A transparent high-hardness polycarbonate material and a preparation method and application thereof

Abstract

The present application relates to a kind of transparent high-hardness polycarbonate material, including polycarbonate structure layer and functional coating;Wherein, the functional coating, by weight parts, it is composed of the following components: organosilicon compound, 20-50 parts;Nano silicon dioxide, 0-10 parts;Macromolecular base acrylate, 5-30 parts;Diluent, 30-60 parts;Photoinitiator, 0.1-10 parts;The polycarbonate structure layer, by weight parts, it is composed of the following components: polycarbonate, 80-100 parts;Styrene-based polymer, 0-20 parts;Flame retardant, 0-10 parts;Antioxidant, 0.001-2 parts.The present application also provides the preparation method of the above-mentioned transparent high-hardness polycarbonate material, and the transparent high-hardness polycarbonate material application in communication electronics, household appliances, automobile, industry and other fields, good technical effect can be achieved.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, and particularly relates to a transparent high-hardness polycarbonate material, its preparation method and application. Background Technology

[0002] Polycarbonate (PC) possesses excellent impact resistance, thermal properties, and processing performance, while also boasting high light transmittance comparable to glass. It is widely used in electronic appliances, home appliances, displays, communication equipment, optical lenses, mobile phone casings, goggles, and automotive headlight covers. Currently, PC is the preferred substrate, and injection-molded plastic glass-like mobile phone back covers have become a hot research and development area for major mobile phone back cover manufacturers. Glass-like back covers require a plastic surface hardness of at least 2H. However, PC has poor surface hardness, is easily worn, yellows easily, and has poor flowability; its hardness is only 2B to 3B, far below the application requirements for glass-like back covers. Common methods include coating the PC surface or adding hardening polymers, scratch-resistant agents, and other modifying additives to improve scratch resistance and surface hardness. However, some modifiers can unavoidably impart color to the PC material, leading to decreased transparency or opacity, thus limiting its applications. Furthermore, scratch resistance modification of PC often results in a decrease in its mechanical properties, especially impact toughness.

[0003] Chinese patent CN102964793A uses a combination of polystyrene (PS), styrene-maleic anhydride (SMA) resin, a transparent toughening agent, and PC to prepare a material with 87% transparency and an impact strength of 7.7 kJ / m. 2 The highest surface hardness of PC material is 2H. Chinese patent CN105504751A discloses a flame-retardant PC / PMMA (polymethyl methacrylate) material with 87% transparency. Chinese patents CN106009580A and CN109593339A report that by adding small amounts of high-hardness wear-resistant modifiers, such as nano-diamond powder, jade powder, microcrystalline stone, and silica, a wear-resistant PC with 85% transparency and 3H hardness was obtained, but the melt flow rate was <15g / 10min, which is not conducive to manufacturing thin-walled shell materials. Chinese patent CN108976747A uses polyester copolymer, styrene copolymer, and PC to prepare a PC material with 90-93% transparency, pencil hardness 3B to HB, and impact strength 30-60kJ / m. 2 .

[0004] However, the transparency, hardness, and toughness of existing PC materials still cannot meet the needs of practical applications. Therefore, the research and development of PC materials with high hardness, high toughness, and good transparency is of great significance. Summary of the Invention

[0005] To address the problem of existing PC materials being unable to simultaneously achieve and balance hardness, scratch resistance, toughness, and transparency, this invention provides a transparent high-hardness polycarbonate material. This transparent high-hardness polycarbonate material possesses high transparency and toughness, while its hardness and scratch resistance are significantly improved, making it suitable for applications in communication electronics, home appliances, automobiles, and industrial fields.

[0006] One objective of this invention is to provide a transparent, high-hardness polycarbonate material, comprising a polycarbonate structural layer and a functional coating, wherein the functional coating comprises an organosilicon compound, a macromolecular-weight acrylate, a diluent, and a photoinitiator; the functional coating optionally comprises nano-silica.

[0007] In the above-mentioned transparent high-hardness polycarbonate material, the thickness of the polycarbonate structural layer is 0.1~5mm, preferably 0.5~3mm; the thickness of the functional coating is 0.05~500µm, preferably 0.1~300µm.

[0008] Specifically, in the above-mentioned transparent high-hardness polycarbonate material:

[0009] The organosilicon compound is selected from at least one of vinyl silane compounds, vinyl silicone resins, terminal vinyl polysiloxanes, and terminal allyl polysiloxanes, preferably from at least one of terminal vinyl polysiloxanes, terminal allyl polysiloxanes, terminal vinyl polysiloxanes, and / or combinations of terminal allyl polysiloxanes and vinyl silane compounds; wherein the vinyl silane compound is selected from at least one of dimethylethoxyvinylsilane, trimethylvinylsilane, methyldiethoxyvinylsilane, triethoxyvinylsilane, dimethylethoxyallylsilane, trimethylallylsilane, methyldiethoxyallylsilane, and triethoxyallylsilane; and the vinyl silicone resin is selected from methyl vinyl silicone resin, ethoxyvinyl silicone resin, and methylallyl... The product comprises at least one of vinyl silicone resin and ethoxyallyl silicone resin, wherein the viscosity of the vinyl silicone resin is 5000~20000 mPa•s, preferably 7500~17000 mPa•s; the terminal vinyl polysiloxane is selected from at least one of terminal vinyl polydimethylsiloxane and terminal vinyl polymethylvinylsiloxane, wherein the viscosity of the terminal vinyl polysiloxane is 5000~20000 mPa•s, preferably 7000~18000 mPa•s; the terminal allyl polysiloxane is selected from at least one of terminal allyl polydimethylsiloxane and terminal allyl polymethylvinylsiloxane, wherein the viscosity of the terminal allyl polysiloxane is 5000~20000 mPa•s, preferably 7000~18000 mPa•s;

[0010] The macromolecular-weight acrylate is selected from at least one of polyester acrylate, polyurethane acrylate, polyethylene oxide acrylate, polyether acrylate, polyester methacrylate, polyurethane methacrylate, polyethylene oxide methacrylate, and polyether methacrylate; wherein, when the organosilicon compound is a combination of terminal vinyl polysiloxane and / or terminal allyl polysiloxane and vinyl silane compounds, the macromolecular-weight acrylate is preferably polyethylene oxide acrylate, and preferably, the mass ratio of terminal vinyl polysiloxane and / or terminal allyl polysiloxane, vinyl silane compound, and polyethylene oxide acrylate is (35~85):(0~65):(5~40), preferably (50~70):(5~30):(15~25);

[0011] The diluent is selected from acrylate diluents, preferably from at least one of the following: isobornyl acrylate, isobornyl methacrylate, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, laurate, methyl laurate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triacryloyloxymethylenebutane, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methoxy polyethylene glycol monoacrylate, and methoxy polyethylene glycol monomethacrylate.

[0012] The photoinitiator is selected from at least one of methyl benzoylformate, benzophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2,2-dimethoxy-2-phenylacetophenone, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 4,4'-bis(9H-carbazole-9-yl)-2,2'-dimethylbiphenyl.

[0013] The particle size of the nano-silica is 5~500nm, preferably 10~200nm, and more preferably 20~100nm.

[0014] In the aforementioned polycarbonate material, the functional coating, by weight, comprises 20-50 parts of an organosilicon compound, 0-10 parts of nano-silica, 5-30 parts of macromolecular-weight acrylate, 30-60 parts of diluent, and 0.1-10 parts of photoinitiator; preferably, the functional coating comprises 25-45 parts of an organosilicon compound, 0.5-7.5 parts of nano-silica, 10-25 parts of macromolecular-weight acrylate, 35-50 parts of diluent, and 0.5-7.5 parts of photoinitiator; more preferably, the functional coating comprises 25-45 parts of an organosilicon compound, 1.5-5.5 parts of nano-silica, 10-25 parts of macromolecular-weight acrylate, 35-50 parts of diluent, and 0.5-7.5 parts of photoinitiator.

[0015] By weight, the polycarbonate structural layer comprises 80-100 parts polycarbonate, 0-20 parts styrene-based polymer, 0-10 parts flame retardant, and 0.001-2 parts antioxidant.

[0016] In the above-mentioned polycarbonate structural layer, the polycarbonate is selected from at least one of aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate; the number average molecular weight of the polycarbonate is 10,000 to 80,000 g / mol, preferably 20,000 to 60,000 g / mol; the melt flow rate of the polycarbonate at 300°C and 1200 g is 2 to 40 g / 10 min, preferably 5 to 30 g / 10 min;

[0017] The styrene-based polymer is selected from at least one of polystyrene, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-alkyl acrylate copolymer, and styrene-alkyl methacrylate copolymer; the number average molecular weight of the styrene-based polymer is 100,000 to 400,000 g / mol, preferably 200,000 to 300,000 g / mol; the melt flow rate of the styrene-based polymer at 220°C and 2160 g is 5 to 60 g / 10 min, preferably 15 to 45 g / 10 min;

[0018] The flame retardant is selected from at least one of 2,4,6-tribromophenoxy-terminated tetrabromobisphenol A carbonate oligomer, phenoxy-terminated tetrabromobisphenol A carbonate oligomer, potassium biphenyl sulfone-3-sulfonate, and potassium perfluorobutyl sulfonate.

[0019] The antioxidant is selected from at least one of hindered phenolic antioxidants and phosphite antioxidants. The hindered phenolic antioxidant is selected from at least one of the following: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, 2,6-di-tert-butyl-4-methylphenol, or antioxidants with market brands 1010, 1076, 1024, 1098, BHT, etc.; the phosphite antioxidant is selected from at least one of the following: tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenol) diphosphite, tris(nonylphenyl) phosphite, or antioxidants with market brands 168, 626, TNPP, etc.

[0020] The second objective of this invention is to provide a method for preparing the above-mentioned transparent high-hardness polycarbonate material, comprising coating a component including the aforementioned functional coating onto the surface of a polycarbonate structural layer to obtain the transparent high-hardness polycarbonate material. Preferably, the preparation method specifically includes the following steps:

[0021] Step a: Mix the components including polycarbonate, optional styrene-based polymer, optional flame retardant, and optional antioxidant evenly, and obtain the polycarbonate modified material by melt extrusion.

[0022] Step b: The polycarbonate modified material obtained in step a is subjected to injection molding, compression molding, extrusion molding, blow molding or casting to obtain a polycarbonate structural layer;

[0023] Step c: Mix the components, including organosilicon compounds, optional nano-silica, macromolecular acrylate, diluent, and photoinitiator, until homogeneous to obtain the coating slurry;

[0024] Step d: Apply the coating slurry obtained in step c onto the polycarbonate structural layer obtained in step b, and after curing, the transparent high-hardness polycarbonate material is obtained.

[0025] In the above preparation method:

[0026] The melt extrusion temperature in step a is 220~350℃, preferably 250~310℃;

[0027] The temperature for injection molding, compression molding, extrusion molding, blow molding, or casting in step b is 220~350℃, preferably 250~310℃;

[0028] The stirring and mixing in step c is performed by ultrasonic dispersion mixing, and the ultrasonic time is 1~30min;

[0029] In step d, the coating method is spraying, spraying or brushing, etc., to uniformly coat the coating slurry onto the surface of the polycarbonate structural layer.

[0030] In step d, curing is performed using ultraviolet (UV) radiation. The wavelength of the UV light is 180–425 nm, preferably 200–400 nm; the intensity of the UV light is 0.5–10 mW / cm². 2 The preferred value is 0.8~8mW / cm 2 The duration of ultraviolet radiation is 0.2 to 30 minutes, preferably 0.5 to 15 minutes.

[0031] In the above preparation method, the coating and curing described in step d are optionally repeated at least once. Preferably, the functional coating can be obtained by spraying, coating or brushing the coating slurry twice or more and then curing it with light.

[0032] The third objective of this invention is to provide the above-mentioned transparent high-hardness polycarbonate material or the transparent high-hardness polycarbonate material obtained by the above preparation method for application in the fields of communication electronics, home appliances, and automobiles.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] This invention provides a functional coating to the surface of a polycarbonate structural layer, which is uniformly coated with a mixture of silicone resin, nano-silica, macromolecular-weight acrylate, and a functional diluent, and then cured by light. This coating imparts excellent hardness and abrasion resistance to the material, along with superior transparency and low haze. The functional coating exhibits strong adhesion, good water resistance, and high impact toughness, demonstrating properties superior to structural materials prepared by conventional products or methods. Furthermore, it outperforms functional coatings without nano-silica components, achieving significant technical advantages. Moreover, the preparation method provided by this invention is simple, easy to perform, and suitable for large-scale production applications. Attached Figure Description

[0035] Figure 1 This is a photograph of the transparent, high-hardness polycarbonate material prepared in Example 1 of the present invention.

[0036] Figure 2 A photograph of the polycarbonate material prepared for Comparative Example 2. Detailed Implementation

[0037] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0038] The testing instruments and conditions used in this embodiment are as follows:

[0039] Pencil hardness test: The coating hardness was determined using the Mitsubishi pencil method according to GB / T 6739-2006 standard.

[0040] Adhesion test: The adhesion of the coating is determined by cross-cut test according to GB / T 9286-1998 standard.

[0041] Transparency / Haze Test: The transparency and haze of the material are determined according to ASTM D1003 standard.

[0042] Boiling test: Temperature 80℃, boiling time 30min, test the appearance changes of the material.

[0043] Drop hammer test: According to GB / T 4893.9-2013 standard, the drop hammer is 500g and the height is 50cm.

[0044] The raw materials and their sources involved in the examples and comparative examples are as follows:

[0045] Bisphenol A polycarbonate: purchased from Covestro

[0046] Polystyrene: Purchased from Chi Mei Corporation

[0047] Potassium perfluorobutane sulfonate: purchased from Hubei Xinrunde Company

[0048] Potassium biphenyl sulfone-3-sulfonate: purchased from Shanghai Kunzhen Materials Co., Ltd.

[0049] Pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]: purchased from TCI Corporation

[0050] β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester: purchased from Hubei Xinrunde Company

[0051] Tris(nonylphenyl) phosphite: purchased from Hubei Qifei Pharmaceutical Company

[0052] Tris(2,4-di-tert-butylphenyl) phosphite: purchased from Sigma-Aldrich (Shanghai) Co., Ltd.

[0053] Methyl vinyl silicone resin: purchased from Wacker Chemie.

[0054] Vinyl-terminated polydimethylsiloxane: purchased from Wuhan Huaxiang Biotechnology Co., Ltd.

[0055] Dimethylethoxyvinylsilane: Purchased from Chenguang Chemical Company

[0056] Nano-silica: Purchased from Shanghai Chaowei Nanotechnology Co., Ltd.

[0057] Polyurethane acrylate: Purchased from Jinan Quanxing New Materials Co., Ltd.

[0058] Polyethylene oxide acrylate: Purchased from Guangzhou Qianxing Import & Export Co., Ltd.

[0059] β-Hydroxyethyl Acrylate: Purchased from Shandong Chuxin Chemical Co., Ltd.

[0060] Isoborneol acrylate: purchased from Shandong Chuxin Chemical Co., Ltd.

[0061] Laurate acrylate: purchased from Shanghai Fushun Trading Company

[0062] Pentaerythritol triacrylate: purchased from Shanghai Hans Chemical Co., Ltd.

[0063] 2-Hydroxy-2-methyl-1-phenylpropanone: Purchased from Hubei Xinrunde Company

[0064] Benzophenone: Purchased from Hubei Xinrunde Company

[0065] Methyl benzoylformate: purchased from Sigma-Aldrich (Shanghai) Co., Ltd.

[0066] 2,4,6-Trimethylbenzoylphenylphosphonic acid ethyl ester: purchased from Jiangsu Juming Chemical Co., Ltd.

[0067]

Example 1

[0068] (1) Preparation of polycarbonate structural layers:

[0069] 4.5 kg of bisphenol A polycarbonate particles (number average molecular weight 20,000 g / mol, melt flow rate 300℃, 25 g / 10 min at 1200 g) were dried in a forced-air oven at 120℃ for 2 h, and 0.5 kg of polystyrene particles (number average molecular weight 210,000 g / mol, melt flow rate 220℃, 23.5 g / 10 min at 2160 g) were dried in a forced-air oven at 100℃ for 2 h. Then, it was mixed with 100 g of potassium perfluorobutane sulfonate, 15 g of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester and 5 g of tris(2,4-di-tert-butylphenyl) phosphite in a high-speed mixer for 3 min at room temperature. The mixture was then fed into the feed port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-to-diameter ratio 40) and subjected to melt meshing, extrusion, cooling and granulation at 275℃, 250 rpm and 8 kg / h to obtain polycarbonate modified material A.

[0070] The prepared polycarbonate modified material A was melt-injected into polycarbonate structural layer a using a BOY injection molding machine at 270℃ and 85 MPa, with a disc diameter of 100 mm. Thickness 3.0 mm.

[0071] (2) Preparation of functional coatings:

[0072] 40 g of methyl vinyl silicone resin (viscosity 18000 mPa•s at 25℃), 2 g of nano silica (particle size 30 nm), 30 g of polyurethane acrylate, 50 g of β-hydroxyethyl acrylate, 5 g of pentaerythritol triacrylate, and 0.5 g of 2-hydroxy-2-methyl-1-phenylpropanone were stirred at 400 rpm for 30 min and then sonicated for 5 min to obtain coating slurry I.

[0073] The prepared coating slurry I was uniformly coated onto the surface of the aforementioned prepared polycarbonate structural layer a using a spraying method, and then subjected to ultraviolet light (wavelength 365 nm, light intensity 0.95 mW / cm²). 2 After being irradiated for 5 minutes and then photocured, a functional coating i (120 µm thick) is formed on the surface of the polycarbonate structural layer a, resulting in a transparent, high-hardness polycarbonate material a / i.

[0074] The performance test results of transparent high-hardness polycarbonate material a / i are shown in Table 1.

[0075]

Example 2

[0076] (1) The preparation of the polycarbonate structural layer is the same as in Example 1.

[0077] (2) Preparation of functional coatings:

[0078] 35 g of methyl vinyl silicone resin, 15 g of dimethyl ethoxy vinyl silane, 0.85 g of nano silica (particle size 30 nm), 15 g of polyethylene oxide acrylate, 35 g of isoborneol acrylate, 25 g of lauric acid acrylate, and 2.5 g of benzophenone were stirred at 400 rpm for 30 min and then sonicated for 5 min to obtain coating slurry II.

[0079] The prepared coating slurry II was uniformly coated onto the surface of the aforementioned prepared polycarbonate structural layer a using a spraying method, and then subjected to ultraviolet light (wavelength 365 nm, light intensity 0.95 mW / cm²). 2 After being irradiated for 5 minutes and then photocured, a functional coating ii (200 µm thick) is formed on the surface of the polycarbonate structural layer a, resulting in a transparent, high-hardness polycarbonate material a / ii.

[0080] The performance test results of transparent high-hardness polycarbonate materials a / ii are shown in Table 1.

[0081]

Example 3

[0082] (1) The preparation of the polycarbonate structural layer is the same as in Example 1.

[0083] (2) Preparation of functional coatings:

[0084] 35 g of methyl vinyl silicone resin, 15 g of dimethyl ethoxy vinyl silane, 0.85 g of nano silica (particle size 30 nm), 15 g of polyethylene oxide acrylate, 35 g of isoborneol acrylate, 25 g of lauric acid acrylate, and 5.5 g of benzophenone were stirred at 400 rpm for 30 min and then sonicated for 5 min to obtain coating slurry III.

[0085] The prepared coating slurry III was uniformly coated onto the surface of the aforementioned polycarbonate structural layer a using a spraying method, and then subjected to ultraviolet light (wavelength 365 nm, light intensity 0.95 mW / cm²). 2 After being irradiated for 5 minutes and then photocured, a functional coating iii (185 µm thick) is formed on the surface of the polycarbonate structural layer a, resulting in a transparent, high-hardness polycarbonate material a / iii.

[0086] The performance test results of transparent high-hardness polycarbonate materials a / iii are shown in Table 1.

[0087]

Example 4

[0088] The preparation of the polycarbonate structural layer and functional coating is the same as in Examples 1 and 3.

[0089] Only under ultraviolet light (wavelength 365 nm, light intensity 1.35 mW / cm²) 2 After being irradiated for 5 minutes and then photocured, a functional coating iv (thickness 210 µm) is formed on the surface of the polycarbonate structural layer a, resulting in a transparent high-hardness polycarbonate material a / iv.

[0090] The performance test results of transparent high-hardness polycarbonate material a / iv are shown in Table 1.

[0091]

Example 5

[0092] The preparation of the polycarbonate structural layer and functional coating is the same as in Examples 1 and 3.

[0093] Only under ultraviolet light (wavelength 365 nm, light intensity 0.95 mW / cm²) 2 After being irradiated for 8.5 min and then photocured, a functional coating v (200 µm thick) is formed on the surface of the polycarbonate structural layer a, resulting in a transparent, high-hardness polycarbonate material a / v.

[0094] The a / v performance test results of the transparent high-hardness polycarbonate material are shown in Table 1.

[0095]

Example 6

[0096] (1) Preparation of polycarbonate structural layers:

[0097] 5 kg of bisphenol A polycarbonate particles (number average molecular weight 20000 g / mol, melt flow rate 300℃, 25 g / 10 min at 1200 g) were dried in a 120℃ forced-air oven for 2 h. They were then mixed with 200 g of potassium biphenyl sulfone-3-sulfonate, 25 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 2 g of tri(nonylphenyl) phosphite in a high-speed mixer at room temperature for 3 min. The mixture was then fed into the feed port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-to-diameter ratio 40) and subjected to melt meshing, extrusion, cooling, and granulation at 280℃, 250 rpm, and 8 kg / h to obtain polycarbonate modified material B.

[0098] The prepared polycarbonate modified material B was melt-injected using a BOY injection molding machine at 280℃ and 85 MPa to obtain the polycarbonate structural layer b, which is long. Width Thickness = 120mm 75mm 1.6mm.

[0099] (2) Preparation of functional coatings:

[0100] 50g of methyl vinyl silicone resin, 25g of polyurethane acrylate, 55g of isobornyl acrylate, 2g of pentaerythritol triacrylate, 0.5g of methyl benzoylformate, and 0.5g of ethyl 2,4,6-trimethylbenzoylphenylphosphonate were stirred at 400 rpm for 30 min and then sonicated for 5 min to obtain coating slurry VI.

[0101] The prepared coating slurry VI was uniformly coated onto the surface of the aforementioned prepared polycarbonate structural layer b using a spraying method, and then subjected to ultraviolet light (wavelength 254nm, light intensity 1.50mW / cm²). 2 After being irradiated for 3 minutes and then photocured, a functional coating vi (150µm thick) is formed on the surface of the polycarbonate structural layer b, resulting in a transparent, high-hardness polycarbonate material b / vi.

[0102] The performance test results of transparent high-hardness polycarbonate material b / vi are shown in Table 1.

[0103]

Example 7

[0104] (1) The preparation of the polycarbonate structural layer is the same as in Example 6.

[0105] (2) Preparation of functional coatings:

[0106] 50g of methyl vinyl silicone resin, 6g of nano silica (particle size 20nm), 25g of polyurethane acrylate, 55g of isobornyl acrylate, 2g of pentaerythritol triacrylate, 0.5g of methyl benzoylformate, and 0.5g of ethyl 2,4,6-trimethylbenzoylphenylphosphonate were stirred at 400 rpm for 30 min, followed by sonication for 5 min to obtain coating slurry VII.

[0107] The prepared coating slurry VII was uniformly coated onto the surface of the aforementioned prepared polycarbonate structural layer b using a spraying method, and then subjected to ultraviolet light (wavelength 254 nm, light intensity 1.50 mW / cm²). 2 After being irradiated for 3 minutes and then photocured, a functional coating vii (135 µm thick) is formed on the surface of the polycarbonate structural layer b, resulting in a transparent, high-hardness polycarbonate material b / vii.

[0108] The performance test results of transparent high-hardness polycarbonate material b / vii are shown in Table 1.

[0109]

Example 8

[0110] The preparation of the polycarbonate structural layer and functional coating is the same as in Example 7.

[0111] Only under ultraviolet light (wavelength 254 nm, light intensity 1.50 mW / cm²) 2After being irradiated for 1.5 min and then photocured, a functional coating viii (100 µm thick) is formed on the surface of the polycarbonate structural layer b, resulting in a transparent, high-hardness polycarbonate material b / viii.

[0112] The performance test results of transparent high-hardness polycarbonate material b / viii are shown in Table 1.

[0113]

Example 9

[0114] The polycarbonate structural layer is the same as in Example 1, and the preparation of the functional coating is the same as in Examples 1 and 6.

[0115] After obtaining the transparent high-hardness polycarbonate material a / i (coating thickness 120 µm) in Example 1, the coating slurry vi is uniformly sprayed onto the surface of a / i. Under the light curing conditions of Example 6, a functional coating vi (thickness 150 µm) is formed on the surface of a / i, resulting in the transparent high-hardness polycarbonate material a / i+vi.

[0116] The performance test results of transparent high-hardness polycarbonate material a / i+vi are shown in Table 1.

[0117]

Example 10

[0118] The preparation of the polycarbonate structural layer and functional coating is the same as in Example 6.

[0119] The only difference was that the methyl vinyl silicone resin was replaced with terminal vinyl polydimethylsiloxane, and the photocuring conditions were the same as in Example 6, resulting in a transparent high-hardness polycarbonate material b / u1. The performance test results of the transparent high-hardness polycarbonate material b / u1 are shown in Table 1.

[0120]

Example 11

[0121] The preparation of the polycarbonate structural layer and functional coating is the same as in Example 2.

[0122] The only difference was that the methyl vinyl silicone resin was replaced with allyl-terminated polydimethylsiloxane, and the photocuring conditions were the same as in Example 2, resulting in a transparent, high-hardness polycarbonate material a / u2. The allyl-terminated polydimethylsiloxane was prepared using the method described in the literature "Research on Allyl Silicon-Terminated Polydimethylsiloxanes". The performance test results of the transparent, high-hardness polycarbonate material a / u2 are shown in Table 1.

[0123]

Example 12

[0124] The preparation of the polycarbonate structural layer and functional coating is the same as in Example 11.

[0125] The amounts of terminal allyl polydimethylsiloxane, dimethylethoxyvinylsilane, and polyethylene oxide acrylate were adjusted to 45g, 5g, and 15g, respectively, and the photocuring conditions were the same as in Example 2, resulting in a transparent high-hardness polycarbonate material a / u3. The performance test results of the transparent high-hardness polycarbonate material a / u3 are shown in Table 1.

[0126]

Example 13

[0127] The preparation of the polycarbonate structural layer and functional coating is the same as in Example 11.

[0128] The amounts of terminal allyl polydimethylsiloxane, dimethylethoxyvinylsilane, and polyethylene oxide acrylate were adjusted to 20g, 36g, and 9g, respectively, and the photocuring conditions were the same as in Example 2, resulting in a transparent high-hardness polycarbonate material a / u4. The performance test results of the transparent high-hardness polycarbonate material a / u4 are shown in Table 1.

[0129] Comparative Example 1

[0130] The preparation of polycarbonate material a is the same as in Example 1, except for the preparation of the non-functional coating.

[0131] The performance test results of polycarbonate material a are shown in Table 1.

[0132] Comparative Example 2

[0133] The polycarbonate structural layer is the same as in Example 6.

[0134] The functional coating was prepared using the method described in the literature "Preparation of Phenylacetyl Acrylate and Study on UV Curing Properties". EA (epoxy acrylate), IBOA (isobornyl acrylate), TPGDA (tripropylene glycol diacrylate), and TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide) were mixed and dissolved in a mass ratio of 30:40:30:4.

[0135] The b / vv performance test results of the prepared transparent high-hardness polycarbonate material are shown in Table 1.

[0136] Table 1. Performance test results of polycarbonate materials obtained in the examples and comparative examples

[0137]

[0138] Compared with Comparative Examples 1 and 2, the transparent high-hardness polycarbonate material designed and prepared by the present invention has significantly improved hardness and wear resistance, strong coating adhesion, excellent transparency, and better resistance to water boiling stress cracking and toughness, demonstrating the advantages of the present invention.

[0139] Meanwhile, comparing Example 6 and Example 7, it can be seen that after the introduction of nano-silica, it forms an organic / inorganic composite silicon compound with methyl vinyl silicone resin, which effectively improves the transparency of the material and significantly enhances the hardness of the coating, showing superior comprehensive performance compared to the single organosilicon component.

[0140] Furthermore, comparing Examples 10 with Examples 6, 11, and 12 with Example 2, the coating performance of terminal alkenyl polysiloxane is superior to that of methyl vinyl silicone resin. This is attributed to the fact that the terminal alkenyl structure of the former is more readily chemically reacting with macromolecular acrylates under the action of photoinitiators. Moreover, due to the unique polyoxyethylene molecular chain of polyethylene oxide acrylate, compared with the molecular chain structures of polyesters and polyurethanes, it has excellent flexibility and wettability. At the same time, the large number of oxygen groups in the polyoxyethylene structure makes it easier to form hydrogen bonds with components such as polysiloxanes and vinyl silanes, which increases the compatibility of the system and improves the chemical reaction efficiency between acrylate groups and terminal alkenyl structures under photoinitiation. Thus, the synergistic effect among terminal alkenyl polysiloxane, vinyl silane, and polyethylene oxide acrylate shows a coating effect superior to that in the prior art.

Claims

1. A transparent, high-hardness polycarbonate material, comprising a polycarbonate structural layer and a functional coating, wherein, The functional coating comprises an organosilicon compound, a macromolecular-weight acrylate, a diluent, and a photoinitiator; optionally, the functional coating comprises nano-silica; the organosilicon compound is selected from at least one of vinyl silane compounds, vinyl silicone resins, terminal vinyl polysiloxanes, and terminal allyl polysiloxanes; the macromolecular-weight acrylate is selected from at least one of polyester acrylates, polyurethane acrylates, polyethylene oxide acrylates, polyether acrylates, polyester methacrylates, polyurethane methacrylates, polyethylene oxide methacrylates, and polyether methacrylates; and the diluent is selected from acrylate diluents. By weight, the functional coating comprises 20-50 parts of organosilicon compound, 0-10 parts of nano-silica, 5-30 parts of macromolecular acrylate, 30-60 parts of diluent, and 0.1-10 parts of photoinitiator; by weight, the polycarbonate structural layer comprises 80-100 parts of polycarbonate, 0-20 parts of styrene polymer, 0-10 parts of flame retardant, and 0.001-2 parts of antioxidant.

2. The polycarbonate material according to claim 1, characterized in that, The thickness of the polycarbonate structural layer is 0.1~5mm; and / or, The thickness of the functional coating is 0.05~500µm.

3. The polycarbonate material according to claim 2, characterized in that, The thickness of the polycarbonate structural layer is 0.5~3mm; and / or, The thickness of the functional coating is 0.1~300µm.

4. The polycarbonate material according to claim 1, characterized in that, The organosilicon compound is selected from at least one of terminal vinyl polysiloxanes, terminal allyl polysiloxanes, terminal vinyl polysiloxanes, and / or combinations of terminal allyl polysiloxanes and vinyl silane compounds; and / or, The diluent is selected from at least one of the following: isobornyl acrylate, isobornyl methacrylate, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, laurate, methyl laurate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triacryloyloxymethylenebutane, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methoxy polyethylene glycol monoacrylate, and methoxy polyethylene glycol monomethacrylate; and / or, The photoinitiator is selected from at least one of methyl benzoylformate, benzophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2,2-dimethoxy-2-phenylacetophenone, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 4,4'-bis(9H-carbazole-9-yl)-2,2'-dimethylbiphenyl; and / or, The particle size of the nano-silica is 5~500nm.

5. The polycarbonate material according to claim 4, characterized in that, The particle size of the nano-silica is 10~200nm.

6. The polycarbonate material according to claim 5, characterized in that, The particle size of the nano-silica is 20~100nm.

7. The polycarbonate material according to claim 4, characterized in that, The vinyl silane compounds are selected from at least one of dimethylethoxyvinylsilane, trimethylvinylsilane, methyldiethoxyvinylsilane, triethoxyvinylsilane, dimethylethoxyallylsilane, trimethylallylsilane, methyldiethoxyallylsilane, and triethoxyallylsilane; and / or, The vinyl silicone resin is selected from at least one of methyl vinyl silicone resin, ethoxy vinyl silicone resin, methyl allyl silicone resin, and ethoxy allyl silicone resin; and / or, The viscosity of the vinyl silicone resin is 5000~20000 mPa•s; and / or, The terminal vinyl polysiloxane is selected from at least one of terminal vinyl polydimethylsiloxane and terminal vinyl polymethylvinylsiloxane; and / or, The viscosity of the terminal vinyl polysiloxane is 5000~20000 mPa•s; and / or, The terminal allyl polysiloxane is selected from at least one of terminal allyl polydimethylsiloxane and terminal allyl polymethylvinylsiloxane; and / or, The viscosity of the terminal allyl polysiloxane is 5000~20000 mPa•s; And / or, When the organosilicon compound is selected from terminal vinyl polysiloxanes and / or combinations of terminal allyl polysiloxanes and vinyl silane compounds, the macromolecular acrylate is selected from polyethylene oxide acrylates.

8. The polycarbonate material according to claim 7, characterized in that, The viscosity of the vinyl silicone resin is 7500~17000 mPa•s; and / or, The viscosity of the end-vinyl polysiloxane is 7000~18000 mPa•s; And / or, The viscosity of the terminal allyl polysiloxane is 7000~18000 mPa•s; And / or, When the organosilicon compound is selected from terminal vinyl polysiloxane and / or a combination of terminal allyl polysiloxane and vinyl silane compounds, the mass ratio of terminal vinyl polysiloxane and / or terminal allyl polysiloxane, vinyl silane compound, and polyethylene oxide acrylate is (35~85):(0~65):(5~40).

9. The polycarbonate material according to claim 8, characterized in that, When the organosilicon compound is selected from terminal vinyl polysiloxane and / or a combination of terminal allyl polysiloxane and vinyl silane compounds, the mass ratio of terminal vinyl polysiloxane and / or terminal allyl polysiloxane, vinyl silane compound, and polyethylene oxide acrylate is (50~70):(5~30):(15~25).

10. The polycarbonate material according to claim 1, characterized in that, By weight, the functional coating comprises 25-45 parts of organosilicon compound, 0.5-7.5 parts of nano-silica, 10-25 parts of macromolecular acrylate, 35-50 parts of diluent, and 0.5-7.5 parts of photoinitiator.

11. The polycarbonate material according to claim 10, characterized in that, By weight, the functional coating comprises 25-45 parts of organosilicon compound, 1.5-5.5 parts of nano-silica, 10-25 parts of macromolecular acrylate, 35-50 parts of diluent, and 0.5-7.5 parts of photoinitiator.

12. The polycarbonate material according to claim 1, characterized in that, The polycarbonate is selected from at least one of aromatic polycarbonates, aliphatic polycarbonates, and aliphatic-aromatic polycarbonates; and / or, The polycarbonate has a number-average molecular weight of 10,000 to 80,000 g / mol; and / or, The polycarbonate described above has a melt flow rate of 2~40 g / 10 min at 300°C and 1200 g; and / or, The styrene-based polymer is selected from at least one of polystyrene, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-alkyl acrylate copolymer, and styrene-alkyl methacrylate copolymer; and / or, The number-average molecular weight of the styrene-based polymer is 100,000 to 400,000 g / mol; and / or, The styrene-based polymer has a melt flow rate of 5-60 g / 10 min at 220°C and 2160 g; and / or, The flame retardant is selected from at least one of 2,4,6-tribromophenoxy-terminated tetrabromobisphenol A carbonate oligomer, phenoxy-terminated tetrabromobisphenol A carbonate oligomer, potassium biphenyl sulfone-3-sulfonate, and potassium perfluorobutane sulfonate; and / or, The antioxidant is selected from at least one of hindered phenolic antioxidants and phosphite antioxidants.

13. The polycarbonate material according to claim 12, characterized in that, The polycarbonate has a number-average molecular weight of 20,000 to 60,000 g / mol; and / or, The polycarbonate described above has a melt flow rate of 5~30 g / 10 min at 300°C and 1200 g; and / or, The number-average molecular weight of the styrene-based polymer is 200,000 to 300,000 g / mol; and / or, The styrene-based polymer has a melt flow rate of 15~45g / 10min at 220℃ and 2160g.

14. A method for preparing the transparent high-hardness polycarbonate material according to any one of claims 1 to 13, comprising coating a component including the functional coating onto the surface of the polycarbonate structural layer to obtain the transparent high-hardness polycarbonate material.

15. The preparation method according to claim 14, characterized in that, The preparation method specifically includes the following steps: Step a: Mix the components including polycarbonate, optional styrene-based polymer, optional flame retardant, and optional antioxidant evenly, and obtain the polycarbonate modified material by melt extrusion. Step b: The polycarbonate modified material obtained in step a is subjected to injection molding, compression molding, extrusion molding, blow molding or casting to obtain a polycarbonate structural layer; Step c: Mix the components, including organosilicon compounds, optional nano-silica, macromolecular acrylate, diluent, and photoinitiator, until homogeneous to obtain the coating slurry; Step d: Apply the coating slurry obtained in step c onto the polycarbonate structural layer obtained in step b, and after curing, the transparent high-hardness polycarbonate material is obtained.

16. The preparation method according to claim 15, characterized in that, The melt extrusion temperature in step a is 220~350℃; and / or, In step b, the temperature for injection molding, compression molding, extrusion molding, blow molding, or casting is 220~350℃; and / or, In step d, curing is performed using ultraviolet radiation.

17. The preparation method according to claim 16, characterized in that, The melt extrusion temperature in step a is 250~310℃; and / or, The temperature for injection molding, compression molding, extrusion molding, blow molding, or casting in step b is 250~310℃.

18. The preparation method according to claim 16, characterized in that, The wavelength of the ultraviolet light is 180~425nm; and / or, The intensity of the ultraviolet light is 0.5~10mW / cm². 2 ; and / or, The duration of ultraviolet radiation is 0.2 to 30 minutes.

19. The preparation method according to claim 18, characterized in that, The wavelength of the ultraviolet light is 200~400nm; and / or, The intensity of the ultraviolet light is 0.8~8 mW / cm². 2 ; and / or, The duration of ultraviolet radiation is 0.5 to 15 minutes.

20. The preparation method according to claim 15, characterized in that, Optionally, the coating and curing process described in step d may be repeated at least once in the preparation method.

21. The transparent high-hardness polycarbonate material according to any one of claims 1 to 13, or the transparent high-hardness polycarbonate material obtained by the preparation method according to any one of claims 14 to 20, characterized in that, It is used in the fields of communication electronics, home appliances, and automobiles.

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