Polyfunctional group-modified silane compound and its manufacturing method, hard coating and its manufacturing method

Abstract

To provide a multifunctional modified silane compound and a manufacturing method thereof, and a hard coating layer and a manufacturing method thereof.SOLUTION: A material of a hard coating includes a multifunctional modified silane compound with a structure including: a cyclic rigid structure R1; a fluorine-containing structure R2; a polar group R3; and a polyfunctional (meth)acrylate R4 having at least three (meth)acryloyloxy groups. Through the cyclic rigid structure R1 and the networked crosslinking of R4, the formed hard coating has very good mechanical properties, a pencil hardness greater than or equal to 4H, and a steel wool abrasion resistance greater than or equal to 100 cycles. Through the perfluoro structure of R2, the formed hardened coating has a very good antifouling and water-repellent effect, and a water contact angle greater than or equal to 115°. The polar groups of R3 can increase the adhesion force between the formed hardened coating and a substrate, so that the adhesion force measured by the crosscut method is 5B.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present application relates to the field of materials, and more particularly to a polyfunctional modified silane compound and a method for producing the same, and a hard coating and a method for producing the same. [Background technology]

[0002] The display device can convert computer data into various characters, numbers, symbols, or intuitive images for display, and can input commands or data into the computer using an input tool such as a keyboard, and can add, delete, or change the displayed content at any time using the system's hardware and software. Display devices are classified into types such as plasma, liquid crystal, light-emitting diode, and cathode ray tube according to the display device used.

[0003] Displays may be scratched during use, so the display surface must be scratch-resistant, hard, and abrasion-resistant.In addition, displays may be contaminated during use, and the contaminants are difficult to remove. Wiping with a solvent will destroy the surface, so the display surface must be stain-resistant and water-repellent.

[0004] There are generally two ways to give the display surface high mechanical performance and anti-soiling performance at the same time. The first method is to add a fluorine-containing auxiliary to the hard coating, which can obtain good mechanical performance, but the fluorine content of the hard coating is low, so the anti-soiling hydrophobic effect is limited and the water contact angle is difficult to exceed 110°. The second method is to form a film on the display surface by curing silicone or fluorocarbon compound materials, but such a film is not highly crosslinked and it is difficult to have good mechanical performance. Summary of the Invention

[0005] The object of the present invention is to provide a polyfunctional modified silane compound and a method for producing the same, and a hard coating and a method for producing the same, which can solve the problems in the prior art, such as the limited anti-fouling and hydrophobic effect when a fluorine-containing auxiliary is added to a hard coating to improve its mechanical performance, and the low mechanical performance when a silicone or fluorocarbon compound material is cured to form a film.

[0006] In order to solve the above problems, the present invention provides a polyfunctional modified silane compound comprising the following structure: [ka] In the formula, R1 comprises a cyclic rigid structure, R2 comprises a fluorine-containing structure, R3 comprises a polar group, and R4 comprises a polyfunctional (meth)acrylate of at least three (meth)acryloyloxy groups.

[0007] Furthermore, R1 is [ka] Contains one of the following:

[0008] Furthermore, R2 is [ka] Contains one of the following:

[0009] Furthermore, R3 is [ka] Contains one of the following:

[0010] In order to solve the above problems, the present invention further provides a method for producing a polyfunctional modified silane compound according to the present invention, the method including the steps of: adding a vinyl group-containing siloxane, a cyclic structure-containing acrylate, and a photoinitiator to a first vessel, bubbling with nitrogen, stirring, and reacting under light irradiation to form a first reaction liquid; adding the vinyl group-containing siloxane, a fluoroacrylate, and the photoinitiator to a second vessel, bubbling with nitrogen, stirring, and reacting under light irradiation to form a second reaction liquid; and adding the vinyl group-containing siloxane, a polar group-containing propylene compound, and the photoinitiator to a third vessel, bubbling with nitrogen, stirring, and reacting under light irradiation to form a third reaction liquid. adding the vinyl-containing siloxane, the acrylate having a functionality of ≧3, and the photoinitiator to a fourth vessel, bubbling with nitrogen, stirring, and reacting under light irradiation to form a fourth reaction liquid; adding K2CO3, ultrapure water, and tetrahydrofuran to a fifth vessel to form a first mixture, adding the first reaction liquid, the second reaction liquid, the third reaction liquid, and the fourth reaction liquid to the first mixture to form a second mixture, stirring to decompose the second mixture into a colorless aqueous phase and a cloudy organic phase; evaporating and removing the organic solvent in the cloudy organic phase, dissolving the remaining solution in DCM, extracting with ultrapure water multiple times, and then evaporating to obtain the polyfunctional modified silane compound.

[0011] Further, the vinyl group-containing siloxane includes one of vinyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(trimethoxysilyl)propyl acrylate, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, dimethoxymethylvinylsilane, methylvinyldiethoxysilane, tetradimethylvinylsiloxysilane, methylbis(trimethylsiloxy)vinylsilane, vinyltris(trimethylsiloxy)silane, trimethoxy(4-vinylphenyl)silane, vinyltris(dimethylsiloxy)silane, triisopropoxy(vinyl)silane, and triethoxyl(1-phenylvinyl)silane.

[0012] Further, the cyclic structure-containing acrylate includes one of isobornyl acrylate, isobornyl methacrylate, tricyclodecane dimethanol diacrylate, 2-phenoxyethyl acrylate, fluorenoacrylate, triallyl trimellitate, bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, bisphenol F diacrylate, ethoxylated bisphenol F diacrylate, o-phenylphenoxyethyl acrylate, phenoxybenzyl acrylate, bisphenol fluorene diacrylate, ethoxylated bisphenol fluorene diacrylate, and triallyl isocyanurate.

[0013] Further, the fluoroacrylate may be 1H,1H-perfluoro-n-octyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 1H,1H,5H-octafluoropentyl acrylate, perfluoroalkylethyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 2,2, 3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane, 2,3,4,5,6-pentafluorostyrene, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 1H,1H,11H-perfluoroundecyl methacrylate, and 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate.

[0014] Further, the polar group-containing propylene compound includes one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-methyl-2-acrylate-2,3-dihydroxypropyl, acrylic acid, 2-hydroxyethyl acrylate, acrylonitrile, ethyl cyanoacrylate, 2-cyano-2-butyl acrylate, 2-cyano-3-phenylmethyl acrylate, ethyl 2-cyano-3-ethoxyacrylate, 2-cyanoethyl acrylate, epoxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-furanacrylic acid, 2-acetaminoacrylic acid, acrylamide, methacrylamide, diacetone acrylamide, dimethylaminopropyl acrylamide, N-tert-butyl acrylamide, N-hydroxymethyl acrylamide, N-ethyl acrylamide, N-[tri(hydroxymethyl)methyl]acrylamide, and N,N'-methylenebisacrylamide.

[0015] Further, the acrylate having a functionality of ≧3 includes one of trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, bis(trimethylolpropane) tri(meth)acrylate, and dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bis(trimethylolpropane) tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, bis(trimethylolpropane) penta(meth)acrylate, dipentaerythritol hexaacrylate, and bis(trimethylolpropane) hexa(meth)acrylate.

[0016] In order to solve the above problems, the present invention further provides a hard coating, the material of which comprises, by weight parts, 90-100 parts of the polyfunctional modified silane compound according to the present invention, 5-10 parts of a photoinitiator, and 900-9000 parts of a first solvent having a boiling point range of 50°C to 150°C.

[0017] Additionally, the photoinitiator includes one of a hydroxyacetophenone, an alkylaminoacetophenone, a benzoin ether, a phosphine oxide compound, a benzil ketal, and a dialkoxyacetophenone.

[0018] Furthermore, the first solvent having a boiling point range of 50° C. to 150° C. includes one of an alcohol-based solvent, an ester-based solvent, a ketone-based solvent, and a benzene-based solvent.

[0019] In order to solve the above problems, the present invention further provides a method for producing a hard coating according to the present invention, the method comprising the steps of mixing the polyfunctional modified silane compound, the photoinitiator and the first solvent having a boiling point range of 50°C to 150°C to form a hard coating liquid, and applying the hard coating liquid onto a substrate to form a hard coating.

[0020] Regarding the advantages of the present invention, the material of the hard coating of the present invention comprises a polyfunctional modified silane compound, the structure of the polyfunctional modified silane compound comprises R1, R2, R3 and R4, R1 comprises a cyclic rigid structure, R2 comprises a fluorine-containing structure, R3 comprises a polar group, and R4 comprises a polyfunctional (meth)acrylate of at least three (meth)acryloyloxy groups. Due to the cyclic rigid structure of R1 and the networked crosslinking of R4, the hard coating formed has very good mechanical performance, pencil hardness ≧4H, steel wool abrasion resistance ≧100 cycles. Due to the perfluoro structure of R2, the hard coating formed has very good antifouling and water repellency, contact angle ≧115°. Due to the polar group of R3, the adhesion between the formed hard coating and the substrate can be increased, and the adhesion measured by the cross-cut method is 5B. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] In the following, in order to fully introduce the technical contents of the present invention to those skilled in the art and illustrate that the present invention can be implemented, preferred embodiments of the present invention are described in detail, so as to make the technical contents disclosed in the present invention clearer and to allow those skilled in the art to more easily understand how to implement the present invention. However, the present invention can be embodied in many different forms of embodiments, and the scope of protection of the present invention is not limited to the embodiments mentioned in the specification, and the following description of the embodiments is not intended to limit the scope of the present invention.

[0022] Example 1 The present invention provides a polyfunctional modified silane compound comprising the following structure: [ka] In the formula, R1 comprises a cyclic rigid structure, R2 comprises a fluorine-containing structure, R3 comprises a polar group, and R4 comprises a polyfunctional (meth)acrylate of at least three (meth)acryloyloxy groups.

[0023] In the formula, R1 is [ka] Contains one of the following:

[0024] In the formula, R2 is [ka] Contains one of the following:

[0025] In the formula, R3 is [ka] Contains one of the following:

[0026] In order to solve the above problems, the present invention further provides a method for producing a polyfunctional modified silane compound according to the present invention, the method including the steps of: adding a vinyl group-containing siloxane, a cyclic structure-containing acrylate, and a photoinitiator to a first container, bubbling with nitrogen, stirring, and reacting under light irradiation to form a first reaction liquid S1; adding the vinyl group-containing siloxane, a fluoroacrylate, and the photoinitiator to a second container, bubbling with nitrogen, stirring, and reacting under light irradiation to form a second reaction liquid S2; and adding the vinyl group-containing siloxane, a polar group-containing propylene compound, and the photoinitiator to a third container, bubbling with nitrogen, stirring, and reacting under light irradiation to form a third reaction liquid S3. Step S3; adding the vinyl group-containing siloxane, the acrylate having a functionality of ≧3, and the photoinitiator to a fourth vessel, bubbling with nitrogen, stirring, and reacting under light irradiation to form a fourth reaction liquid; Step S4; adding K2CO3, ultrapure water, and tetrahydrofuran to a fifth vessel to form a first mixture, adding the first reaction liquid, the second reaction liquid, the third reaction liquid, and the fourth reaction liquid to the first mixture to form a second mixture, stirring to decompose the second mixture into a colorless aqueous phase and a cloudy organic phase; and evaporating and removing the organic solvent in the cloudy organic phase, dissolving the remaining solution in DCM, extracting with ultrapure water multiple times, and then evaporating to obtain the polyfunctional modified silane compound.

[0027] In S1, the reaction structure of vinyl group-containing siloxane and cyclic structure-containing acrylate is as follows: [ka]

[0028] In S1, the vinyl group-containing siloxane comprises one of vinyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(trimethoxysilyl)propyl acrylate, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, dimethoxymethylvinylsilane, methylvinyldiethoxysilane, tetradimethylvinylsiloxysilane, methylbis(trimethylsiloxy)vinylsilane, vinyltris(trimethylsiloxy)silane, trimethoxy(4-vinylphenyl)silane, vinyltris(dimethylsiloxy)silane, triisopropoxy(vinyl)silane and triethoxyl(1-phenylvinyl)silane, where R5 and R6 each comprise an alkyl group.

[0029] In S1, the cyclic structure-containing acrylate includes one of isobornyl acrylate, isobornyl methacrylate, tricyclodecane dimethanol diacrylate, 2-phenoxyethyl acrylate, fluorenoacrylate, triallyl trimellitate, bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, bisphenol F diacrylate, ethoxylated bisphenol F diacrylate, o-phenylphenoxyethyl acrylate, phenoxybenzyl acrylate, bisphenol fluorene diacrylate, ethoxylated bisphenol fluorene diacrylate, and triallyl isocyanurate.

[0030] In S2, the reaction structure of vinyl-containing siloxane and fluoroacrylate is as follows: [ka]

[0031] S2, the fluoroacrylate is 1H,1H-perfluoro-n-octyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 1H,1H,5H-octafluoropentyl acrylate, perfluoroalkylethyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 2,2, 3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane, 2,3,4,5,6-pentafluorostyrene, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 1H,1H,11H-perfluoroundecyl methacrylate, and 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate.

[0032] In S3, the reaction structure of the vinyl group-containing siloxane and the polar group-containing propylene compound is as follows: [ka]

[0033] In S3, the polar group-containing propylene compound comprises one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-methyl-2-acrylate-2,3-dihydroxypropyl, acrylic acid, 2-hydroxyethyl acrylate, acrylonitrile, ethyl cyanoacrylate, 2-cyano-2-butyl acrylate, 2-cyano-3-phenylmethyl acrylate, ethyl 2-cyano-3-ethoxyacrylate, 2-cyanoethyl acrylate, epoxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-furanacrylic acid, 2-acetaminoacrylic acid, acrylamide, methacrylamide, diacetone acrylamide, dimethylaminopropyl acrylamide, N-tert-butyl acrylamide, N-hydroxymethyl acrylamide, N-ethyl acrylamide, N-[tri(hydroxymethyl)methyl]acrylamide, and N,N'-methylenebisacrylamide.

[0034] In S4, the reaction structure of vinyl-containing siloxane and acrylate with a functionality of ≧3 is as follows: [ka]

[0035] In S4, the acrylate having a functionality of ≧3 includes one of trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, bis(trimethylolpropane) tri(meth)acrylate, and dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bis(trimethylolpropane) tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, bis(trimethylolpropane) penta(meth)acrylate, dipentaerythritol hexaacrylate, and bis(trimethylolpropane) hexa(meth)acrylate.

[0036] In S5, the reaction structural formulas of K2CO3, ultrapure water, the initiator, the first reaction liquid, the second reaction liquid, the third reaction liquid and the fourth reaction liquid are as follows: [ka]

[0037] In this embodiment, in S1, 10 g of 3-(methacryloyloxy)propyltrimethoxysilane, 8.95 g of isobornyl methacrylate, and 0.5 g of ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate are added to a first flask (three-neck flask), and the mixture is stirred with nitrogen bubbling, and reacted for 1 hour under 365 nm LED light irradiation to form a first reaction liquid. That is, in this embodiment, the vinyl group-containing siloxane is 3-(methacryloyloxy)propyltrimethoxysilane, the cyclic structure-containing acrylate is isobornyl methacrylate, and the photoinitiator is a phosphine oxide compound, specifically, the photoinitiator is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate.

[0038] In this embodiment, in S2, 10 g of 3-(methacryloyloxy)propyltrimethoxysilane, 15.55 g of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, and 0.8 g of phenyl(2,4,6-trimethylbenzoyl)ethyl phosphinate are added to the second flask (three-neck flask), and the mixture is stirred with nitrogen bubbling, and reacted for 2 hours under 365 nm LED light irradiation to form a second reaction liquid. That is, in this embodiment, the vinyl group-containing siloxane is 3-(methacryloyloxy)propyltrimethoxysilane, the fluoroacrylate is 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, and the photoinitiator is a phosphine oxide compound, specifically, the photoinitiator is phenyl(2,4,6-trimethylbenzoyl)ethyl phosphinate.

[0039] In this embodiment, in S3, 10g of 3-(methacryloyloxy)propyltrimethoxysilane, 6.29g of tetrahydrofurfuryl acrylate, and 0.5g of ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate are added to the third flask (three-neck flask), and the mixture is stirred with nitrogen bubbling, and reacted for 1h under 365nm LED light irradiation to form a third reaction liquid. That is, in this embodiment, the vinyl group-containing siloxane is 3-(methacryloyloxy)propyltrimethoxysilane, the polar group-containing propylene compound is tetrahydrofurfuryl acrylate, and the photoinitiator is a phosphine oxide compound, specifically, the photoinitiator is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate.

[0040] In this embodiment, in S4, 10g of 3-(methacryloyloxy)propyltrimethoxysilane, 13.63g of trimethylolpropane tri(meth)acrylate, and 0.6g of ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate are added to the fourth flask (three-neck flask), and the mixture is stirred with nitrogen bubbling, and reacted for 1h under 365nm LED light irradiation to form a fourth reaction liquid. That is, in this embodiment, the vinyl group-containing siloxane is 3-(methacryloyloxy)propyltrimethoxysilane, the acrylate with a functionality of ≧3 is trimethylolpropane tri(meth)acrylate, and the photoinitiator is a phosphine oxide compound, specifically, the photoinitiator is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate.

[0041] In this example, in S5, 0.1 g of K2CO3, 9 g of ultrapure water, and 15 g of tetrahydrofuran are added to the fourth flask (250 mL round-bottom flask) to form a first mixture. 12 g of the first reaction liquid, 12 g of the second reaction liquid, 12 g of the third reaction liquid, and 4 g of the fourth reaction liquid are added to the first mixture sprayed with nitrogen to form a second mixture, which is vigorously stirred at room temperature for 48 h. The second mixture is then decomposed into a colorless aqueous phase and a cloudy organic phase containing the product. The organic solvent in the cloudy organic phase is evaporated and removed, and the remaining white viscous solution is dissolved in DCM and extracted multiple times with ultrapure water. In order to remove traces of water in the DCM solution, MgSO4 is added as a desiccant, stirred, left overnight, and then filtered. Then, the DCM is evaporated at 40 ° C for 2 h to obtain a transparent oily polyfunctional modified silane compound.

[0042] This embodiment further provides a hard coating material comprising, by weight, 90-100 parts of the polyfunctional modified silane compound described in this embodiment, 5-10 parts of a photoinitiator, and 900-9000 parts of a first solvent having a boiling point range of 50°C to 150°C.

[0043] In this embodiment, the hard coating formed by the cyclic rigid structure of R1 and the network crosslinking of R4 has very good mechanical performance, with pencil hardness ≧4H and steel wool abrasion resistance ≧100 cycles. The hard coating formed by the perfluoro structure of R2 has very good antifouling and water repellency, with a contact angle ≧115°. The polar group of R3 can increase the adhesion between the hard coating formed and the substrate, with the adhesion measured by the cross-cut method being 5B.

[0044] wherein the photoinitiator comprises one of hydroxyacetophenones, alkylaminoacetophenones, benzoin ethers, phosphine oxide compounds, benzil ketals, and dialkoxyacetophenones.

[0045] Here, if the first solvent has a boiling point below 50°C, it becomes highly volatile, affecting the resin solid content and coating thickness, and if it exceeds 150°C, the drying process becomes difficult, affecting efficiency and increasing costs. The first solvent having a boiling point range of 50°C to 150°C includes one of alcohol-based solvents, ester-based solvents, ketone-based solvents, and benzene-based solvents.

[0046] Here, the alcohol-based solvent includes one of methanol, ethanol, and isopropanol, the ester-based solvent includes one of ethyl acetate, propyl acetate, and butyl acetate, the ketone-based solvent includes one of acetone, butanone, and cyclohexanone, and the benzene-based solvent includes one of toluene and xylene.

[0047] The present invention further provides a method for producing the hard coating described in the present embodiment, the method including the steps of mixing the multifunctional modified silane compound, the photoinitiator, and the first solvent having a boiling point range of 50°C to 150°C to form a hard coating liquid, and applying the hard coating liquid onto a substrate to form a hard coating.

[0048] Specifically, in this embodiment, 10g of a multifunctional modified silane compound, 0.3g of phenyl(2,4,6-trimethylbenzoyl)ethyl phosphinate, and 19g of ethyl acetate are mixed to form a hard coating solution, which is then applied onto a PET substrate and formed into a film using a wire bar to form a hard coating. That is, in this embodiment, the photoinitiator is a phosphine oxide compound, specifically, the photoinitiator is phenyl(2,4,6-trimethylbenzoyl)ethyl phosphinate. The thickness of the hard coating produced is 3um.

[0049] The hard coating produced in this embodiment has been tested to have a pencil hardness of 5H, a steel wool abrasion resistance of 150 cycles, a water contact angle of 123°, and an adhesion of 5B.

[0050] As can be seen from the above, the hard coating of the present invention has very good mechanical properties, with a pencil hardness of ≧4H, a steel wool abrasion resistance of ≧100 cycles, very good stain-proofing and water-repellent effect, with a contact angle of ≧115°, and good adhesion to the substrate, with an adhesion of 5B measured by the cross-cut method.

[0051] Example 2 In this embodiment, in S1, 10g of 3-(trimethoxysilyl)propyl acrylate, 8.95g of tricyclodecane dimethanol diacrylate, and 0.7g of 1-hydroxycyclohexyl phenyl ketone are added to a first flask (three-neck flask), and the mixture is stirred with nitrogen bubbling, and reacted for 1 hour under 365nm LED light irradiation to form a first reaction liquid, but it also includes most of the technical features of embodiment 1. That is, the first compound in this embodiment is 3-(trimethoxysilyl)propyl acrylate, the second compound is tricyclodecane dimethanol diacrylate, and the photoinitiator is hydroxyacetophenone, specifically, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0052] In this embodiment, in S2, 10 g of 3-(trimethoxysilyl)propyl acrylate, 17.84 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, and 0.6 g of 1-hydroxycyclohexyl phenyl ketone are added to the second flask (three-neck flask), and the mixture is stirred with nitrogen bubbling, and reacted for 2 hours under 365 nm LED light irradiation to form a second reaction liquid. That is, in this embodiment, the first compound is 3-(trimethoxysilyl)propyl acrylate, the third compound is 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, and the photoinitiator is hydroxyacetophenone, specifically, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0053] In this embodiment, in S3, 10 g of 3-(trimethoxysilyl)propyl acrylate, 6.15 g of 4-hydroxybutyl acrylate, and 0.5 g of 1-hydroxycyclohexyl phenyl ketone are added to a third flask (three-neck flask), and the mixture is stirred with nitrogen bubbling, and reacted for 1 hour under 365 nm LED light irradiation to form a third reaction solution. That is, in this embodiment, the first compound is 3-(trimethoxysilyl)propyl acrylate, the fourth compound is 4-hydroxybutyl acrylate, and the photoinitiator is hydroxyacetophenone, specifically, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0054] In this embodiment, in S4, 10 g of 3-(trimethoxysilyl)propyl acrylate, 30.07 g of dipentaerythritol hexaacrylate, and 0.8 g of 1-hydroxycyclohexyl phenyl ketone are added to a fourth flask (three-neck flask), and the mixture is stirred with nitrogen bubbling, and reacted for 1 hour under 365 nm LED light irradiation to form a fourth reaction solution. That is, in this embodiment, the first compound is 3-(trimethoxysilyl)propyl acrylate, the fifth compound is dipentaerythritol hexaacrylate, and the photoinitiator is hydroxyacetophenone, specifically, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0055] In this example, in S5, 0.1 g of K2CO3, 9 g of ultrapure water, and 15 g of the second solvent (tetrahydrofuran) are added to the fourth flask (250 mL round-bottom flask) to form a first mixture. 12 g of the first reaction liquid, 12 g of the second reaction liquid, 12 g of the third reaction liquid, and 4 g of the fourth reaction liquid are added to the first mixture sprayed with nitrogen to form a second mixture, which is vigorously stirred at room temperature for 48 h. The second mixture is then decomposed into a colorless aqueous phase and a cloudy organic phase containing the product. The organic solvent in the cloudy organic phase is evaporated and removed, and the remaining white viscous solution is dissolved in a third solvent (DCM) and extracted multiple times with ultrapure water. In order to remove traces of water in the DCM solution, MgSO4 is added as a desiccant, stirred, left overnight, and then filtered. Then, the DCM is evaporated at 40 ° C for 2 h to obtain a transparent oily polyfunctional modified silane compound.

[0056] In this embodiment, in S6, 10g of multifunctional modified silane compound, 0.3g of 1-hydroxycyclohexyl phenyl ketone and 19g of isopropanol are mixed to form a hard coating solution, and the hard coating solution is applied onto a PET substrate and formed into a film by a wire bar to form a hard coating. That is, in this embodiment, the photoinitiator is hydroxyacetophenone, specifically, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone. The thickness of the produced hard coating is 3um.

[0057] The hard coating produced in this example was measured to have a pencil hardness of 6H, a steel wool abrasion resistance of 200 cycles, a water contact angle of 125°, and an adhesion of 5B.

[0058] As can be seen from the above, the hard coating according to this embodiment has very good mechanical properties, with a pencil hardness of ≧4H, a steel wool abrasion resistance of ≧100 cycles, very good stain-proofing and water-repellent properties, with a contact angle of ≧115°, and good adhesion to the substrate, with an adhesion strength of 5B measured by the cross-cut method.

[0059] Furthermore, the above provides a detailed introduction of the multifunctional modified silane compound and its manufacturing method, and the hard coating and its manufacturing method provided in the present application, and the present specification describes the principles and embodiments of the present application using specific examples, but the above explanation of the examples is only intended to assist in understanding the method and gist of the present application. In addition, those skilled in the art will recognize that there are changes in the specific embodiments and application scope based on the gist of the present application, and as such, the contents of the present specification should not be understood as limitations on the present application.

Claims

1. It comprises the following structure: 【Chemistry 1】 In the formula, R1 comprises a cyclic rigid structure, R2 comprises a fluorine-containing structure, R3 comprises a polar group, and R4 comprises a polyfunctional (meth)acrylate group containing at least two (meth)acryloyloxy groups, and R1, R2, R3, and R4 are randomly included. A polyfunctional group-modified silane compound.

2. The R1 is 【Chemistry 2】 The polyfunctional modified silane compound according to claim 1, characterized in that it contains one of the following:

3. The R2 is 【Chemistry 3】 The polyfunctional modified silane compound according to claim 1, characterized in that it contains one of the following:

4. The R3 is 【Chemistry 4】 The polyfunctional modified silane compound according to claim 1, characterized in that it contains one of the following:

5. Adding a vinyl group-containing siloxane, a cyclic structure-containing acrylate and a photoinitiator to a first container, bubbling nitrogen and stirring the mixture, and reacting the mixture under light irradiation to form a first reaction liquid; Adding the vinyl group-containing siloxane, the fluoroacrylate, and the photoinitiator to a second container, bubbling with nitrogen, stirring, and reacting under light irradiation to form a second reaction liquid; adding the vinyl group-containing siloxane, the polar group-containing compound and the photoinitiator to a third vessel, bubbling with nitrogen, stirring and reacting under light irradiation to form a third reaction liquid; Adding the vinyl group-containing siloxane, the acrylate having a functionality of ≧3, and the photoinitiator into a fourth vessel, bubbling with nitrogen, stirring, and reacting under light irradiation to form a fourth reaction liquid; K in the fifth container ２ CO ３ adding ultrapure water and tetrahydrofuran to form a first mixture; adding the first reaction liquid, the second reaction liquid, the third reaction liquid, and the fourth reaction liquid to the first mixture to form a second mixture; and stirring to decompose the second mixture into a colorless aqueous phase and a cloudy organic phase. and removing the organic solvent in the turbid organic phase by evaporation, dissolving the remaining solution in DCM, extracting with ultrapure water multiple times, and then evaporating to obtain the polyfunctional modified silane compound.

6. The method for producing a polyfunctional modified silane compound according to claim 5, characterized in that the vinyl group-containing siloxane includes one of vinyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(trimethoxysilyl)propyl acrylate, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, dimethoxymethylvinylsilane, methylvinyldiethoxysilane, tetradimethylvinylsiloxysilane, methylbis(trimethylsiloxy)vinylsilane, vinyltris(trimethylsiloxy)silane, trimethoxy(4-vinylphenyl)silane, vinyltris(dimethylsiloxy)silane, triisopropoxy(vinyl)silane, and triethoxyl(1-phenylvinyl)silane.

7. The method for producing a polyfunctional modified silane compound according to claim 5, wherein the cyclic structure-containing acrylate is one of isobornyl acrylate, isobornyl methacrylate, tricyclodecane dimethanol diacrylate, 2-phenoxyethyl acrylate, fluorenoacrylate, bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, bisphenol F diacrylate, ethoxylated bisphenol F diacrylate, o-phenylphenoxyethyl acrylate, phenoxybenzyl acrylate, bisphenol fluorene diacrylate, and ethoxylated bisphenol fluorene diacrylate.

8. The fluoroacrylates include 1H,1H-perfluoro-n-octyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 1H,1H,5H-octafluoropentyl acrylate, perfluoroalkylethyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, The method for producing a polyfunctional modified silane compound according to claim 5, characterized in that the compound contains one of 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane, 2,3,4,5,6-pentafluorostyrene, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 1H,1H,11H-perfluoroundecyl methacrylate, and 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate.

9. The polar group-containing compound is, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-methyl-2-acrylate-2,3-dihydroxypropyl, acrylic acid, 2-hydroxyethyl acrylate, acrylonitrile, ethyl cyanoacrylate, 2-cyano-2-butyl acrylate, 2-cyano-3-methyl acrylate, 2-cyano-3-ethoxyethyl acrylate, 2-cyano-3-methyl acrylate, 2-cyano-3-ethyl ... The method for producing a polyfunctional group-modified silane compound according to claim 5, characterized in that the polyfunctional group-modified silane compound contains one of the following: anoethyl acrylate, epoxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-furanacrylic acid, 2-acetaminoacrylic acid, acrylamide, methacrylamide, diacetone acrylamide, dimethylaminopropyl acrylamide, N-tert-butyl acrylamide, N-hydroxymethyl acrylamide, N-ethyl acrylamide, N-[tri(hydroxymethyl)methyl]acrylamide, and N,N'-methylenebisacrylamide.

10. 6. The method for producing a polyfunctional modified silane compound according to claim 5, wherein the acrylate having a functionality of ≧3 comprises one of trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, bis(trimethylolpropane) tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bis(trimethylolpropane) tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, bis(trimethylolpropane) penta(meth)acrylate, dipentaerythritol hexaacrylate, and bis(trimethylolpropane) hexa(meth)acrylate.

11. A hard coating comprising, in parts by weight of material of said hard coating, 90 to 100 parts of the polyfunctional modified silane compound according to any one of claims 1 to 4; 5 to 10 parts of a photoinitiator; 900 to 9000 parts of a first solvent having a boiling point range of 50° C. to 150° C.

12. 12. The hard coating of claim 11, wherein the photoinitiator comprises one of a hydroxyacetophenone, an alkylaminoacetophenone, a benzoin ether, a phosphine oxide compound, a benzil ketal, and a dialkoxyacetophenone.

13. 12. The hard coating of claim 11, wherein the first solvent having a boiling point range of 50°C to 150°C includes one of an alcohol-based solvent, an ester-based solvent, a ketone-based solvent, and a benzene-based solvent.

14. 12. The method for producing a hard coating according to claim 11, comprising the steps of: mixing the multifunctional modified silane compound, the photoinitiator, and the first solvent having a boiling point range of 50° C. to 150° C. to form a hard coating liquid; and applying the hard coating liquid onto a substrate to form a hard coating.

Images