EB-cured scratch-resistant and stain-resistant decorative film and preparation method thereof

Abstract

The present invention relates to an EB-cured anti-scratch and stain-resistant decorative film and a preparation method thereof, belonging to the technical field of decorative films. The EB-cured anti-scratch and stain-resistant decorative film comprises the following components: 35-50 parts of polyurethane acrylate, 10-20 parts of reactive diluent, 15-30 parts of multifunctional fluorine-containing modified nano-silicon dioxide, 0.7-1.5 parts of auxiliary agent, and 0-10 parts of solvent; the polyurethane acrylate is a mixture of monofunctional polyurethane acrylate and trifunctional polyurethane acrylate. In the technical scheme of the present invention, by adding multifunctional fluorine-containing modified nano-silicon dioxide to the coating, the anti-scratch and stain-resistant performance of the decorative film is significantly improved. The multifunctional fluorine-containing modified nano-silicon dioxide provided by the present invention solves the problem of easy migration of fluorine-containing anti-fouling auxiliary agents and easy agglomeration of nano-silicon dioxide, and at the same time improves the cross-linking density of the system.

Description

Technical Field

[0001] The present invention belongs to the technical field of decorative films, and in particular, relates to an EB-cured scratch-resistant and stain-resistant decorative film and a preparation method thereof. Background Art

[0002] Electron beam (EB) curing uses an electric field to linearly accelerate the electron beam emitted by a cathode ray tube to reach an energy of 100-400keV, thereby inducing a polymerization reaction of oligomers containing unsaturated carbon-carbon double bonds in the coating, and obtaining a coating after curing. It has the advantages of fast curing speed, instant completion, strong penetration, uniform curing inside and outside, 100% curing film, and no pollution. With the improvement of people's living standards and aesthetic tastes, people have higher and higher requirements for decorative films, and new decorative films with functions such as scratch resistance, stain resistance, and easy cleaning have attracted widespread attention.

[0003] At present, in order to improve the anti-fouling performance of decorative films, fluorine-containing anti-fouling additives are often added, but fluorine-containing additives are easy to migrate, and the anti-fouling performance will gradually decrease. Adding nano-silicon dioxide to the decorative film can improve its anti-scratch and wear resistance, but nano-silicon dioxide particles are easy to agglomerate, resulting in poor anti-scratch and wear resistance. Therefore, it is necessary to solve the above problems and provide a decorative film with excellent anti-scratch and anti-fouling performance. Summary of the invention

[0004] The purpose of the present invention is to provide an EB-cured scratch-resistant and stain-resistant decorative film and a preparation method thereof, by adding multifunctional fluorine-containing modified nano-silica to the coating, the scratch-resistant and stain-resistant performance of the decorative film is significantly improved. The multifunctional fluorine-containing modified nano-silica provided by the present invention solves the problem of easy migration of fluorine-containing anti-fouling additives and easy agglomeration of nano-silica, and at the same time improves the cross-linking density of the system.

[0005] The technical problem to be solved by the present invention is that fluorine-containing anti-fouling agents are often added to improve the anti-fouling performance of decorative films, but fluorine-containing agents are easy to migrate, and the anti-fouling performance will gradually decrease. Adding nano-silicon dioxide to the decorative film can improve its anti-scratch and wear resistance, but nano-silicon dioxide particles are easy to agglomerate, resulting in poor anti-scratch and wear resistance.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] An EB-cured scratch-resistant and stain-resistant decorative film comprises the following components in parts by weight: 35-50 parts of polyurethane acrylate, 10-20 parts of active diluent, 15-30 parts of multifunctional fluorine-containing modified nano silicon dioxide, 0.7-1.5 parts of auxiliary agent and 0-10 parts of solvent.

[0008] Furthermore, the polyurethane acrylate is a mixture of monofunctional polyurethane acrylate and trifunctional polyurethane acrylate; the mass ratio of the monofunctional polyurethane acrylate to the trifunctional polyurethane acrylate is 1:(1-2).

[0009] Furthermore, the active diluent is a mixture of a monofunctional acrylate monomer and a trifunctional acrylate monomer; the mass ratio of the monofunctional acrylate monomer to the trifunctional acrylate monomer is 1:(0.1-0.3).

[0010] Furthermore, the monofunctional acrylate monomer is at least one of isobornyl acrylate, hydroxyethyl methacrylate, ethyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate.

[0011] Furthermore, the trifunctional acrylate monomer is at least one of trimethylolpropane triacrylate and pentaerythritol triacrylate.

[0012] Furthermore, the auxiliary agent includes at least one of a leveling agent, a dispersant and a defoaming agent.

[0013] Furthermore, the solvent is at least one of xylene, ethyl acetate, butyl acetate and acetone.

[0014] Furthermore, the preparation method of multi-functional fluorine-containing modified nano-silicon dioxide comprises the following steps:

[0015] A1. Under inert gas conditions, add fluoroacrylate and aminosilane coupling agent to anhydrous ethanol, stir and react for 18-32 hours, and remove anhydrous ethanol by reduced pressure distillation to obtain a fluorine-containing aminosilane coupling agent;

[0016] In the above preparation process, the unsaturated carbon-carbon double bond in the fluoroacrylate and the primary amine group in the aminosilane coupling agent undergo Michael addition reaction to obtain a fluorine-containing aminosilane coupling agent containing two secondary amine groups.

[0017] Furthermore, in step A1, the molar ratio of fluoroacrylate to aminosilane coupling agent is (1-1.1):1.

[0018] Further, in step A1, the fluoroacrylate is CH2=C(CH3)-COOR, wherein R=-CH2(CF2) X H, X = 5-8.

[0019] Furthermore, in step A1, the aminosilane coupling agent is at least one of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane.

[0020] A2, dispersing nano-silica in a mixed solution of ethanol and deionized water, and then adding a fluorine-containing aminosilane coupling agent for modification to obtain fluorine-containing modified nano-silica;

[0021] Furthermore, in step A2, the volume ratio of ethanol to deionized water is 1:(1-3).

[0022] Furthermore, in step A2, the ratio of the mixed solution of nano-silica, ethanol and deionized water to the fluorine-containing aminosilane coupling agent is 1 g: (30-60) mL: (0.4-1) g.

[0023] A3. Dissolve hydroxy acrylate monomer and hydroquinone in acetone to obtain a mixed solution; mix diisocyanate and catalyst, heat to 30-45°C and then drop the mixed solution, heat to 50-60°C after the addition is complete, react for 2-4 hours, monitor the -NCO content in the reaction system and when it reaches a threshold value, obtain isocyanate-acrylate monomer, then add a mixed solution of fluorine-modified nano-silica and acetone, react for 3-8 hours, and obtain multi-functional fluorine-modified nano-silica.

[0024] In the above preparation process, hydroxy acrylate monomer and diisocyanate are reacted to obtain isocyanate-acrylate monomer, and the isocyanate group in the isocyanate-acrylate monomer structure reacts with two secondary amine groups in the fluorine-containing modified nano-silica molecular chain, thereby grafting acrylate onto the fluorine-containing modified nano-silica to obtain multi-functional fluorine-containing modified nano-silica. The multi-functional fluorine-containing modified nano-silica can participate in the polymerization reaction, thereby avoiding the problem of easy migration of fluorine-containing additives, enhancing the anti-fouling performance of the decorative film, and at the same time making the nano-silica uniformly dispersed in the matrix, not easy to agglomerate, thereby improving the anti-scratch performance of the decorative film. The surface of the nano-silica contains multiple acrylates that can undergo polymerization reactions with polyurethane acrylate and acrylate monomers to cross-link, and the nano-silica can serve as a cross-linking point, thereby significantly improving the cross-linking density and hardness of the system.

[0025] Furthermore, in step A3, the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate.

[0026] Furthermore, in step A3, the hydroxyacrylate monomer is at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate.

[0027] Furthermore, in step A3, the catalyst is at least one of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate.

[0028] Furthermore, in step A3, the usage ratio of hydroxyacrylate monomer, hydroquinone and acetone is (10-11) g: (0.01-0.02) g: (3.5-4.2) mL.

[0029] Furthermore, in step A3, the molar ratio of the hydroxy acrylate monomer to the diisocyanate is 1:(1-1.1).

[0030] Furthermore, in step A3, the amount of catalyst added is 0.4-0.8% of the total amount of hydroxy acrylate monomer and diisocyanate.

[0031] Furthermore, in step A3, the mass ratio of isocyanate-acrylate monomer to fluorine-modified nano-silica is (1-4.8): (1.3-1.9).

[0032] A method for preparing an EB-cured scratch-resistant and stain-resistant decorative film comprises the following steps:

[0033] B1, polyurethane acrylate, acrylate monomer, multifunctional fluorine-containing modified nano-silica, auxiliary silicone surfactant and solvent are mixed evenly to form a coating, and the coating is applied on the surface of the substrate to form a slurry layer;

[0034] B2. Electron beam (EB) curing treatment is performed under anaerobic conditions to obtain an EB-cured scratch-resistant and stain-resistant decorative film.

[0035] In the above operation process, EB curing treatment is used to form a decorative film, which has high production efficiency, strong curing and no pollution. The polyurethane acrylate in the coating raw material includes monofunctional polyurethane acrylate and trifunctional polyurethane acrylate. Through the combination of two polyurethane acrylates with different functionalities and multifunctional fluorine-containing modified nano-silica, the cross-linking degree of the coating can be adjusted, so that the coating can achieve a balance between flexibility and hardness, thereby improving the density and hardness of the coating.

[0036] Furthermore, in step B2, the dose of EB curing is 30-70 kGy, and the voltage of EB curing is 140-280 keV.

[0037] Furthermore, in step B2, the coating amount of the coating is 10-30 g / m 2 .

[0038] Furthermore, in step B2, the substrate includes at least one of a PVC film, a PP film, and a PET film.

[0039] Furthermore, in step B2, the thickness of the substrate is 0.1-0.3 mm.

[0040] Beneficial effects of the present invention:

[0041] (1) In the technical solution of the present invention, monofunctional polyurethane acrylate, trifunctional polyurethane acrylate, multifunctional fluorine-containing modified nano-silica, etc. are used as raw materials, which significantly improves the scratch and stain resistance of the decorative film. The polyurethane acrylate in the raw materials includes monofunctional polyurethane acrylate and trifunctional polyurethane acrylate. By combining two polyurethane acrylates with different functionalities and multifunctional fluorine-containing modified nano-silica, the cross-linking degree of the coating can be adjusted, so that the coating achieves a balance between flexibility and hardness, thereby improving the density of the coating.

[0042] (2) In the technical scheme of the present invention, a hydroxy acrylate monomer and a diisocyanate are reacted to obtain an isocyanate-acrylate monomer, and the isocyanate group in the isocyanate-acrylate monomer structure reacts with two secondary amine groups in the fluorine-containing modified nano-silica molecular chain, thereby grafting acrylate onto the fluorine-containing modified nano-silica to obtain multi-functional fluorine-containing modified nano-silica, thereby solving the problems of easy migration of fluorine-containing anti-fouling agents and easy agglomeration of nano-silica, thereby significantly improving the scratch and stain resistance of the decorative film. DETAILED DESCRIPTION

[0043] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0044] Example 1

[0045] This embodiment provides a method for preparing multi-functional fluorine-containing modified nano-silicon dioxide, comprising the following steps:

[0046] A1. Under the condition of inert gas N2, fluoroacrylate (X=5) and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane in a molar ratio of 1:1 were added to anhydrous ethanol, stirred and reacted for 18 hours, and the anhydrous ethanol was removed by reduced pressure distillation at 70°C to obtain a fluorine-containing aminosilane coupling agent;

[0047] A2, dispersing 100g of nano-silica in a mixed solution of 1.5L of ethanol and 1.5L of deionized water, then adding 40g of fluorine-containing aminosilane coupling agent to react for 12h, filtering, washing and drying to obtain fluorine-containing modified nano-silica;

[0048] A3. Dissolve 100 g of hydroxyethyl methacrylate and 0.1 g of hydroquinone in 35 mL of acetone to obtain a mixed solution; mix 133.9 g of toluene diisocyanate and 0.9 g of dibutyltin dilaurate, heat to 30 ° C and add the mixed solution dropwise, heat to 50 ° C after the addition is complete, react for 2 hours, monitor the -NCO content in the reaction system and stop the reaction when it reaches half of the initial value to obtain isocyanate-acrylate monomer, then add a mixed solution of 130 g of fluorine-modified nano-silica and 430 mL of acetone to 100 g of isocyanate-acrylate monomer, react for 3 hours to obtain multi-functional fluorine-modified nano-silica.

[0049] Example 2

[0050] This embodiment provides a method for preparing multi-functional fluorine-containing modified nano-silicon dioxide, comprising the following steps:

[0051] A1. Under the condition of inert gas N2, fluoroacrylate (X=6) and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane in a molar ratio of 1.05:1 were added to anhydrous ethanol, stirred and reacted for 24 hours, and the anhydrous ethanol was removed by reduced pressure distillation at 70°C to obtain a fluorine-containing aminosilane coupling agent;

[0052] A2, dispersing 100g of nano-silica in a mixed solution of 1.3L of ethanol and 2.7L of deionized water, then adding 70g of fluorine-containing aminosilane coupling agent to react for 18h, filtering, washing and drying to obtain fluorine-containing modified nano-silica;

[0053] A3. Dissolve 106 g of hydroxypropyl methacrylate and 0.15 g of hydroquinone in 39 mL of acetone to obtain a mixed solution; mix 171 g of isophorone diisocyanate and 1.67 g of dibutyltin dilaurate, heat to 40 ° C and then drop the mixed solution, heat to 60 ° C after the addition is complete, react for 3 hours, monitor the -NCO content in the reaction system and stop the reaction when it reaches half of the initial value to obtain isocyanate-acrylate monomer, then add a mixed solution of 157 g of fluorine-modified nano-silica and 524 mL of acetone to 200 g of isocyanate-acrylate monomer, and react for 5 hours to obtain multi-functional fluorine-modified nano-silica.

[0054] Example 3

[0055] This embodiment provides a method for preparing multi-functional fluorine-containing modified nano-silicon dioxide, comprising the following steps:

[0056] A1. Under the condition of inert gas N2, fluoroacrylate (X=8) and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane in a molar ratio of 1.1:1 were added to anhydrous ethanol, stirred and reacted for 32 hours, and the anhydrous ethanol was removed by reduced pressure distillation at 70°C to obtain a fluorine-containing aminosilane coupling agent;

[0057] A2, dispersing 100g of nano-silica in a mixed solution of 1.5L of ethanol and 4.5L of deionized water, then adding 100g of fluorine-containing aminosilane coupling agent to react for 24h, filtering, washing and drying to obtain fluorine-containing modified nano-silica;

[0058] A3. Dissolve 110 g of hydroxyethyl acrylate and 0.2 g of hydroquinone in 42 mL of acetone to obtain a mixed solution; mix 175 g of hexamethylene diisocyanate and 2.28 g of stannous octoate, heat to 45 ° C and drop the mixed solution, heat to 60 ° C after the addition is complete, react for 4 hours, monitor the -NCO content in the reaction system and stop the reaction when it reaches half of the initial value to obtain isocyanate-acrylate monomer, then add a mixed solution of 100 g of fluorine-modified nano-silica and 335 mL of acetone to 237 g of isocyanate-acrylate monomer, and react for 8 hours to obtain multi-functional fluorine-modified nano-silica.

[0059] Comparative Example 1

[0060] Perfluoropolyether diol (M=2000), isophorone diisocyanate and dibutyltin dilaurate were mixed evenly, the temperature was raised to 60°C and kept for reaction for 2 hours, and then hydroxyethyl acrylate and hydroquinone were added, and the reaction was continued at 60°C for 3 hours to obtain fluorine-containing polyurethane acrylate.

[0061] Comparative Example 2

[0062] Compared with Example 1, the aminosilane coupling agent in Comparative Example 2 is replaced by KH550, that is, the structure contains only one amino group, and the other steps and raw materials are the same as those in Example 1.

[0063] Example 4

[0064] An EB-cured anti-scratch and anti-fouling decorative film comprises the following components in parts by weight: 35 parts of polyurethane acrylate (17 parts of monofunctional polyurethane acrylate and 18 parts of trifunctional polyurethane acrylate), 10 parts of reactive diluent (9 parts of isobornyl acrylate and 1 part of trimethylolpropane triacrylate), 30 parts of multifunctional fluorine-containing modified nano-silica prepared in Example 1, 0.7 parts of leveling agent BYK306, and 2 parts of xylene.

[0065] A method for preparing an EB-cured scratch-resistant and stain-resistant decorative film comprises the following steps:

[0066] B1. Mix the above components in proportion to form a coating, and apply it on the surface of a PVC film substrate with a thickness of 0.1 mm. The coating amount is 10 g / m 2 , forming a slurry layer;

[0067] B2. Electron beam (EB) curing treatment is performed under anaerobic conditions, the EB curing dose is 30 kGy, and the EB curing voltage is 140 keV, to obtain an EB-cured scratch-resistant and stain-resistant decorative film.

[0068] Example 5

[0069] An EB-cured anti-scratch and anti-fouling decorative film comprises the following components in parts by weight: 42 parts of polyurethane acrylate (19 parts of monofunctional polyurethane acrylate and 23 parts of trifunctional polyurethane acrylate), 13 parts of reactive diluent (11.3 parts of isobornyl acrylate and 1.7 parts of pentaerythritol triacrylate), 21 parts of multifunctional fluorine-containing modified nano-silica prepared in Example 2, 0.9 parts of leveling agent BYK306, and 2 parts of ethyl acetate.

[0070] A method for preparing an EB-cured scratch-resistant and stain-resistant decorative film comprises the following steps:

[0071] B1. Mix the above components in proportion to form a coating, and apply it on the surface of a PVC film substrate with a thickness of 0.2 mm. The coating amount is 19 g / m 2 , forming a slurry layer;

[0072] B2. Electron beam (EB) curing treatment was performed under anaerobic conditions, the EB curing dose was 43 kGy, and the EB curing voltage was 160 keV, to obtain an EB-cured scratch-resistant and stain-resistant decorative film.

[0073] Example 6

[0074] An EB-cured scratch-resistant and stain-resistant decorative film comprises the following components in parts by weight: 46 parts of polyurethane acrylate (16.4 parts of monofunctional polyurethane acrylate and 29.6 parts of trifunctional polyurethane acrylate), 16 parts of reactive diluent (13.3 parts of ethyl methacrylate and 2.7 parts of trimethylolpropane triacrylate), 19 parts of multifunctional fluorine-containing modified nano-silica prepared in Example 2, 1 part of leveling agent BYK306, and 4 parts of ethyl acetate.

[0075] A method for preparing an EB-cured scratch-resistant and stain-resistant decorative film comprises the following steps:

[0076] B1. Mix the above components in proportion to form a coating, and apply it on the surface of a PVC film substrate with a thickness of 0.2 mm. The coating amount is 24 g / m 2 , forming a slurry layer;

[0077] B2. Electron beam (EB) curing treatment was performed under anaerobic conditions, the EB curing dose was 54 kGy, and the EB curing voltage was 210 keV, to obtain an EB-cured scratch-resistant and stain-resistant decorative film.

[0078] Example 7

[0079] An EB-cured scratch-resistant and stain-resistant decorative film comprises the following components in parts by weight: 48 parts of polyurethane acrylate (16 parts of monofunctional polyurethane acrylate and 32 parts of trifunctional polyurethane acrylate), 15 parts of reactive diluent (12 parts of isobutyl methacrylate and 3 parts of trimethylolpropane triacrylate), 18 parts of multifunctional fluorine-containing modified nano-silica prepared in Example 2, 1.2 parts of leveling agent BYK306, and 5 parts of butyl acetate.

[0080] A method for preparing an EB-cured scratch-resistant and stain-resistant decorative film comprises the following steps:

[0081] B1. Mix the above components in proportion to form a coating, and apply it on the surface of a PVC film substrate with a thickness of 0.2 mm. The coating amount is 27 g / m 2 , forming a slurry layer;

[0082] B2. Electron beam (EB) curing treatment is performed under anaerobic conditions, the EB curing dose is 60 kGy, and the EB curing voltage is 237 keV, to obtain an EB-cured scratch-resistant and stain-resistant decorative film.

[0083] Example 8

[0084] An EB-cured scratch-resistant and stain-resistant decorative film comprises the following components in parts by weight: 50 parts of polyurethane acrylate (16.7 parts of monofunctional polyurethane acrylate and 33.3 parts of trifunctional polyurethane acrylate), 20 parts of reactive diluent (15.4 parts of tert-butyl methacrylate and 4.6 parts of pentaerythritol triacrylate), 15 parts of multifunctional fluorine-containing modified nano-silica prepared in Example 3, 1.5 parts of leveling agent BYK306, and 7 parts of acetone.

[0085] A method for preparing an EB-cured scratch-resistant and stain-resistant decorative film comprises the following steps:

[0086] B1. Mix the above components in proportion to form a coating, and apply it on the surface of a PVC film substrate with a thickness of 0.2 mm. The coating amount is 30 g / m 2 , forming a slurry layer;

[0087] B2. Electron beam (EB) curing treatment is performed under anaerobic conditions, the EB curing dose is 68 kGy, and the EB curing voltage is 280 keV, to obtain an EB-cured scratch-resistant and stain-resistant decorative film.

[0088] Comparative Example 3

[0089] Compared with Example 4, in Comparative Example 3, the multi-functional fluorine-containing modified nano-silica prepared in Example 1 is replaced by the fluorine-containing polyurethane acrylate and nano-silica prepared in Comparative Example 1, and the fluorine-containing polyurethane acrylate and nano-silica are physically blended into the coating matrix; wherein, 17 parts of fluorine-containing polyurethane acrylate and 13 parts of nano-silica are used, and the other steps and raw materials are synchronized with Example 4.

[0090] Comparative Example 4

[0091] Compared with Example 4, in Comparative Example 4, the multifunctional fluorine-containing modified nano-silica prepared in Example 1 is replaced with 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane and nano-silica, and 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane and nano-silica are physically blended into the coating matrix; wherein, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane is 17 parts, nano-silica is 13 parts, and other steps and raw materials are synchronized with Example 4.

[0092] Comparative Example 5

[0093] Compared with Example 4, in Comparative Example 5, the multi-functional fluorine-containing modified nano-silica prepared in Example 1 is replaced by the multi-functional fluorine-containing modified nano-silica prepared in Comparative Example 2, and the other steps and raw materials are the same as those in Example 4.

[0094] Comparative Example 6

[0095] Compared with Example 4, in Comparative Example 6, 17 parts of monofunctional polyurethane acrylate and 18 parts of trifunctional polyurethane acrylate are replaced with 35 parts of monofunctional polyurethane acrylate, and other steps and raw materials are the same as those in Example 4.

[0096] Performance Testing

[0097] The scratch resistance and stain resistance tests were carried out with reference to GB / T 17657-2022 "Test methods for physical and chemical properties of wood-based panels and veneered wood-based panels", and the results are shown in Table 1.

[0098] Table 1

[0099]

[0100]

[0101] It can be seen from the data in Table 1 that the decorative film prepared by the present invention has excellent scratch resistance and stain resistance. It can be seen from the data of Comparative Example 4 and Comparative Examples 3 and 4 that the scratch resistance is reduced because the nano-silicon dioxide is directly physically added to the coating matrix. At the same time, it can be seen from the data of Comparative Example 4 that the stain resistance of the decorative film obtained by using 1H, 1H, 2H, 2H-perfluorooctyl triethoxysilane as a fluorine-containing anti-fouling additive is significantly reduced. It can be seen from the data of Comparative Example 4 and Comparative Example 5 that the aminosilane coupling agent is replaced with a silane coupling agent with only one amino group on the molecular chain, so that the isocyanate-acrylate monomer grafted on the obtained multi-functional fluorine-containing modified nano-silicon dioxide is less, resulting in a decrease in the degree of crosslinking, and then resulting in a decrease in scratch resistance. It can be seen from the data of Comparative Example 4 and Comparative Example 6 that since only monofunctional polyurethane acrylate is used as a raw material in Comparative Example 6, the crosslinking density of the coating is reduced, the hardness is reduced, and the scratch resistance of the decorative film is significantly reduced.

[0102] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0103] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. An EB-cured scratch-resistant and stain-resistant decorative film, characterized in that: The invention comprises the following components in parts by weight: 35-50 parts of polyurethane acrylate, 10-20 parts of active diluent, 15-30 parts of multifunctional fluorine-containing modified nano-silicon dioxide, 0.7-1.5 parts of auxiliary agent, and 0-10 parts of solvent; The polyurethane acrylate is a mixture of monofunctional polyurethane acrylate and trifunctional polyurethane acrylate; the mass ratio of the monofunctional polyurethane acrylate to the trifunctional polyurethane acrylate is 1:(1-2); The active diluent is a mixture of a monofunctional acrylate monomer and a trifunctional acrylate monomer; the mass ratio of the monofunctional acrylate monomer to the trifunctional acrylate monomer is 1:(0.1-0.3); The preparation method of the multi-functional fluorine-containing modified nano-silicon dioxide comprises the following steps: A1. Under inert gas conditions, add fluoroacrylate and aminosilane coupling agent to anhydrous ethanol, stir and react for 18-32 hours, and remove anhydrous ethanol by reduced pressure distillation to obtain a fluorine-containing aminosilane coupling agent; A2, dispersing nano-silica in a mixed solution of ethanol and deionized water, and then adding a fluorine-containing aminosilane coupling agent for modification to obtain fluorine-containing modified nano-silica; A3, dissolving hydroxy acrylate monomer and hydroquinone in acetone to obtain a mixed solution; mixing diisocyanate and catalyst, heating to 30-45°C and then dropping the mixed solution, heating to 50-60°C after the dropping is complete to react for 2-4h, monitoring the -NCO content in the reaction system to reach a threshold, obtaining isocyanate-acrylate monomer, then adding a mixed solution of fluorine-modified nano-silica and acetone, reacting for 3-8h, and obtaining multifunctional fluorine-modified nano-silica; In the step A1, the molar ratio of fluoroacrylate to aminosilane coupling agent is (1-1.1):1; In step A1, the fluoroacrylate is CH2=C(CH3)-COOR, wherein R=-CH2(CF2) X H, X=5-8; the aminosilane coupling agent is at least one of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane.

2. The EB-cured scratch-resistant and stain-resistant decorative film according to claim 1, characterized in that: In the step A2, the ratio of the mixed solution of nano-silica, ethanol and deionized water to the fluorine-containing aminosilane coupling agent is 1 g: (30-60) mL: (0.4-1) g.

3. The EB-cured scratch-resistant and stain-resistant decorative film according to claim 1, characterized in that: In the step A3, the usage ratio of hydroxyacrylate monomer, hydroquinone and acetone is (10-11) g: (0.01-0.02)g:(3.5-4.2)mL.

4. The EB-cured scratch-resistant and stain-resistant decorative film according to claim 1, characterized in that: In the step A3, the molar ratio of the hydroxy acrylate monomer to the diisocyanate is 1:(1-1.1).

5. The EB-cured scratch-resistant and stain-resistant decorative film according to claim 1, characterized in that: In the step A3, the mass ratio of the isocyanate-acrylate monomer to the fluorine-modified nano-silica is (1-4.8): (1.3-1.9).

6. The method for preparing the EB-cured scratch-resistant and stain-resistant decorative film according to any one of claims 1 to 5, characterized in that: The following steps are involved: B1, polyurethane acrylate, acrylate monomer, multifunctional fluorine-containing modified nano-silica, auxiliary silicone surfactant and solvent are mixed evenly to form a coating, and the coating is applied on the surface of the substrate to form a slurry layer; B2. Electron beam (EB) curing treatment is performed under anaerobic conditions to obtain an EB-cured scratch-resistant and stain-resistant decorative film.

7. The method for preparing an EB-cured scratch-resistant and stain-resistant decorative film according to claim 6, characterized in that: In the step B2, the dose of EB curing is 30-70 kGy, and the voltage of EB curing is 140-280 keV.

8. The method for preparing an EB-cured scratch-resistant and stain-resistant decorative film according to claim 6, characterized in that: In step B2, the coating amount of the coating is 10-30 g / m 2 .

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