Electron beam cured anti-glare coating, anti-glare coating and preparation method

Abstract

This application discloses an electron beam-cured anti-glare coating, an anti-glare coating layer, and a preparation method. The provided electron beam-cured anti-glare coating, by weight percentage, comprises 30%–40% epoxy acrylate, 25%–35% high-functionality aliphatic polyurethane acrylate, 3%–8% flexible aliphatic polyurethane acrylate, 20%–30% reactive diluent, 4%–8% silica matting agent, 2%–4% adhesion promoter, 0.3%–0.7% leveling agent, 0.8%–1.5% dispersant, and 1%–3% toughness modifier. The provided electron beam-cured anti-glare coating uses a photoinitiator-free electron beam curing system. By combining specific types and proportions of resins, along with functional additives, the resulting coating possesses excellent anti-glare performance, high hardness, strong adhesion, good toughness, and no small molecule residue, making it suitable for electronic device display covers or electronic device housings.

Description

Technical Field

[0001] This application belongs to the field of radiation-cured coating technology, and relates to electron beam-cured anti-glare coatings, anti-glare coatings, and preparation methods. Background Technology

[0002] Anti-glare coatings (AG coatings) are widely used in displays, touch screens, instrument panels and other fields. By forming a micron-level rough structure on the coating surface, specular reflected light is scattered into diffuse reflection, thereby reducing glare interference and improving visual comfort.

[0003] Currently, most mainstream AG coatings utilize ultraviolet (UV) curing technology. However, UV curing systems have some inherent drawbacks: First, photoinitiators must be added, and the small molecules produced after their degradation are prone to residue and migration, potentially causing odor, yellowing, and biosafety issues, making them unsuitable for high-end electronics and medical fields; second, UV light has limited penetration, which may lead to uneven curing for thick coatings or systems containing high levels of matting particles; third, UV curing is susceptible to oxygen inhibition, and surface curing efficiency needs improvement.

[0004] Electron beam curing, as a highly efficient radiation curing technology, boasts advantages such as no need for photoinitiators, strong penetration, fast curing speed, and no color limitations. However, directly applying traditional UV-curable AG coating formulations to EB curing presents several problems: removing the photoinitiator may result in insufficient system reactivity, leading to incomplete curing and performance degradation; the extremely fast EB curing rate may worsen the coating's adhesion to the substrate; simultaneously, ensuring the stable dispersion of matting agents in an EB system without small-molecule photoinitiators and achieving controllable AG effects is also a significant challenge. Therefore, developing a solvent-free AG coating adapted to EB curing processes and possessing excellent optical, mechanical, and adhesion properties is of great importance. Summary of the Invention

[0005] Therefore, it is necessary to provide an electron beam-cured anti-glare coating, an anti-glare coating layer, and a preparation method that have excellent optical properties, mechanical properties, and adhesion.

[0006] In some embodiments, an electron beam-cured anti-glare coating is provided, comprising, by weight percentage: 30%–40% epoxy acrylate, 25%–35% high-functionality aliphatic polyurethane acrylate, 3%–8% flexible aliphatic polyurethane acrylate, 20%–30% reactive diluent, 4%–8% silica matting agent, 2%–4% adhesion promoter, 0.3%–0.7% leveling agent, 0.8%–1.5% dispersant, and 1%–3% toughness modifier;

[0007] The functionality refers to the amount of CH2=C(R) contained in a single molecule. 1The number of )-CO- groups, R 1 The high-functionality aliphatic polyurethane acrylate has a functionality of 6 or greater than or equal to that of hydrogen atoms or methyl groups.

[0008] The glass transition temperature of the flexible aliphatic polyurethane acrylate is less than or equal to -60°C.

[0009] In some embodiments, the provided electron beam-cured anti-glare coating satisfies one or more of the following conditions:

[0010] (1) The functionality of the high-functionality aliphatic polyurethane acrylate is 6 to 9;

[0011] (2) The flexible aliphatic polyurethane acrylate comprises a low-functionality aliphatic polyurethane acrylate with a functionality of 1 to 2, and may be selected as 2-functionality.

[0012] (3) The soft segment of the flexible aliphatic polyurethane acrylate includes one or more of polyether polyol, polyester polyol and polybutadiene, and the number average molecular weight of the soft segment is 1000 Da~4000 Da; the hard segment includes one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the end-capping agent includes hydroxyl-containing acrylate and / or isocyanate-containing acrylate; wherein, the mass fraction of the soft segment in the flexible aliphatic polyurethane acrylate is 60%~85%, the mass fraction of the hard segment in the flexible aliphatic polyurethane acrylate is 10%~30%, and the mass fraction of the end-capping agent in the flexible aliphatic polyurethane acrylate is 5%~15%; optionally, the polyether polyol includes one or more of polypropylene glycol and polytetrahydrofuran diol, and the polyester polyol includes one or more of polybutylene adipate diol and polycaprolactone diol;

[0013] (4) The elongation at break of the flexible aliphatic polyurethane acrylate is 150%~500%.

[0014] In some embodiments, the provided electron beam-cured anti-glare coating satisfies one or more of the following conditions:

[0015] (1) The high-functionality aliphatic polyurethane acrylate includes one or more of hexafunctional aliphatic polyurethane acrylate and nonafunctional aliphatic polyurethane acrylate.

[0016] (2) The weight-average molecular weight of the high-functionality aliphatic polyurethane acrylate is 1000 Da to 3000 Da;

[0017] (3) The weight-average molecular weight of the flexible aliphatic polyurethane acrylate is 2000 Da to 10000 Da;

[0018] (4) The weight average molecular weight of the epoxy acrylate is 500 Da to 1500 Da.

[0019] In some embodiments, the provided electron beam-cured anti-glare coating satisfies one or both of the following conditions:

[0020] (1) The epoxy acrylate comprises bisphenol A type epoxy acrylate; optionally, the bisphenol A type epoxy acrylate comprises one or more of standard bisphenol A type epoxy acrylate and modified bisphenol A type epoxy acrylate; optionally, the bisphenol A type epoxy acrylate comprises one or more of the following commercial models: AgiSyn TM 1010-A80 (available from Covestro), CN-104A80 NS (available from Sartoma), CN 120 NS (available from Sartoma), B-113 (available from Changxing Materials), B-123 (available from Changxing Materials), 9104 (available from Litian Technology), 9105M-80 (available from Litian Technology), EA-1010N (available from Sartoma or Changxing Materials) and EA-1020LC3 (available from Sartoma or Changxing Materials);

[0021] (2) The reactive diluent comprises one or more of monofunctional acrylates, difunctional acrylates, acrylates with a functionality of at least 3, and acrylates with higher functionality; optionally, the monofunctional acrylate comprises one or more of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), isobornyl acrylate (IBOA), lauryl acrylate (LA), ethyl 2-(2-ethoxyethoxy)acrylate (EOEOEA), methyl methacrylate (MMA), and isobornyl methacrylate (IBOMA); the difunctional acrylate comprises 1,6-hexanediol diacrylate. The acrylate comprises one or more of the following: HDDA, tripropylene glycol diacrylate (TPGDA), diethylene glycol diacrylate (DEGDA), neopentyl glycol diacrylate (NPGDA), 1,4-butanediol diacrylate (BDDA), and ethylene glycol dimethacrylate (EGDMA); wherein the acrylate having a functionality of at least 3 comprises one or more of the following: trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), trimethylolpropane trimethacrylate (TMPTMA), and propoxylated glycerol triacrylate (GPTA).

[0022] In some embodiments, the provided electron beam-cured anti-glare coating satisfies one or more of the following conditions:

[0023] (1) The adhesion promoter is a phosphate ester acrylate;

[0024] (2) The toughness modifier is an amine-modified acrylate; optionally, the amine-modified acrylate includes one or more of amine-modified polyester acrylate, amine-modified epoxy acrylate, and amino acrylate; further optionally, it includes one or two of EBECRYL® 81 and EBECRYL® 3600;

[0025] (3) The average particle size of the silica matting agent is 3-12 μm;

[0026] (4) The leveling agent comprises one or more of non-silicone leveling agents and modified acrylate leveling agents; optionally, the leveling agent comprises polyacrylate non-silicone leveling agents; further optionally, it comprises one or more of GS-1358, GS-1853, LD-100A, Tech-1392 and Dowsen FL-29, and the aforementioned products can be purchased from Zhongshan Qianyou Chemical, Guangzhou Guanxin New Materials, Guangzhou Sluco, Haimings Company or Foshan Sanhua New Materials Technology Co., Ltd.

[0027] (5) The dispersant comprises a polymeric dispersant having a number average molecular weight of 3,000 Da to 40,000 Da; optionally, the dispersant comprises one or more of a polymeric copolymer containing acidic groups and a polymeric copolymer containing pigment affinity groups; further optionally, it comprises one or more of BYK-161, BYK-163, Solsperse 24000 and Solsperse 32000, the aforementioned products being available from BYK Chemical or Lubrizol.

[0028] In some embodiments, a method for preparing the electron beam-cured anti-glare coating is provided, comprising the following steps: under light-protected conditions, stirring and mixing epoxy acrylate, high-functionality aliphatic polyurethane acrylate, flexible aliphatic polyurethane acrylate and reactive diluent;

[0029] Add dispersant and leveling agent, and mix thoroughly.

[0030] After adding silica matting agent, the material temperature is controlled to be less than or equal to 50℃ for basket mill dispersion;

[0031] An adhesion promoter and a toughness modifier are added, and the mixture is stirred and mixed. The mixture is then filtered using a filter bag, and the filtrate is collected to prepare the electron beam cured anti-glare coating.

[0032] In some embodiments, an anti-glare coating is provided, which is prepared by curing the electron beam-cured anti-glare coating by electron beam radiation.

[0033] In some embodiments, the method for preparing the anti-glare coating involves coating the electron beam-cured anti-glare coating onto the surface of a substrate to form a wet film, and curing the wet film with an electron beam under an inert atmosphere. The oxygen concentration in the inert atmosphere is <200 ppm, and the absorbed dose of the electron beam curing is 30 kGy to 80 kGy.

[0034] Optionally, one or both of the following conditions must be met:

[0035] The inert atmosphere is nitrogen;

[0036] The accelerating voltage during electron beam curing is 120keV~200keV.

[0037] In some embodiments, an electronic device display cover or electronic device housing is provided, the surface of which contains the aforementioned anti-glare coating.

[0038] In some embodiments, an industrial device, vehicle, home building material product, optical device, energy device, or retail device is provided, including the aforementioned electronic device display cover or electronic device housing.

[0039] The aforementioned electron beam cured anti-glare coating uses an electron beam curing system without photoinitiators. By combining specific types and proportions of resins and adding functional additives, the resulting coating has excellent anti-glare effect, high hardness, strong adhesion, good toughness, and no small molecule residue. It can be used for electronic device display covers or electronic device housings. Detailed Implementation

[0040] To facilitate understanding of the present invention, a more comprehensive description will be given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0041] It should be noted that when a component is said to be "fixed to" another component, it can be directly attached to the other component or there may be an intervening component. When a component is said to be "connected to" another component, it can be directly connected to the other component or there may be an intervening component.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0043] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0044] The terms "and / or," "or / and," and "and / or" as used in this application encompass any one of two or more related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected using at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that in this application, the technical solution undoubtedly includes solutions connected by "logical AND," and also undoubtedly includes solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: A, B, and "a combination of A and B."

[0045] In this application, the terms "multiple", "various", "multiple times", "multi-dimensional", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0046] The terms “combinations thereof,” “any combination thereof,” and “any combination thereof” as used in this application include all suitable combinations of any two or more of the listed items.

[0047] In this application, the term "suitable" as used in "suitable combination", "suitable method", "any suitable method", etc., refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0048] In this application, terms such as "preferred," "better," "more suitable," and "ideal" are merely used to describe implementation methods or embodiments that achieve better results, and should be understood not to limit the scope of protection of this application.

[0049] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0050] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0051] In this invention, the terms "first aspect," "second aspect," "third aspect," and "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," and "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0052] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0053] In this application, numerical intervals (i.e., numerical ranges) are involved. Unless otherwise specified, the selected numerical distributions within the aforementioned numerical intervals are considered continuous and include the two endpoints (i.e., the minimum and maximum values) of the numerical range, as well as every value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints. In this document, this is equivalent to directly listing every integer. For example, if t is an integer selected from 1 to 10, it means that t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Furthermore, when multiple ranges are provided to describe features or characteristics, these ranges can be merged. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0054] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0055] In this application, % (w / w) and wt% both represent weight percentage, % (v / v) refers to volume percentage, and % (w / v) refers to mass-volume percentage.

[0056] In this application, "room temperature" generally refers to 5℃~30℃, and more preferably 25±5℃.

[0057] In some embodiments, an electron beam-cured anti-glare coating is provided, comprising, by weight percentage: 30%–40% epoxy acrylate, 25%–35% high-functionality aliphatic polyurethane acrylate, 3%–8% flexible aliphatic polyurethane acrylate, 20%–30% reactive diluent, 4%–8% silica matting agent, 2%–4% adhesion promoter, 0.3%–0.7% leveling agent, 0.8%–1.5% dispersant, and 1%–3% toughness modifier; wherein, the functionality refers to the CH2=C(R) content in a single molecule. 1 The number of )-CO- groups, R 1 The high-functionality aliphatic polyurethane acrylate has a functionality of 6 or greater than or equal to that of hydrogen atoms or methyl groups.

[0058] The glass transition temperature of the flexible aliphatic polyurethane acrylate is less than or equal to -60°C.

[0059] The provided electron beam cured anti-glare coating overcomes the technical defects of current UV-cured AG coatings, requires no photoinitiator, cures thoroughly, and has excellent performance.

[0060] In some embodiments, the provided electron beam-cured anti-glare coating does not contain an initiator.

[0061] The provided electron beam cured anti-glare coating is initiator-free, safe, and environmentally friendly, with good storage stability. It provides a stable and uniform anti-glare effect, high hardness, strong adhesion, and good toughness. Utilizing EB curing eliminates photoinitiators, avoiding issues such as odor, migration, yellowing, and potential toxicity caused by small molecule residues, making the product safer and suitable for high-end electronic products. The absence of photoinitiators also avoids the risk of prepolymerization due to heat or weak light during storage, resulting in a longer shelf life and better storage stability. The provided electron beam-cured anti-glare coating allows for precise control of gloss within the 15-50 GU range at 60°, achieving a stable and uniform anti-glare effect. High-functionality aliphatic polyurethane acrylate ensures high cross-linking density and hardness, achieving a pencil hardness ≥3H. The introduction of adhesion promoters and flexible aliphatic polyurethane acrylate ensures excellent adhesion to substrates such as PC and PMMA, reaching 5B. The flexible aliphatic polyurethane acrylate provides flexibility; through the scientific compounding of flexible aliphatic polyurethane acrylate and toughness modifiers, the internal stress of the highly cross-linked system is effectively balanced, resulting in a coating with good toughness and resistance to cracking. Electron beam curing is insensitive to oxygen inhibition (under an inert atmosphere), offering fast curing speed and suitability for continuous sheet or roll production with high efficiency.

[0062] The high-functionality aliphatic polyurethane acrylate used can provide extremely high reactivity and crosslinking density to compensate for the lack of exogenous initiators in EB curing, ensuring that the coating achieves the required hardness, abrasion resistance and chemical resistance.

[0063] The epoxy acrylate used serves as a rigid framework, providing basic hardness and chemical resistance.

[0064] The flexible aliphatic polyurethane acrylate used is employed to regulate the internal stress of the system, improve flexibility and adhesion, and works synergistically with the high-functionality resin to balance the hardness and toughness of the coating.

[0065] Reactive diluents can effectively reduce the viscosity of the system and provide high reactivity.

[0066] Silica matting agents can create an anti-glare effect, and the gloss and haze of the coating can be adjusted by controlling its dosage.

[0067] Adhesion promoters can improve the adhesion of coatings to plastic substrates under electron beam rapid curing conditions.

[0068] Leveling agents can achieve a smooth surface within an extremely short leveling window during rapid electron beam curing.

[0069] Dispersants can ensure that matting agents are stably dispersed in the system over a long period of time.

[0070] Toughness modifiers have both co-initiating and toughening effects, which can further improve curing rate and coating toughness.

[0071] In some embodiments, the provided electron beam cured anti-glare coating does not contain solvents. It is understood that the electron beam cured anti-glare coating, by weight percentage, contains 30% to 40% epoxy acrylate, for example, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, etc., or may be a range consisting of any two of the aforementioned values.

[0072] Understandably, electron beam cured anti-glare coatings contain 25% to 35% high-functionality aliphatic polyurethane acrylate by weight percentage, for example, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, etc., or any range of the aforementioned two values.

[0073] Understandably, electron beam cured anti-glare coatings contain 3% to 8% flexible aliphatic polyurethane acrylate by weight percentage, for example, 3%, 4%, 5%, 6%, 7%, 8%, etc., or any range of two of the aforementioned values.

[0074] Understandably, electron beam cured anti-glare coatings contain 20% to 30% reactive diluent by weight percentage, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc., or any range of the aforementioned two values.

[0075] Understandably, electron beam cured anti-glare coatings contain 4% to 8% silica matting agent by weight percentage, for example, 4%, 5%, 6%, 7%, 8%, etc., or any range of the aforementioned two values.

[0076] Understandably, electron beam cured anti-glare coatings contain 2% to 4% adhesion promoter by weight, for example, 2%, 3%, 4%, etc., or any combination of the two aforementioned values.

[0077] Understandably, electron beam cured anti-glare coatings contain 0.3% to 0.7% leveling agent by weight, for example, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, etc., or any range of two of the aforementioned values.

[0078] Understandably, electron beam cured anti-glare coatings contain 0.8% to 1.5% dispersant by weight, for example, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc., or any range of two of the aforementioned values.

[0079] Understandably, electron beam cured anti-glare coatings contain 1% to 3% toughness modifier by weight percentage, for example, 1%, 2%, 3%, etc., or any combination of the two aforementioned values.

[0080] In some embodiments, the provided electron beam cured anti-glare coating has a functionality of 6 to 9 for the high-functionality aliphatic polyurethane acrylate, such as 6, 7, 8, 9, etc., or it can be a range composed of any two of the aforementioned values.

[0081] In some embodiments, the provided electron beam-cured anti-glare coating comprises a low-functionality aliphatic polyurethane acrylate, wherein the functionality of the low-functionality aliphatic polyurethane acrylate is 1 to 2; in some embodiments, the low-functionality aliphatic polyurethane acrylate has a functionality of 2.

[0082] In some embodiments, the provided electron beam-cured anti-glare coating comprises a flexible aliphatic polyurethane acrylate whose soft segments include one or more of polyether polyols, polyester polyols, and polybutadiene, with a number average molecular weight of 1000 Da to 4000 Da; a hard segment includes one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate; and a capping agent includes hydroxyl-containing acrylates and / or isocyanate-containing acrylates. The soft segments constitute 60% to 85% of the flexible aliphatic polyurethane acrylate by mass, the hard segments constitute 10% to 30% of the flexible aliphatic polyurethane acrylate by mass, and the capping agent constitutes 5% to 15% of the flexible aliphatic polyurethane acrylate by mass. Optionally, the polyether polyol includes one or more of polypropylene glycol and polytetrahydrofuran glycol, and the polyester polyol includes one or more of polybutylene adipate diol and polycaprolactone diol.

[0083] In some embodiments, the provided electron beam-cured anti-glare coating has a breakage elongation of 150% to 500% for the flexible aliphatic polyurethane acrylate.

[0084] In some embodiments, the provided electron beam-cured anti-glare coating comprises one or more of hexafunctional aliphatic polyurethane acrylates and nonafunctional aliphatic polyurethane acrylates.

[0085] In some embodiments, the provided electron beam-cured anti-glare coating has a weight-average molecular weight of 1000 Da to 3000 Da for high-functionality aliphatic polyurethane acrylate, such as 1000 Da, 1200 Da, 1400 Da, 1600 Da, 1800 Da, 2000 Da, 2200 Da, 2400 Da, 2600 Da, 2800 Da, 3000 Da, etc., or it can be a range composed of any two of the aforementioned values.

[0086] In some embodiments, the electron beam-cured anti-glare coating provided has a weight-average molecular weight of 2000 Da to 10000 Da for the flexible aliphatic polyurethane acrylate, or it can be 5000 Da to 10000 Da, for example, 2000 Da, 3000 Da, 4000 Da, 5000 Da, 6000 Da, 7000 Da, 8000 Da, 9000 Da, 10000 Da, etc., or it can be a range composed of any two of the aforementioned values.

[0087] In some embodiments, the provided electron beam-cured anti-glare coating has an epoxy acrylate with a weight-average molecular weight of 500 Da to 1500 Da, for example, 500 Da, 600 Da, 700 Da, 800 Da, 900 Da, 1000 Da, 1100 Da, 1200 Da, 1300 Da, 1400 Da, 1500 Da, etc., or it can be a range composed of any two of the aforementioned values.

[0088] In some embodiments, the provided electron beam-cured anti-glare coating comprises a bisphenol A type epoxy acrylate.

[0089] In some embodiments, the bisphenol A epoxy acrylate comprises one or more of standard bisphenol A epoxy acrylate and modified bisphenol A epoxy acrylate.

[0090] In some embodiments, the bisphenol A epoxy acrylate comprises one or more of the following commercial brands: AgiSyn TM 1010-A80 (can be purchased from Covestro), CN-104A80 NS (can be purchased from Sartoma), CN 120 NS (can be purchased from Sartoma), B-113 (can be purchased from Changxing Materials), B-123 (can be purchased from Changxing Materials), 9104 (can be purchased from Litian Technology), 9105M-80 (can be purchased from Litian Technology), EA-1010N (can be purchased from Sartoma or Changxing Materials) and EA-1020LC3 (can be purchased from Sartoma or Changxing Materials).

[0091] In some embodiments, the provided electron beam-cured anti-glare coating includes one or more of monofunctional acrylates, difunctional acrylates, acrylates with a functionality of at least 3, and acrylates with higher functionality.

[0092] In some embodiments, the provided electron beam-cured anti-glare coating includes one or more of the following monofunctional acrylates: hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), isobornyl acrylate (IBOA), lauryl acrylate (LA), ethyl 2-(2-ethoxyethoxy)acrylate (EOEOEA), methyl methacrylate (MMA), and isobornyl methacrylate (IBOMA).

[0093] The bifunctional acrylates include one or more of 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), diethylene glycol diacrylate (DEGDA), neopentyl glycol diacrylate (NPGDA), 1,4-butanediol diacrylate (BDDA), and ethylene glycol dimethacrylate (EGDMA).

[0094] The acrylate with a functionality of at least 3 includes one or more of trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), trimethylolpropane trimethacrylate (TMPTMA), and propoxylated glycerol triacrylate (GPTA).

[0095] In some embodiments, the adhesion promoter in the provided electron beam cured anti-glare coating is a phosphate ester acrylate.

[0096] In some embodiments, the provided electron beam-cured anti-glare coating uses an amine-modified acrylate as the toughness modifier; in some embodiments, the amine-modified acrylate comprises one or more of amine-modified polyester acrylate, amine-modified epoxy acrylate, and amino acrylate; in some embodiments, it comprises one or both of EBECRYL® 81 and EBECRYL® 3600.

[0097] In some embodiments, the provided electron beam cured anti-glare coating has an average particle size of 3-12 μm for the silica matting agent, such as 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, etc., or it can be a range composed of any two of the aforementioned values.

[0098] In some embodiments, the provided electron beam cured anti-glare coating includes a leveling agent comprising one or more of non-silicone leveling agents and modified acrylate leveling agents; optionally, the leveling agent comprises a polyacrylate non-silicone leveling agent; further optionally, it comprises one or more of GS-1358, GS-1853, LD-100A, Tech-1392 and Dowsen FL-29, the aforementioned products being available from Zhongshan Qianyou Chemical, Guangzhou Guanxin New Materials, Guangzhou Sloco, Haimings Company or Foshan Sanhua New Materials Technology Co., Ltd.

[0099] In some embodiments, the provided electron beam-cured anti-glare coating includes a polymeric dispersant having a number average molecular weight of 3,000 Da to 40,000 Da; optionally, the dispersant includes one or more of a polymer copolymer containing acidic groups and a polymer copolymer containing pigment affinity groups; further optionally, it includes one or more of BYK-161, BYK-163, Solsperse 24000, and Solsperse 32000, the aforementioned products being available from BYK Chemical or Lubrizol, respectively.

[0100] In some embodiments, a method for preparing an electron beam-cured anti-glare coating is provided, comprising the following steps: under light-shielding conditions, stirring and mixing the epoxy acrylate, high-functionality aliphatic polyurethane acrylate, flexible aliphatic polyurethane acrylate, and reactive diluent;

[0101] Add dispersant and leveling agent, and mix thoroughly.

[0102] After adding silica matting agent, the material temperature is controlled to be less than or equal to 50℃ for basket mill dispersion;

[0103] An adhesion promoter and a toughness modifier are added, and the mixture is stirred and mixed. The mixture is then filtered using a filter bag, and the filtrate is collected to prepare the electron beam cured anti-glare coating.

[0104] The provided method for preparing electron beam cured anti-glare coatings is a process that is controllable and can ensure the full dispersion of silica matting agent and the stability of the system.

[0105] In some embodiments, during the dispersion step of adding silica matting agent, a sand mill is used for dispersion at a linear velocity of 10 m / s to 15 m / s. For example, the linear velocity of the sand mill can be 10 m / s, 11 m / s, 12 m / s, 13 m / s, 14 m / s, 15 m / s, etc., or it can be any range of two of the aforementioned values.

[0106] In some embodiments, during the dispersion step of adding silica matting agent, the material temperature is controlled to be less than or equal to 50°C.

[0107] In a non-limiting manner, by using a sand mill at a linear velocity of 10-15 m / s and controlling the material temperature to be less than or equal to 50°C during the dispersion step of adding silica matting agent, it is possible to achieve precise control of 60° gloss within the range of 15-50 GU, thereby obtaining a stable and uniform anti-glare effect.

[0108] In some embodiments, the method for preparing the electron beam-cured anti-glare coating includes the following steps:

[0109] S1. Premixing: Under light-protected conditions, epoxy acrylate, high-functionality and flexible aliphatic polyurethane acrylate, and reactive diluent are added to the container in sequence and stirred at low speed until uniformly mixed.

[0110] S2. Dispersion: Add dispersant and leveling agent to the mixture in step S1, stir evenly, add silica matting agent, and disperse by circulating the mixture 3-5 times at a linear velocity of 10-15 m / s using a sand mill, controlling the material temperature to be less than or equal to 50℃, to obtain a uniformly dispersed slurry.

[0111] S3. Final adjustment: Add adhesion promoter and toughness modifier to the slurry obtained in step S2, stir at medium speed until completely uniform, filter with a filter bag, collect the filtrate, and obtain the electron beam cured anti-glare coating.

[0112] Bag filtration removes impurities and undispersed particles. During coating preparation, after basket milling, a small amount of insufficiently dispersed silica matting agent agglomerates, mechanical impurities introduced from the raw materials, or gel particles may still remain in the system. Bag filtration effectively retains these large particles, ensuring the fineness and uniformity of the coating.

[0113] In some implementations, the filter bag has a mesh size of 300 to 500 mesh. Using a filter bag with this mesh size can ensure the filtration effect without excessively prolonging the filtration time.

[0114] In some embodiments, an anti-glare coating is provided, which is prepared by electron beam curing of an anti-glare coating through electron beam radiation curing.

[0115] In some embodiments, the provided coating cures to form a dry film with a thickness of 10 μm to 30 μm.

[0116] In some embodiments, the provided coating has a gloss level of 15 GU to 50 GU at 60°.

[0117] In some embodiments, the provided coating has a pencil hardness greater than or equal to 3H.

[0118] In some embodiments, a method for preparing an anti-glare coating is provided, wherein an electron beam-cured anti-glare coating is applied to the surface of a substrate to form a wet film, and the wet film is cured by electron beam curing under an inert atmosphere, wherein the oxygen concentration in the inert atmosphere is <200ppm and the absorbed dose of the electron beam curing is 30kGy~80kGy.

[0119] In some embodiments, the substrate comprises one or more of polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyethylene terephthalate (PET), glass, and silicon wafers.

[0120] In some embodiments, the coating method includes blade coating, roller coating, or spray coating.

[0121] In some implementations, the inert atmosphere is nitrogen.

[0122] In some implementations, the accelerating voltage during electron beam curing is 120keV to 200keV.

[0123] In some embodiments, an electronic device display cover or electronic device housing is provided, the surface of which contains the aforementioned anti-glare coating.

[0124] In some embodiments, an industrial device, vehicle, home building material product, optical device, energy device, or retail device is provided, including the aforementioned electronic device display cover or electronic device housing.

[0125] In some embodiments, the means of transport is selected from one or more of automobiles, airplanes, ships, and rail vehicles. It is understood that the central control display screen, instrument panel, or in-vehicle navigation system of an automobile or rail vehicle uses the aforementioned electronic device display cover or electronic device housing; the cockpit display panel of an aircraft uses the aforementioned electronic device display cover or electronic device housing; and the navigation display of a ship uses the aforementioned electronic device display cover or electronic device housing.

[0126] In some embodiments, the industrial equipment is selected from one or more of the following: human-machine interface, industrial control all-in-one computer, instrument panel, rail transit vehicle display panel, medical display equipment, and military and aerospace display equipment.

[0127] In some embodiments, the home building materials are selected from one or more of the following: high-end cabinet panels, countertops, furniture finishes, architectural curtain wall glass, interior partitions, and bathroom mirrors.

[0128] In some embodiments, the optical device is selected from optical lenses or anti-glare street lamp covers.

[0129] In some embodiments, the energy device is selected from solar photovoltaic panels.

[0130] In some embodiments, the retail device is selected from one or more of the following: anti-glare screen protector, advertising display screen, vending machine touch screen, and retail display counter.

[0131] The following are specific embodiments. They are intended to provide a more detailed description of this application to help those skilled in the art and researchers better understand it. The technical conditions described do not constitute any limitation on this application. Any modifications made within the scope of the claims of this application are protected by the claims.

[0132] Unless otherwise stated, all raw materials and reagents used in the following examples are commercially available or can be prepared by known methods. Experimental methods not specifying particular conditions in the examples were performed under conventional conditions, such as those described in literature, books, or methods recommended by the manufacturer.

[0133] The reagent information used in the examples and comparative examples is as follows:

[0134] The epoxy acrylate is a bisphenol A type epoxy acrylate, CAS number 71281-65-7, purchased from Allnex, model EBECRIL® 600;

[0135] The high-functionality aliphatic polyurethane acrylate is a 9-functionality aliphatic polyurethane acrylate, CAS number 68987-79-1, purchased from Sartomer, model CN ​​9013 NS.

[0136] Flexible aliphatic polyurethane acrylate (2-functionality) and 2-functional aliphatic polyurethane acrylate, CAS No. 68987-79-1, purchased from IGM Resins, model Photomer 6643, with glass transition temperature of -70℃ to -80℃, elongation at break of 200% to 400%, and weight-average molecular weight of 5000 Da to 10000 Da.

[0137] TPGDA is tripropylene glycol diacrylate, CAS number 42978-66-5, purchased from Sartomer, model SR306;

[0138] HDDA is 1,6-hexanediol diacrylate, CAS number 13048-33-4, purchased from Sartomer, model SR238;

[0139] The silica matting agent was purchased from Jingzhijie Technology Co., Ltd., with an average particle size of 6.3μm and model number HF-650.

[0140] The leveling agent is a modified acrylate non-silicone leveling agent, purchased from Foshan Sanhua New Material Technology Co., Ltd., model Dowsen FL-29;

[0141] The dispersant is a polymeric copolymer containing acidic groups, purchased from BYK Company, model BYK-163;

[0142] The adhesion promoter was phosphate acrylate, purchased from Hubei Xingyan New Material Technology Co., Ltd., model AD1771;

[0143] The toughness modifier is an amine-modified polyester acrylate, purchased from Allnex, model EBECRIL® 81.

[0144] Examples 1-3

[0145] Electron beam cured anti-glare coatings with different AG effects were prepared according to the formulations (mass percentages) shown in Table 1.

[0146] Table 1. Coating formulations (wt%) for Examples 1-3

[0147]

[0148] In Table 1, the content of each component in the examples and comparative examples is the percentage of the total weight of the electron beam cured anti-glare coating. In Table 1, TPGDA refers to tripropylene glycol diacrylate, and HDDA refers to difunctional 1,6-hexanediol diacrylate. Examples 1-3 achieved different anti-glare effects by adjusting the amount of silica matting agent and the ratio of reactive diluent.

[0149] Preparation method:

[0150] 1. Weigh each component according to the proportions.

[0151] 2. Add epoxy acrylate, high-functionality PUA (9-functional), flexible PUA, TPGDA and HDDA to the brown mixing tank and stir at 500 rpm for 10 minutes until well mixed.

[0152] 3. Add leveling agent and dispersant, and continue stirring for 5 minutes.

[0153] 4. Slowly add silica matting agent, and after adding, increase the speed to 800 rpm for pre-dispersion for 15 minutes.

[0154] 5. Transfer to a basket mill, use zirconia beads as the grinding media, circulate and disperse 4 times at a linear velocity of 12 m / s, and control the discharge temperature to be below 50℃.

[0155] 6. Transfer the dispersed slurry back to the mixing tank, add the adhesion promoter and toughness modifier, and stir at 600 rpm for 20 minutes until completely homogeneous.

[0156] 7. Filter with a 500-mesh filter bag to obtain the finished coating.

[0157] Effect test

[0158] The obtained coating was applied to a 5mm thick corona-treated PC board using a wire bar coater, resulting in a wet film thickness of 30μm. The sample was then placed in an electron beam curing apparatus (nitrogen atmosphere, O2 < 200ppm) and cured under an accelerating voltage of 120keV and an absorbed dose of 30kGy. The dry film thickness after curing was approximately 15μm. After the sample was placed under standard conditions for 24 hours, performance tests were performed according to the standards shown in Table 2.

[0159] Table 2. Coating performance test results for Examples 1-3

[0160]

[0161] As can be seen from the data in Table 2, the anti-glare coating prepared by the provided electron beam cured anti-glare coating has excellent optical properties, mechanical properties and adhesion.

[0162] The anti-glare effect of the prepared anti-glare coating is controllable and adjustable. By adjusting the content of silica matting agent in the formulation (5.0%, 6.0%, and 7.0% in Examples 1-3, respectively), the 60° gloss can be gradually reduced from 35 GU to 15 GU, and the haze can be gradually increased from 18% to 38%. This indicates that the coating system has good controllability of anti-glare effect and can be precisely designed according to different application requirements (such as velvety feel or strong matte feel).

[0163] The prepared anti-glare coating exhibits high hardness and excellent adhesion. The pencil hardness of the anti-glare coatings provided in the examples all reached 3H or higher (with Examples 1 and 2 reaching 4H), and the cross-cut adhesion was the highest grade 5B. This demonstrates that the electron beam-cured anti-glare coating combines the hardness resulting from high cross-linking density with excellent substrate adhesion, solving the technical problems of high-hardness coatings being prone to brittleness and having poor adhesion.

[0164] The prepared anti-glare coating exhibits excellent chemical resistance. After being wiped more than 500 times with an alcohol swab under a 500g load, the coating showed no change, indicating that it has excellent solvent resistance and is suitable for applications requiring frequent contact and cleaning.

[0165] The prepared anti-glare coatings have a uniform appearance. Visual observation shows that the coating surfaces of each embodiment are uniform, exhibiting either a "uniform velvety feel" or a "uniform strong matte finish," indicating that the matting agent is well dispersed in the electron beam curing system without photoinitiator, and no agglomeration or surface unevenness occurs.

[0166] Example 4

[0167] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the silica matting agent with an average particle size of 6 μm in Example 2 is replaced with an equal amount of silica matting agent with an average particle size of 20 μm.

[0168] The same test method as in Table 2 was used for testing, and the results are as follows: gloss 18GU, haze 45%, pencil hardness 3H, adhesion 4B (local edge peeling), rough appearance, poor feel, obvious graininess, gloss slightly increased after 400 alcohol wiping cycles.

[0169] Example 5

[0170] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those in Example 2, except that the reactive diluent (TPGDA+HDDA) in Example 2 is completely replaced with an equal amount of monofunctional diluent isobornyl acrylate (IBOA).

[0171] The same test method as in Table 2 was used for testing, and the results are as follows: gloss 26GU, pencil hardness HB~F, adhesion 4B, and the coating turned white and lost its gloss after 200 alcohol wiping cycles.

[0172] Example 6

[0173] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those in Example 2, except that the basket milling linear speed in step S2 is reduced from 12 m / s to 5 m / s, while other conditions are the same as in Example 2.

[0174] The same test method as in Table 2 was used for testing, and the results are as follows: gloss 28 GU, haze 20%, gloss increased after 450 alcohol wipes, and the coating surface had a fine grainy feel.

[0175] Example 7

[0176] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those in Example 2, except that the number of cyclic dispersion passes in step S2 is reduced from 4 to 1, while other conditions are the same as in Example 2.

[0177] The same test method as in Table 2 was used for testing, and the results are as follows: the gloss fluctuated between 20 and 30 GU, the haze was uneven, and there were local areas with higher gloss in the coating.

[0178] Example 8

[0179] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those in Example 2, except that the 500-mesh filter bag in step S3 is replaced with a 100-mesh filter bag, and other conditions are the same as in Example 2.

[0180] The same test method as in Table 2 was used for testing, and the results are as follows: a small number of scratches or particle protrusions appeared on the coating surface.

[0181] Example 9

[0182] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those in Example 2, except that the wet film thickness is increased from 30 μm to 60 μm (the dry film thickness is about 30 μm). Other conditions are the same as in Example 2.

[0183] The same test method as in Table 2 was used for testing, and the results are as follows: gloss 18 GU, pencil hardness 3H, adhesion 3B, and microcracks appeared in the coating.

[0184] Comparative Example 1

[0185] The target is similar to that of Example 2 in terms of anti-glare effect, but a UV curing system is used. Its formulation, by weight percentage, includes:

[0186] 30% epoxy acrylate (bisphenol A type, Allnex EBECRYL® 600), 25% difunctional aliphatic polyurethane acrylate (Sartomer CN228 NS), 5% flexible aliphatic polyurethane acrylate (difunctional, low Tg type, IGM Resins Photomer 6643), 16.6% tripropylene glycol diacrylate (TPGDA, Sartomer SR 306), 6.7% 1,6-hexanediol diacrylate (HDDA, Sartomer SR 238), 6% silica matting agent (average particle size 6μm, Jingzhijie HF-650), 0.5% leveling agent (modified acrylate non-silicone leveling agent, Sanhua New Materials Dowsen). FL-29), 1.2% dispersant (acid-containing polymer copolymer, BYK-163), 3% adhesion promoter (phosphate ester acrylate, Xingyan New Materials AD1771), 2% toughness modifier (amine-modified polyester acrylate, Allnex EBECRYL® 81), 3% photoinitiator Irgacure 184 (BASF, CAS No. 947-19-3) and 1% photoinitiator TPO (BASF, CAS No. 75980-60-8).

[0187] The preparation method is the same as in Example 2 except for the following differences: no strict control of the nitrogen environment is required; curing is performed using 1000 mJ / cm³. 2 UV LED energy irradiation.

[0188] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 25 GU, hardness 2H, adhesion 4B (local edge peeling), and gloss slightly increased after 300 alcohol wiping cycles. Compared with Example 2, hardness, adhesion, and chemical resistance all decreased, and the system contained a photoinitiator.

[0189] Comparative Example 2

[0190] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the high-functionality aliphatic polyurethane acrylate (9-functional) in Example 2 is completely replaced with an equal amount of 2-functionality aliphatic polyurethane acrylate.

[0191] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 24 GU, hardness H, adhesion 3B (significant peeling occurred after cross-cutting with a cross-cutting tool), and slight loss of gloss after 200 alcohol wiping cycles. Compared with Example 2, due to the lack of high cross-linking density provided by high-functionality resin, the hardness and chemical resistance of the coating decreased significantly, and the adhesion also deteriorated due to insufficient cross-linking.

[0192] Comparative Example 3

[0193] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the flexible aliphatic polyurethane acrylate (5.0%) in Example 2 is completely replaced with an equal amount of high-functionality PUA (9-functional).

[0194] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 23 GU, hardness 4H, adhesion 2B (the coating is brittle, and large areas of edge chipping and peeling occur during cross-cutting), and no change after >500 alcohol wiping cycles. Compared with Example 2, although the hardness and chemical resistance remain good, the coating brittleness is significantly increased due to the lack of flexible resin to regulate internal stress, resulting in a serious deterioration in adhesion.

[0195] Comparative Example 4

[0196] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the epoxy acrylate (30.0%) in Example 2 is completely replaced with an equal amount of high-functionality PUA (9-functional), that is, the total amount of high-functionality PUA is increased to 60.0%.

[0197] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 23 GU, pencil hardness 3H, adhesion 3B, and gloss significantly increased after 300 alcohol rubs. Compared with Example 2, although a higher crosslinking density was maintained, the coating hardness and adhesion to the PC substrate decreased due to the lack of a rigid skeleton and polar groups provided by epoxy acrylate, and the chemical resistance was also inferior to Example 2.

[0198] Comparative Example 5

[0199] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the adhesion promoter (3.0%) in Example 2 is completely replaced with an equal amount of reactive diluent TPGDA.

[0200] The same test method as in Table 2 was used for testing, and the results are as follows: gloss 24GU, hardness 4H, adhesion 1B~2B (the coating peeled off significantly in the cross-cut adhesion test), and edge lifting after 300 alcohol wiping cycles. The electron beam curing rate is extremely fast; in the absence of adhesion promoters, the coating shrinkage stress cannot be effectively anchored to the substrate surface, leading to a sharp decrease in adhesion.

[0201] Comparative Example 6

[0202] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the toughness modifier (2.0%) in Example 2 is completely replaced with an equal amount of reactive diluent TPGDA.

[0203] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 23 GU, pencil hardness 4H, adhesion 3B, and no change after >500 alcohol wiping cycles. However, the coating showed obvious cracks in the bending test (or drop ball impact test). Compared with Example 2, although the crosslinking density and chemical resistance were maintained, the coating's internal stress increased, toughness decreased significantly, and impact resistance deteriorated due to the lack of toughening effect and synergistic curing effect provided by amine-modified acrylate.

[0204] Comparative Example 7

[0205] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the dispersant (1.2%) in Example 2 is completely replaced with an equal amount of reactive diluent TPGDA.

[0206] The same test method as in Table 2 was used for testing, and the results are as follows: the gloss value fluctuated greatly at different locations, the haze was high and uneven, a small number of white spots or agglomerated particles appeared on the coating surface, and the gloss increased significantly after 400 alcohol wipes. Compared with Example 2, the anti-glare effect was out of control due to the flocculation and sedimentation of the silica matting agent in the absence of a dispersant, and the uniformity and stability of the coating decreased significantly.

[0207] Comparative Example 8

[0208] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the leveling agent (0.5%) in Example 2 is completely replaced with an equal amount of reactive diluent TPGDA.

[0209] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 22 GU, pencil hardness 4H, adhesion 4B, slight orange peel, pinholes and brush marks appeared on the coating surface, and the appearance was visually uneven. Compared with Example 2, due to the extremely short electron beam curing leveling time, the coating could not be fully spread before curing when there was a lack of leveling agent, resulting in more surface defects and a decrease in appearance quality.

[0210] Comparative Example 9

[0211] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the flexible PUA in Example 2 is increased from 5.0% to 15.0%, and the high-functionality PUA is correspondingly reduced to 20.0%.

[0212] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 25 GU, pencil hardness HB, adhesion 5B, and softening of the coating after 150 alcohol rubs. Compared with Example 2, the coating was too soft due to insufficient crosslinking density caused by excessive flexible resin, resulting in significantly reduced scratch resistance and chemical resistance.

[0213] Comparative Example 10

[0214] This comparative example provides an electron beam-cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the conventional silica in Example 2 is replaced with an equal amount of hydrophilic untreated fumed silica.

[0215] The same test method as in Table 2 was used for testing, and the results are as follows: severe agglomeration occurred during dispersion, the fineness of the slurry exceeded the standard, the coating surface was rough with obvious white spots, the gloss could not be stably controlled (fluctuating between 15 and 35 GU), and the adhesion was 3B. Compared with Example 2, due to the poor compatibility between hydrophilic silica and the acrylate system, stable dispersion was not possible, and the coating uniformity, appearance, and anti-glare effect were significantly deteriorated.

[0216] Comparative Example 11

[0217] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those of Example 2, except that the material temperature is not controlled in step S2, and the temperature is allowed to rise to above 70°C. Other conditions are the same as in Example 2.

[0218] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 26 GU, pencil hardness 3H, adhesion 3B, a small number of microbubbles or pinholes appeared in the coating, and the gloss increased after 400 alcohol wiping cycles. Compared with Example 2, excessively high temperature led to a decrease in system viscosity, volatilization or thermal polymerization of some low molecular weight components, and the introduction of air bubbles, affecting the coating density and adhesion.

[0219] Comparative Example 12

[0220] This comparative example provides an electron beam-cured anti-glare coating. The formulation and preparation method are similar to those in Example 2, except that the curing absorption dose is reduced from 30 kGy to 10 kGy, while other conditions are the same as in Example 2.

[0221] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 26 GU, pencil hardness HB, adhesion 2B, and the coating dissolved or severely lost its gloss after 100 alcohol wiping cycles. Compared with Example 2, insufficient dosage led to incomplete cross-linking, and the coating could not achieve the required hardness and chemical resistance.

[0222] Comparative Example 13

[0223] This comparative example provides an electron beam cured anti-glare coating. The formulation and preparation method are similar to those in Example 2, except that the oxygen concentration in the nitrogen atmosphere is increased from <200ppm to 1000ppm, while other conditions are the same as in Example 2.

[0224] The same test methods as in Table 2 were used for testing, and the results are as follows: gloss 27 GU, pencil hardness 2H, adhesion 3B, the coating surface showed stickiness or poor curing, and the gloss increased after 300 alcohol wipes. Compared with Example 2, although electron beam curing is not sensitive to oxygen inhibition, high oxygen concentrations can still lead to incomplete surface curing, affecting surface properties and adhesion.

[0225] As can be seen from the above embodiments and comparative examples, the electron beam cured anti-glare coating provided by the present invention, through a unique combination of photoinitiator-free resins and additives, combined with a specific process, successfully obtains an AG coating with comprehensive performance superior to that of the traditional UV curing system, especially in terms of hardness, adhesion and environmental safety.

[0226] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

[0227] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0228] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. An electron beam-cured anti-glare coating, characterized in that, By weight percentage, it contains 30%~40% epoxy acrylate, 25%~35% high-functionality aliphatic polyurethane acrylate, 3%~8% flexible aliphatic polyurethane acrylate, 20%~30% reactive diluent, 4%~8% silica matting agent, 2%~4% adhesion promoter, 0.3%~0.7% leveling agent, 0.8%~1.5% dispersant, and 1%~3% toughness modifier; The functionality refers to the amount of CH2=C(R) contained in a single molecule. 1 The number of )-CO- groups, R 1 The high-functionality aliphatic polyurethane acrylate has a functionality of 6 or greater than or equal to that of hydrogen atoms or methyl groups. The glass transition temperature of the flexible aliphatic polyurethane acrylate is less than or equal to -60°C.

2. The electron beam cured anti-glare coating according to claim 1, characterized in that, One or more of the following conditions must be met: (1) The functionality of the high-functionality aliphatic polyurethane acrylate is 6 to 9; (2) The flexible aliphatic polyurethane acrylate includes a low-functionality aliphatic polyurethane acrylate, wherein the functionality of the low-functionality aliphatic polyurethane acrylate is 1 to 2, and optionally, the low-functionality aliphatic polyurethane acrylate has a functionality of 2. (3) The soft segment of the flexible aliphatic polyurethane acrylate includes one or more of polyether polyol, polyester polyol and polybutadiene, and the number average molecular weight of the soft segment is 1000 Da~4000 Da; the hard segment includes one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the end-capping agent includes hydroxyl-containing acrylate and / or isocyanate-containing acrylate; wherein, the mass fraction of the soft segment in the flexible aliphatic polyurethane acrylate is 60%~85%, the mass fraction of the hard segment in the flexible aliphatic polyurethane acrylate is 10%~30%, and the mass fraction of the end-capping agent in the flexible aliphatic polyurethane acrylate is 5%~15%; optionally, the polyether polyol includes one or more of polypropylene glycol and polytetrahydrofuran diol, and the polyester polyol includes one or more of polybutylene adipate diol and polycaprolactone diol; (4) The elongation at break of the flexible aliphatic polyurethane acrylate is 150%~500%.

3. The electron beam cured anti-glare coating according to claim 1, characterized in that, One or more of the following conditions must be met: (1) The high-functionality aliphatic polyurethane acrylate includes one or more of hexafunctional aliphatic polyurethane acrylate and nonafunctional aliphatic polyurethane acrylate. (2) The weight-average molecular weight of the high-functionality aliphatic polyurethane acrylate is 1000 Da to 3000 Da; (3) The weight-average molecular weight of the flexible aliphatic polyurethane acrylate is 2000 Da to 10000 Da; (4) The weight average molecular weight of the epoxy acrylate is 500 Da to 1500 Da.

4. The electron beam-cured anti-glare coating according to any one of claims 1 to 3, characterized in that, One or both of the following conditions must be met: (1) The epoxy acrylate comprises bisphenol A type epoxy acrylate; optionally, the bisphenol A type epoxy acrylate comprises one or more of standard bisphenol A type epoxy acrylate and modified bisphenol A type epoxy acrylate; optionally, the bisphenol A type epoxy acrylate comprises one or more of the following commercial models: AgiSyn TM 1010-A80, CN-104A80NS, CN 120 NS, B-113, B-123, 9104, 9105M-80, EA-1010N and EA-1020LC3; (2) The reactive diluent comprises one or more of monofunctional acrylates, difunctional acrylates, acrylates with a functionality of at least 3, and acrylates with higher functionality; optionally, the monofunctional acrylates comprise one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, isobornyl acrylate, lauryl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, methyl methacrylate, and isobornyl methacrylate; the difunctional acrylates comprise one or more of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, and dimethacrylate; the acrylates with a functionality of at least 3 comprise one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, and propoxylated glycerol triacrylate.

5. The electron beam-cured anti-glare coating according to any one of claims 1 to 3, characterized in that, One or more of the following conditions must be met: (1) The adhesion promoter is a phosphate ester acrylate; (2) The toughness modifier is an amine-modified acrylate; optionally, the amine-modified acrylate includes one or more of amine-modified polyester acrylate, amine-modified epoxy acrylate, and amino acrylate; further optionally, it includes one or two of EBECRYL® 81 and EBECRYL® 3600; (3) The average particle size of the silica matting agent is 3-12 μm; (4) The leveling agent comprises one or more of non-silicone leveling agents and modified acrylate leveling agents; optionally, the leveling agent comprises polyacrylate non-silicone leveling agents; further optionally, it comprises one or more of GS-1358, GS-1853, LD-100A, Tech-1392 and Dowsen FL-29; (5) The dispersant comprises a polymeric dispersant having a number average molecular weight of 3000 Da to 40000 Da; optionally, the dispersant comprises one or more of a polymeric copolymer containing acidic groups and a polymeric copolymer containing pigment affinity groups; further optionally, it comprises one or more of BYK-161, BYK-163, Solsperse 24000 and Solsperse 32000.

6. The method for preparing the electron beam cured anti-glare coating according to any one of claims 1 to 5, characterized in that, Includes the following steps: Under light-protected conditions, epoxy acrylate, high-functionality aliphatic polyurethane acrylate, flexible aliphatic polyurethane acrylate, and reactive diluent are stirred and mixed. Add dispersant and leveling agent, and mix thoroughly. After adding silica matting agent, the material temperature is controlled to be less than or equal to 50℃ for basket mill dispersion; An adhesion promoter and a toughness modifier are added, and the mixture is stirred and mixed. The mixture is then filtered using a filter bag, and the filtrate is collected to prepare the electron beam cured anti-glare coating.

7. An anti-glare coating, characterized in that, The electron beam curable anti-glare coating according to any one of claims 1 to 5 is prepared by electron beam radiation curing.

8. The method for preparing the anti-glare coating according to claim 7, characterized in that, The electron beam curable anti-glare coating according to any one of claims 1 to 5 is applied to the surface of a substrate to form a wet film. The wet film is cured by an electron beam under the protection of an inert atmosphere, wherein the oxygen concentration in the inert atmosphere is <200ppm and the absorbed dose of the electron beam curing is 30kGy to 80kGy. Optionally, one or both of the following conditions must be met: The inert atmosphere is nitrogen; The accelerating voltage during electron beam curing is 120keV~200keV.

9. A display cover or housing for an electronic device, characterized in that, The surface of the electronic device display cover or electronic device housing contains the anti-glare coating as described in claim 7.

10. An industrial equipment, vehicle, home building material product, optical device, energy device, or retail device, characterized in that, It includes the electronic device display cover or electronic device housing as described in claim 9.

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