substrate layer from ultraviolet degradation; the slow cooling process optimizes the molecular chain arrangement, reduces the internal stress, and reduces the micro-cracks during the aging process. Through the synergistic effect of multi-layer structure and additives, the mechanical property stability of the plate under xenon arc lamp aging is significantly improved, and the application is suitable for outdoor decoration and other long-term exposure environments.

[0031] 5、The application uses composite inorganic pigments uniformly mixed by a ball mill, combined with modified nano titanium dioxide, and the color difference variation is much lower than that of traditional organic pigment plates; in addition, KH-570 modification enhances the compatibility of nano titanium dioxide and weather-resistant PC, reduces agglomeration, and ensures the uniformity of the stripes; the multi-channel distributor forms fine stripe patterns, improving color stability; UV absorbers and HALS inhibit photooxidation reaction and protect pigments from degradation. Compared with the prior art, the application significantly improves color fastness through inorganic pigments and process optimization, and is suitable for application scenarios that require high aesthetics and long-term color stability. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The tensile strength change graph of the color striped board before and after aging is prepared for Examples 1-3 and Comparative Examples 13-16. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0034] The Tg of the polycarbonate is 150 DEG C, the melt index is 10 g / 10 min; the PBAT is polybutylene adipate terephthalate, the processing temperature is 180-230 DEG C, the melt index is 5-10 g / 10 min; the PMMA is polymethyl methacrylate, the processing temperature is 180-250 DEG C, the melt index is 6-8 g / 10 min; the MBS is a methyl methacrylate-butadiene-styrene copolymer core-shell structure toughening agent; the maleic anhydride grafting rate of the maleic anhydride grafted polycarbonate is 1-2%; the particle size of the nano titanium dioxide is 20-50 nm; the polyether dispersant is BYK-310; the HALS is a hindered amine light stabilizer, the CAS number is 82451-48-7; the UV-326 is a triazole ultraviolet absorber, the CAS number is 3896-11-5; the UV-1600 is a triazine ultraviolet absorber, the CAS number is 204583-39-1, and the raw materials used are all commercially available products.

[0035] Please refer to Figure 1 The present application provides a kind of high light transmission weathering impact resistant color striped board and manufacturing method, technical scheme as follows:

[0036] Example 1

[0037] Polycarbonate 80 parts and polybutylene adipate terephthalate 20 parts are placed in a vacuum drying oven, dried at 80 DEG C for 4 h to obtain dry raw materials; the dry raw materials are added to a twin-screw extruder, 0.4 parts of tetrabutyl titanate is added, the melt temperature is 250-260 DEG C, the screw rotation speed is 250 rpm, and the melt copolymerization is carried out for 20 min to obtain a copolymer; 8 parts of MBS, 0.3 parts of antioxidant 10100 and 0.5 parts of zinc stearate are added to the copolymer, and the screw rotation speed is kept at 400 rpm to obtain a matrix layer.

[0038] Put 60 parts of polymethyl methacrylate and 40 parts of polycarbonate into a vacuum drying oven, dry at 90℃ for 4h to obtain dry materials; add the dry materials into a twin-screw extruder, add 4 parts of maleic anhydride grafted polycarbonate, 0.5 parts of ultraviolet absorber-326, 0.5 parts of ultraviolet absorber 1600, 0.8 parts of HALS, 0.5 parts of zinc stearate, and keep the screw speed at 300 rpm to obtain the weather-resistant layer;

[0039] Disperse 10 parts of nano-titanium dioxide in 50 parts of 95% ethanol aqueous solution, adjust the pH of the system to 5 with acetic acid, and stir in a 50℃ magnetic stirrer for 3h to obtain an inorganic dispersion; slowly add 1 part of KH-570 to the inorganic dispersion, and react at 80℃ for 2h to obtain a modified system; dry and grind the modified system to obtain modified nano-titanium dioxide;

[0040] Put 80 parts of weather-resistant PC into a vacuum drying oven, dry at 80℃ for 4h to obtain a dry system; add the dry system into a high-speed mixer, add 6 parts of modified nano-titanium dioxide, keep the speed at 600 rpm, and stir for 5 min to obtain a mixture; add 10 parts of composite inorganic pigment to the mixture, keep the speed at 400 rpm, and stir for 10 min to obtain a mixed system; add 0.6 parts of polyether dispersant, 0.5 parts of zinc stearate, and 0.3 parts of antioxidant 1010 to the mixed system, and add them into a twin-screw extruder, keep the screw speed at 300 rpm to obtain the stripe layer; the composite inorganic pigment is obtained by mixing titanium dioxide and iron oxide red at a mass ratio of 1:1, the mixing process is carried out by a ball mill with a ball-to-material ratio of 10:1, a ball mill speed of 400 rpm, and a ball milling time of 3h.

[0041] From top to bottom, they are weather-resistant layer, substrate layer, and weather-resistant layer; add the substrate layer into the main extruder, add the weather-resistant layer into the planetary extruder, and add the stripe layer into the small extruder; at the end of the homogenization section of the main extruder, accurately inject the dicumyl peroxide initiator through the metering pump, and the amount is 0.15% of the total mass of the substrate layer; the three main melts (weather-resistant layer, substrate layer, and weather-resistant layer) enter the multi-channel distributor to form a three-layer structure, and at the same time, the stripe layer melt is divided into multiple streams by the distribution channel in the distributor and injected into the weather-resistant layer melt and the substrate layer melt to obtain a composite melt; the composite melt enters the die, and the temperature is kept to obtain a multi-layer melt; the multi-layer melt enters the three-roll calender, the three-roll temperature is controlled at 110℃, 125℃, and 130℃ respectively, the thickness of the plate is accurately controlled by the gap between the rollers, and the plate precursor is obtained after preliminary shaping and cooling; the plate precursor passes through the online annealing furnace, is slowly heated to 130℃, and is kept for 30 min; then it is slowly cooled to below 60℃ at a cooling rate of 1.5℃ / min, and air-cooled to room temperature to obtain a color stripe plate.

[0042] Example 2-5 Refer to the preparation method and parameters of Example 1, the difference is shown in Table 1.

[0043] Table 1 Parameter changes of Examples 1-5

[0044]

[0045]

[0046] Comparative Example 1 Refer to Example 1, the difference is that PBAT is not added in the matrix layer, and other components remain unchanged.

[0047] Comparative Example 2 Refer to Example 1, the difference is that MBS is not added in the matrix layer, and other components remain unchanged.

[0048] Comparative Example 3 Refer to Example 1, the difference is that PBAT and MBS are not added in the matrix layer, and polycarbonate is directly used as the matrix layer.

[0049] Comparative Example 4 Refer to Example 1, the difference is that tetrabutyl titanate is not introduced during the melting process of the matrix layer, and direct melting mixing is performed.

[0050] Comparative Example 5 Refer to Example 1, the difference is that the slow cooling treatment is not performed during the annealing process.

[0051] Comparative Example 6 Refer to Example 1, the difference is that dicumyl peroxide is not injected during the extrusion process of the main extruder.

[0052] Comparative Example 7 Refer to Example 1, the difference is that the multilayer structure is not used, and the matrix layer, the weather-resistant layer, and the stripe layer are directly melt-blended, and the colored stripe plate is obtained after processing.

[0053] Experimental Example 1 Mechanical property test

[0054] The colored stripe plates prepared in Examples 1-5 and Comparative Examples 1-7 are subjected to mechanical property tests, the tensile strength is tested according to GB / T1040-2018, and the impact strength is tested according to GB / T 1843-2008, and the test results are shown in Table 2.

[0055] Table 2 Performance test results of examples and comparative examples

[0056] Example Tensile strength / MPa Impact strength / kJ / m 2 ]] Example 1 65.5 56.8 Example 2 65.2 56.5 Example 3 65.4 56.6 Example 4 65.1 56.2 Example 5 65.3 56.4 Comparative Example 1 68.2 42.6 Comparative Example 2 66.8 40.7 Comparative Example 3 70.5 38.5 Comparative Example 4 58.6 41.8 Comparative Example 5 54.6 39.6 Comparative Example 6 58.2 41.2 Comparative Example 7 54.8 36.9

[0057] From the results of Table 2, it can be seen that in the comparative examples, by adjusting the components and changing the process, the mechanical properties of the color striped plate prepared are obviously different from those of the examples; in Comparative Examples 1-3, after not adding PBAT, the content of the rigid material polycarbonate is relatively increased, which leads to a slight increase in tensile strength, but the toughness of the material is greatly reduced, and the impact strength is significantly reduced; the lack of MBS will lead to the fact that the matrix layer cannot effectively absorb and disperse impact energy when it is impacted, and the stress concentration phenomenon is serious, thereby causing the impact strength of the material to decrease sharply; at the same time, lacking the two toughening modifiers PBAT and MBS, using only polycarbonate as the matrix layer has very high tensile strength and rigidity, but it has high notch sensitivity, poor toughness, and significantly reduced impact strength; in Comparative Example 7, without using the multi-layer structure treatment, directly melt blending destroys the order of the layered structure, leading to uneven dispersion of the functional components of the weather-resistant layer and the striped layer, reducing the surface protection ability and internal toughening effect of the material, and in addition, the blending process can lead to a decrease in the compatibility of the components, resulting in phase separation, further affecting the mechanical properties; in Comparative Example 4, tetrabutyl titanate as a coupling agent can improve the interfacial compatibility between PC, PBAT and MBS, promote the crosslinking and copolymerization of the molecular chains, and not adding tetrabutyl titanate leads to weak interfacial bonding force of the copolymer, micro defects in the material, and reduced tensile strength and impact strength; in combination with Comparative Example 6, DCP as an initiator can initiate the chemical crosslinking of the matrix layer, the weather-resistant layer and the striped layer during the multi-layer compounding process, and enhance the interlayer bonding force; in addition, DCP can also promote the slight crosslinking of the PC molecular chains, and improve the strength of the material; not adding DCP leads to weak interlayer bonding, and the composite material is prone to interlayer peeling under stress, thereby reducing the overall mechanical properties; in Comparative Example 5, slow cooling treatment can effectively release the residual stress in the material, improve the arrangement of the molecular chains and the crystallinity, and if it is not used, it will lead to stress concentration in the material, disordered arrangement of the molecular chains, and reduced mechanical properties of the material; in addition, too fast cooling speed leads to inconsistent cooling rates between the surface and the interior, resulting in micro-cracks, and further affecting the tensile strength and impact strength.

[0058] In summary, the present application combines the rigidity of PC, the flexibility of PBAT and the impact resistance of MBS, and under the action of tetrabutyl titanate, promotes the formation of a chemical bonded copolymer of PC and PBAT, the matrix layer formed is responsible for providing excellent mechanical support and toughness, in addition, the addition of DCP initiates the micro-crosslinking of the interlayer structure, and enhances the mechanical properties of the matrix; finally, through the introduction of online annealing and slow cooling process, the color striped plate with excellent mechanical properties is obtained under the synergistic effect.

[0059] Examples 6-8 refer to the preparation method and parameter conditions of Example 1, and the differences are shown in Table 3.

[0060] Table 3 Parameter changes of Example 1, Examples 6-8

[0061]

[0062] Comparative Example 7 refers to Example 1, the difference is that no multi-layer structure is used, the base layer, weather-resistant layer and stripe layer are directly melt-blended, and the color stripe plate is obtained after post-processing.

[0063] Comparative Example 8 refers to Example 1, the difference is that no stripe layer is used, only the base layer and weather-resistant layer are used, and melt-extrusion is not affected by the multi-channel distributor.

[0064] Comparative Example 9 refers to Example 1, the difference is that no polymethyl methacrylate is used in the weather-resistant layer, and the other components remain unchanged.

[0065] Comparative Example 10 refers to Example 1, the difference is that no maleic anhydride grafted polycarbonate is added in the weather-resistant layer, and the other components remain unchanged.

[0066] Comparative Example 11 refers to Example 1, the difference is that no modified nano-titanium dioxide is added in the stripe layer.

[0067] Comparative Example 12 refers to Example 1, the difference is that the nano-titanium dioxide in the stripe layer is not modified.

[0068] Comparative Example 13 refers to Example 1, the difference is that the stripe layer is not processed by the multi-channel distributor, and the color stripe plate is directly melt-extruded by multiple extruders.

[0069] Comparative Example 14 refers to Example 1, the difference is that the composite inorganic pigment is replaced by an organic pigment, and the amount remains unchanged.

[0070] Comparative Example 15 refers to Example 1, the difference is that the stripe layer is not processed by the high-speed mixer during preparation.

[0071] Experimental Example 2: Light transmission performance test

[0072] The color stripe plates prepared by Example 1, Examples 6-8 and Comparative Examples 7-15 were tested for light transmission performance. The light transmission rate was tested according to the test method of GB / T 2410-2008, and the light transmission rate tester was used to measure at a wavelength of 550 nm. The sample thickness was uniformly 3 mm. The test results are shown in Table 4.

[0073] Table 4: Test results of examples and comparative examples

[0074] Example Light transmission / % Example 1 85.6 Example 6 85.4 Example 7 85.3 Example 8 85.5 Comparative Example 7 72.5 Comparative Example 8 88.2 Comparative Example 9 78.5 Comparative Example 10 80.3 Comparative Example 11 90.4 Comparative Example 12 76.8 Comparative Example 13 73.4 Comparative Example 14 70.9 Comparative Example 15 74.2

[0075] From the results of Table 4, it can be seen that in the comparative examples, by adjusting the components and changing the process, the light transmission performance of the color stripe plate prepared is obviously different from that of the examples; in Comparative Example 7, direct melt blending destroys the layered structure of the matrix layer, the weather-resistant layer and the stripe layer, resulting in blurred material interface, and the nanometer titanium dioxide and pigments in the stripe layer are dispersed into the entire plate, causing enhanced light scattering and significantly reduced light transmission; in Comparative Example 8, the high-transmittance base plate is formed by the matrix layer and the weather-resistant layer, without introducing the stripe layer, which does not have the visual effect of color stripes, but proves that the matrix layer and the weather-resistant layer themselves have excellent transparency; in Comparative Examples 9-10, PMMA itself has excellent transparency and weather resistance, and the introduction of the post-weathering layer and the compatibility with other additives are reduced, resulting in micro-phase separation or reduced transparency of the material, affecting the light transmission performance of the plate; and the absence of maleic anhydride grafted polycarbonate will cause serious phase separation during melt blending, forming micron-sized sea-island structures that strongly scatter light, resulting in a significant reduction in the overall light transmission of the plate; in Comparative Examples 11-12, the aesthetic effect of the stripe layer depends on the modified nanometer titanium dioxide, and without its introduction, the stripe area is mainly composed of PC resin and a small amount of pigment, becoming nearly transparent, losing contrast with the matrix layer and failing to form clear stripes; the absence of modified nanometer titanium dioxide will cause severe agglomeration of the particles, forming large pigment aggregates, which not only make the stripes rough and uneven, but also become light scattering centers, significantly reducing the light transmission of the material; in Comparative Example 13, the core function of the multi-channel distributor is to divide the melt of the stripe layer into multiple small "streams" and uniformly inject it between the weather-resistant layer and the matrix layer, thereby forming fine and parallel stripe patterns; without the multi-channel distributor, the melt of the stripe layer will only form one or a few thick and irregular color bands, resulting in a rough overall appearance, uneven light transmission and a significant reduction in light transmission; in Comparative Example 14, the organic pigment has poor optical stability and is less compatible with the PC matrix than the composite inorganic pigment, and in addition, it is easily decomposed and discolored during melt extrusion, thereby affecting the color stability and light transmission performance of the product; in Comparative Example 15, using the direct mixing method, the nanometer titanium dioxide is easily wrapped by other pigment particles, forming agglomerates, and cannot achieve uniform dispersion at the nanometer level; uneven dispersion will directly lead to poor optical performance of the stripe layer and a reduction in the light transmission of the plate.

[0076] In summary, at the component level, the application ensures the mechanical properties and basic transparency of the plate by using a toughened polycarbonate system; PMMA is used in conjunction with PC to form a high-transparency, anti-aging weather-resistant layer by using maleic anhydride grafted polycarbonate as a compatibilizer; finally, by adding modified nano-titanium dioxide and composite inorganic pigments, a striped layer is formed; at the process level, the preparation of the striped layer uses a step-by-step mixing process to ensure that the nano-filler is fully and uniformly dispersed in the resin; a multi-channel distributor is used to divide and accurately inject the striped layer melt, forming fine, uniform, and parallel striped patterns to reduce light scattering; the synergistic effect of the components and processes improves the light transmittance of the plate.

[0077] Comparative Example 13 refers to Example 1, except that the striped layer is not processed by a multi-channel distributor, but is directly melt-extruded by multiple extruders to obtain a colored striped plate.

[0078] Comparative Example 14 refers to Example 1, except that the composite inorganic pigment is replaced by an organic pigment, and the amount remains unchanged.

[0079] Comparative Example 15 refers to Example 1, except that the striped layer is not subjected to a step-by-step mixing process by a high-speed mixer during preparation.

[0080] Comparative Example 16 refers to Example 1, except that no ultraviolet absorber and HALS are introduced into the weather-resistant layer, and the remaining components remain unchanged.

[0081] Comparative Example 17 refers to Example 1, except that only ultraviolet absorber-326 and HALS are added to the weather-resistant layer, and the remaining components remain unchanged.

[0082] Comparative Example 18 refers to Example 1, except that the same polycarbonate as the base layer and the weather-resistant layer is used in the striped layer, and no weather-resistant PC is used.

[0083] Experimental Example 3 Weather Resistance and Color Fastness Test

[0084] The colored striped plates prepared in Examples 1-5 and Comparative Examples 13-18 were tested for weather resistance and color fastness. According to GB / T 16422.2-2014, a xenon arc lamp aging oven was used with an irradiation intensity of 0.51 W / (m 2 ·nm) / 340 nm, a cycle mode of 102 min light (no water spraying) + 18 min light (water spraying), a blackboard temperature of 65±3℃, a relative humidity of 50±5%, and an aging time of 1000h; the change in tensile strength before and after testing was determined according to GB / T 1040-2018; the color difference values before and after aging were measured using a color difference meter according to GB / T 7921-2008; the test results are shown in Table 5; the changes in tensile strength of the colored striped plates prepared in Examples 1-3 and Comparative Examples 13-16 before and after aging are shown in Table 6. Figure 1 Table 5

[0085] Table 5 Test results of examples and comparative examples

[0086]

[0087] From Table 5, Figure 1 It can be seen from the results that, in the comparative examples, by adjusting the components and changing the process, the weather resistance and color fastness of the color striped plate prepared are obviously different from those of the examples; in Comparative Example 13, no distributor is used, resulting in a macro, thick, and fuzzy layered structure of the striped layer and the base layer. When subjected to thermal stress or ultraviolet aging, due to the difference in thermal expansion coefficient and aging rate between different materials, stress concentration is easily generated at the interface, resulting in delamination and cracking, thereby significantly reducing the tensile strength of the material. In addition, uneven stripes will also cause visual mottling and more obvious local discoloration, increasing the overall color difference. In Comparative Example 14, the inorganic pigment has excellent light resistance, heat resistance, and chemical stability. Although the organic pigment has bright colors, the conjugated double bonds and other color groups in its molecular structure are easily destroyed under ultraviolet light and thermal oxygen environment, leading to chemical degradation and discoloration, resulting in a significant increase in color difference. In Comparative Example 15, without stepwise mixing, the nano titanium dioxide and the pigment will agglomerate, forming agglomerates that not only cause uneven color and color spots, but also become stress concentration points inside the material. Under external force or during the aging process, microcracks are easily initiated and expanded, reducing the overall performance. In Comparative Examples 16-17, the role of the ultraviolet absorber is to absorb high-energy ultraviolet light and convert it into harmless heat energy. The light stabilizer interrupts the chain reaction by capturing free radicals generated during polymer degradation. Without these two key additives, ultraviolet light will directly act on the polymer chains, causing photooxidation and photodegradation reactions, leading to molecular chain breakage, material brittleness, yellowing, and discoloration. Through synergistic action, the overall ultraviolet absorption spectral range and efficiency are improved. In Comparative Example 18, the use of ordinary PC will result in insufficient stability of the striped layer itself. During long-term aging, the striped layer will degrade and discolor faster than the weather-resistant PC. This not only affects the overall color fastness, but also degrades the interface bonding with the surrounding material, which may cause interface separation and reduce the overall mechanical properties of the material.

[0088] In summary, the present application covers different ultraviolet bands by UV-326 and UV-1600, absorbs ultraviolet light comprehensively; HALS captures free radicals generated by photo-oxidation, inhibits chain reaction; the composite matrix of polymethyl methacrylate and polycarbonate provides high transparency and weather resistance, and protects the stripe layer pigment and the matrix layer together; in addition, the composite inorganic pigment is uniformly mixed by a ball mill, providing excellent ultraviolet shielding and color stability; the modified nano titanium dioxide is treated by KH-570 surface treatment, enhancing the compatibility with weather-resistant PC, reducing agglomeration, and improving dispersion uniformity; and then through the step-by-step mixing process and the multi-channel distribution process, the stability and aesthetics of the colored stripe plate under long-term aging are ensured by the synergistic effect of components and processes.

[0089] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for manufacturing a high-transmittance, weather-resistant, and impact-resistant colored striped plate, characterized in that, The manufacturing process includes the following steps: The base layer is melt-extruded to obtain a base layer melt; the weather-resistant layer is melt-extruded to obtain a weather-resistant layer melt; the stripe layer is melt-extruded to obtain a stripe layer melt; the weather-resistant layer melt, the base layer melt, and the stripe layer melt are processed by a multi-channel distributor to form a three-layer structure, and after distribution, a composite melt is obtained; the composite melt enters the die head and undergoes a post-processing process to obtain the colored stripe plate; The matrix layer is obtained by melt copolymerization of polycarbonate and polybutylene terephthalate, and by melt extrusion of MBS and additives. The weather-resistant layer is obtained by melt extrusion of polymethyl methacrylate and polycarbonate; The striped layer is obtained by melt extrusion of weather-resistant PC, modified nano-titanium dioxide, and composite inorganic pigments.

2. The method for manufacturing a high-transmittance, weather-resistant, and impact-resistant colored striped plate according to claim 1, characterized in that, The multi-channel distributor processing includes the following steps: In a top-to-bottom order, the weather-resistant layer, the base layer, and the weather-resistant layer are fed into the multi-channel distributor to form a three-layer structure. At the same time, the striped layer melt is divided into multiple fluids by the distribution channels in the distributor, which are injected into the weather-resistant layer melt and the base layer melt respectively to obtain the composite melt.

3. The method for manufacturing a high-transmittance, weather-resistant, and impact-resistant colored striped plate according to claim 1, characterized in that, The post-processing procedure includes the following steps: The composite melt enters the die head and is heat-treated to obtain a multi-layer melt. The multi-layer melt is then fed into a three-roll calender, where the thickness of the sheet is precisely controlled by the gap between the rollers, and preliminary shaping and cooling are performed to obtain the sheet precursor. The sheet precursor is then passed through an online annealing furnace for heat treatment, followed by cooling treatment and air cooling to room temperature to obtain the colored striped sheet.

4. The method for manufacturing a high-transmittance, weather-resistant, and impact-resistant colored striped plate according to claim 1, characterized in that, The fabrication of the substrate layer includes the following steps: The polycarbonate and the polybutylene terephthalate adipate were placed in a vacuum drying oven and dried to obtain a dried raw material. The dried raw material was added to a twin-screw extruder, and tetrabutyl titanate was added. The mixture was melt copolymerized to obtain a copolymer. MBS, antioxidant 1010, and zinc stearate were added to the copolymer. The mixture was melt extruded to obtain the matrix layer.

5. The method for manufacturing a high-transmittance, weather-resistant, and impact-resistant colored striped plate according to claim 1, characterized in that, The manufacturing of the weather-resistant layer includes the following steps: The polymethyl methacrylate and the polycarbonate were placed in a vacuum drying oven and dried to obtain a dried material. The dried material was then added to a twin-screw extruder, along with maleic anhydride-grafted polycarbonate, UV absorber-326, UV absorber-1600, HALS, and zinc stearate. The mixture was then melt-extruded to obtain a weather-resistant layer.

6. The method for manufacturing a high-transmittance, weather-resistant, and impact-resistant colored striped plate according to claim 1, characterized in that, The manufacturing of the striped layer includes the following steps: The weather-resistant PC is placed in a vacuum drying oven and dried to obtain a dried system; the dried system is added to a high-speed mixer, and the modified nano-titanium dioxide is added and stirred to obtain a mixture; the composite inorganic pigment is added to the mixture and stirred to obtain a mixed system; a polyether dispersant, zinc stearate and antioxidant 1010 are added to the mixed system, and the mixture is added to a twin-screw extruder and melt-extruded to obtain a striped layer; wherein the composite inorganic pigment is obtained by mixing titanium dioxide and iron oxide red in a certain mass ratio.

7. The method for manufacturing a high-transmittance, weather-resistant, and impact-resistant colored striped plate according to claim 6, characterized in that, The preparation of the modified nano-titanium dioxide includes the following steps: Nano-titanium dioxide was dispersed in a 95% ethanol aqueous solution, the pH of the system was adjusted with acetic acid, and the mixture was stirred in a magnetic stirrer to obtain an inorganic dispersion; KH-570 was added to the inorganic dispersion, and a modification reaction was carried out to obtain a modified system; the modified system was dried and ground to obtain the modified nano-titanium dioxide.

8. A high-transmittance, weather-resistant, and impact-resistant colored striped plate, characterized in that: The colored striped plate consists of a weather-resistant layer, a substrate layer, and a weather-resistant layer from top to bottom, wherein the stripe layer is injected between the weather-resistant layer and the substrate layer to form a uniform and parallel stripe pattern; the high-transmittance, weather-resistant, and impact-resistant colored striped plate is prepared by the manufacturing method described in any one of claims 1-7.

Images