Wear-resistant decorative paper and method for producing the same

Abstract

The application relates to the field of decorative materials, in particular to a wear-resistant decorative paper and a preparation method thereof. The preparation method of the wear-resistant decorative paper comprises the following steps: coating wear-resistant paint on the surface of base paper to form a wear-resistant coating layer through drying treatment, so that the wear-resistant decorative paper is prepared; the wear-resistant paint is prepared by using acrylic acid hydroxy ester, ethyl acrylate and methyl methacrylate, so that the wear-resistant paint has good adhesion; the wear-resistant paint is prepared by using divinylbenzene and styrene, so that the hardness and strength of the film layer formed by the wear-resistant paint are improved; the wear-resistant paint is prepared by using vinyl silicone oil, so that the flexibility and water / oil repellency of the film layer formed by the wear-resistant paint are improved; the wear-resistant paint is prepared by using acrylic acid hydroxy ester, ethyl acrylate, methyl methacrylate, divinylbenzene, styrene and vinyl silicone oil, so that the prepared wear-resistant decorative paper has excellent wear resistance.

Description

Technical Field

[0001] This application relates to the field of decorative materials, and in particular to a wear-resistant decorative paper and a method for preparing the same. Background Technology

[0002] Decorative paper is a type of industrial specialty paper made from wood pulp fiber and organic fillers through papermaking processes, followed by printing or embossing and impregnation processes. Decorative paper is mainly used for decorating the surfaces of wood flooring, door panels, and engineered wood products, and its applications are quite widespread.

[0003] However, due to the poor abrasion resistance of existing general decorative paper, powder and lint will fall off during printing or use, which will reduce the gloss of the surface and the clarity of the pattern, affecting the appearance and shortening the service life of the decorative paper. Summary of the Invention

[0004] To address the problem of poor abrasion resistance in existing decorative papers, this application provides an abrasion-resistant decorative paper and its preparation method.

[0005] In a first aspect, this application provides a method for preparing wear-resistant decorative paper.

[0006] A method for preparing wear-resistant decorative paper includes the following preparation steps:

[0007] Preparation of wear-resistant decorative paper: A wear-resistant coating is applied to the surface of the base paper, and then dried to form a wear-resistant coating, thus preparing wear-resistant decorative paper;

[0008] The method for preparing the wear-resistant coating is as follows:

[0009] A wear-resistant coating is prepared by mixing 5-8 parts of divinylbenzene, 4-6 parts of styrene, 10-15 parts of vinyl silicone oil, 3-10 parts of ethyl acrylate, 3-6 parts of methyl methacrylate, 3-8 parts of hydroxyl acrylate, 15-20 parts of xylene, 1-2 parts of polyoxypropylene glycerol ether, and 0.001-0.01 parts of azobisisobutyronitrile (AIBN). The mixture is stirred and reacted at 70-90°C for 1.5-4 hours.

[0010] By adopting the above technical solutions, the use of hydroxyl acrylate, ethyl acrylate, and methyl methacrylate in the wear-resistant coating results in good adhesion performance; the use of divinylbenzene and styrene in the wear-resistant coating enhances the hardness and strength of the film formed by the wear-resistant coating; the use of vinyl silicone oil in the wear-resistant coating improves the flexibility and water and oil repellency of the film formed by the wear-resistant coating; and the combined use of hydroxyl acrylate, ethyl acrylate, methyl methacrylate, divinylbenzene, styrene, and vinyl silicone oil in the wear-resistant coating results in excellent wear resistance in the prepared wear-resistant decorative paper.

[0011] Preferably, the hydroxy acrylate is at least one of hydroxyethyl methacrylate, caprolactone acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl phosphate acrylate, and N-hydroxymethylacrylamide.

[0012] By adopting the above technical solution and optimizing the type of hydroxyl acrylate, the adhesion performance of the wear-resistant coating is improved, thereby enhancing the wear resistance of the wear-resistant decorative paper.

[0013] Preferably, during the preparation of the wear-resistant coating, 1-5 parts by weight of modified silica, 0.001-0.01 parts by weight of dibutyltin disilicate and 3-8 parts by weight of glycidyl acrylate are added. The modified silica is prepared by modifying the surface of nano silica with a vinyl silane coupling agent.

[0014] By adopting the above technical solutions, silica improves the hardness and adhesion of the coating, thereby enhancing the wear resistance of the formed coating; the surface modification of silica using a vinyl silane coupling agent allows the vinyl groups in the vinyl silane coupling agent to undergo polymerization with the unsaturated bonds in the raw materials of the wear-resistant coating, improving the dispersion performance of silica and its bonding strength with other raw materials in the coating; the use of glycidyl acrylate can enhance the cohesion and adhesion of the wear-resistant coating, thereby improving the wear resistance of the wear-resistant decorative paper.

[0015] Preferably, 3-6 parts by weight of fluorinated acrylic acid are added during the preparation of the wear-resistant coating;

[0016] The fluorinated acrylic acid is at least one of the following: fluorooctyl ethyl acrylate, dodecafluoroheptyl methacrylate, fluorooctyl acrylate, hexafluorobutyl methacrylate, and perfluorodecyl acrylate.

[0017] By adopting the above technical solution, fluorinated acrylic acid is used in the wear-resistant coating to improve the adhesion and hardness of the wear-resistant coating, while reducing the surface energy of the film layer, thereby improving the wear resistance and water and oil repellency of the wear-resistant decorative paper.

[0018] Preferably, 2-4 parts by weight of cationic unsaturated substances are added during the preparation of the wear-resistant coating;

[0019] The cationic unsaturated substance is 1-allyl-3-vinylimidazolium chloride and / or 1-allyl-3-methylimidazolium chloride.

[0020] By adopting the above technical solution, 1-allyl-3-vinylimidazolium chloride and / or 1-allyl-3-methylimidazolium chloride containing unsaturated bonds and cations are used in the wear-resistant coating to improve the adhesion and hardness of the wear-resistant coating on the base paper, thereby improving the wear resistance of the wear-resistant decorative paper.

[0021] Preferably, the vinyl silicone oil has a viscosity of 1000-10000 mPa·s and a vinyl content of 0.35-0.8%.

[0022] By adopting the above technical solution, the viscosity and vinyl content of the vinyl silicone oil are optimized, and the vinyl silicone oil is more evenly distributed in the wear-resistant coating and the formed film layer, thereby improving the flexibility of the wear-resistant coating and reducing the surface energy of the wear-resistant coating, thus improving the wear resistance and water and oil repellency of the wear-resistant decorative paper.

[0023] Preferably, a primer layer is provided between the base paper and the wear-resistant coating;

[0024] Preparation of the primer layer: The primer coating is applied to the surface of the base paper and dried to form the primer layer; The wear-resistant coating is applied to the primer layer on the surface of the base paper to form a wear-resistant coating.

[0025] The raw materials of the primer coating, by weight, include 25-35 parts of melamine-formaldehyde resin, 0.1-0.6 parts of ammonium chloride, 6-12 parts of modified titanium dioxide, 0.3-0.6 parts of polysorbate-40, 0.5-1 parts of sodium dodecylbenzenesulfonate, 3-5 parts of triglycerides, and 0.2-0.6 parts of polyoxypropylene glycerol ether.

[0026] The modified titanium dioxide is prepared by modifying the surface of nano-titanium dioxide with a silane coupling agent.

[0027] By adopting the above technical solution, melamine-formaldehyde resin and ammonium chloride are used to form a network structure in the primer coating, which has good viscosity and mechanical properties, and improves the bonding force between the wear-resistant coating and the base paper. In addition, the hydroxyl groups in the melamine-formaldehyde resin react with the epoxy groups of glycidyl acrylate in the wear-resistant coating, and can form hydrogen bonds with the hydroxyl groups in the hydroxyl acrylate, which can improve the bonding force between the wear-resistant coating and the base paper, thereby improving the wear resistance of the wear-resistant decorative paper.

[0028] Modified titanium dioxide with a silane coupling agent on its surface exhibits good dispersion performance in melamine-formaldehyde resin in primer coatings and enhances its bonding performance with melamine-formaldehyde resin. Furthermore, the photosensitive nano-titanium dioxide containing multiple hydroxyl groups can react with the epoxy groups of glycidyl acrylate and form hydrogen bonds with the hydroxyl groups in the acrylate, thereby improving the adhesion of the primer coating and further enhancing the bonding force between the wear-resistant coating and the base paper, thus improving the wear resistance of the wear-resistant decorative paper.

[0029] Triglycerides have good wetting, penetrating and adhesive properties, and can penetrate into the base paper, which not only improves the strength and toughness of the base paper, but also enhances the bonding force between the primer coating and the base paper, thereby improving the abrasion resistance of the abrasion-resistant decorative paper.

[0030] Preferably, the silane coupling agent is an epoxy-based silane coupling agent.

[0031] By adopting the above technical solution, the preferred silane coupling agent is an epoxy-type silane coupling agent. The epoxy-type silane coupling agent has a strong binding force with the hydroxyl groups in melamine-formaldehyde resin and / or the hydroxyl groups in acrylic hydroxy esters in wear-resistant coatings, which further enhances the cohesive force of the primer layer and the bonding force between the primer layer and the wear-resistant coating, thereby improving the wear resistance of the wear-resistant decorative paper.

[0032] Preferably, the raw materials of the primer coating also include 0.5-1.5 parts by weight of carboxycellulose.

[0033] By adopting the above technical solution, carboxycellulose is used to improve the adhesion and stability of the primer layer, thereby improving the wear resistance of the wear-resistant decorative paper.

[0034] On the other hand, this application provides a wear-resistant decorative paper.

[0035] A wear-resistant decorative paper is prepared using the wear-resistant decorative paper preparation method of this application.

[0036] By adopting the above technical solution, the prepared abrasion-resistant decorative paper has excellent abrasion resistance and water and oil repellency.

[0037] In summary, this application has the following beneficial effects:

[0038] A method for preparing wear-resistant decorative paper involves coating a wear-resistant coating onto the surface of a base paper, followed by drying to form a wear-resistant coating layer, thereby obtaining the wear-resistant decorative paper. The wear-resistant coating incorporates hydroxyl acrylate, ethyl acrylate, and methyl methacrylate to improve its adhesion. Divinylbenzene and styrene are also incorporated to enhance the hardness and strength of the film formed by the wear-resistant coating. Vinyl silicone oil is used to improve the flexibility and waterproof, water-repellent, and oil-repellent properties of the film formed by the wear-resistant coating. The combined use of hydroxyl acrylate, ethyl acrylate, methyl methacrylate, divinylbenzene, styrene, and vinyl silicone oil in the wear-resistant coating results in a wear-resistant decorative paper with excellent wear resistance.

[0039] 2. Further modifications of silica, fluorinated acrylic acid, 1-allyl-3-vinylimidazolium chloride and / or 1-allyl-3-methylimidazolium chloride and glycidyl acrylate are used in combination with hydroxyl acrylate, ethyl acrylate, methyl methacrylate, divinylbenzene, styrene and vinyl silicone oil in the wear-resistant coating to further enhance the cohesiveness of the wear-resistant coating and the bonding force between the wear-resistant coating and the base paper, thereby improving the wear resistance of the wear-resistant decorative paper.

[0040] 3. Furthermore, a primer layer is provided between the base paper and the wear-resistant coating; the raw materials of the primer coating include melamine-formaldehyde resin, ammonium chloride, modified titanium dioxide, polysorbate-40, sodium dodecylbenzene sulfonate, triglycerides and polyoxypropylene glycerol ether; this further enhances the bonding force between the wear-resistant coating and the base paper, thereby improving the wear resistance of the wear-resistant decorative paper. Detailed Implementation

[0041] raw material

[0042] Melamine-formaldehyde resin (liquid, 50% solids content, 0.3% free formaldehyde, viscosity: 25℃, 4-cup, 20 seconds), carboxymethyl cellulose (2% aqueous solution, viscosity 900 mPa·s), base paper (kraft paper, burst strength index: 10 Pa·s). 2 / g, ignition point 220℃), polyoxypropylene glycerol ether (average molecular weight 1000).

[0043] Preparation Example

[0044] Preparation Example 1-1: A modified silica, the preparation method of which is as follows:

[0045] 10 g of vinyltrimethoxysilane was added to a 5 L aqueous solution with pH 4 and stirred for 15 min. Then, 1 kg of silica (D50 particle size of 20 nm) was added for surface modification. The silica was filtered and washed with water until neutral to obtain modified silica.

[0046] Preparation Examples 1-2: A modified silica, prepared by the following method:

[0047] Surface modification: 15g of tritert-butoxyvinylsilane was added to 5L of aqueous solution with pH 5 and stirred for 20min. Then 1kg of silica (D50 particle size of 30nm) was added to carry out surface modification. The silica was filtered and washed with water until neutral to obtain modified silica.

[0048] Preparation Examples 1-3: A modified silica, prepared by the following method:

[0049] Surface modification: 20g of tritert-butoxyvinylsilane was added to 5L of aqueous solution at pH 6 and stirred for 10min. Then 1kg of silica (D50 particle size of 10nm) was added to carry out surface modification. The silica was filtered and washed with water until neutral to obtain modified silica.

[0050] Preparation Examples 1-4, a modified silica, differs from Preparation Example 1-1 in that γ-aminopropyltrimethoxysilane is used to replace vinyltrimethoxysilane in an equal amount.

[0051] Preparation Examples 1-5, a modified silica, differs from Preparation Example 1-1 in that γ-mercaptopropyltrimethoxysilane is used to replace vinyltrimethoxysilane in an equal amount.

[0052] Preparation Example 2-1: A modified titanium dioxide, prepared by the following method:

[0053] 15g of γ-glycidyl ether propyltrimethoxysilane was added to a 5L aqueous solution with pH 4 and stirred for 15min. Then, 1kg of titanium dioxide (D50 particle size of 20nm) was added for surface modification. The mixture was filtered and washed with water until neutral to obtain modified titanium dioxide.

[0054] Preparation Example 2-2: A modified titanium dioxide, prepared by the following method:

[0055] 25g of 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane was added to a 3L aqueous solution with pH 4 and stirred for 10min. Then, 1kg of titanium dioxide (D50 particle size of 30nm) was added for surface modification. After filtration and washing with water until neutral, the mixture was dried to obtain modified titanium dioxide.

[0056] Preparation Examples 2-3: A modified titanium dioxide, prepared by the following method:

[0057] 35g of 2γ-glycidyl ether propyltrimethoxysilane was added to a 3L aqueous solution with pH 4 and stirred for 20min. Then, 1kg of titanium dioxide (D50 particle size of 10nm) was added for surface modification. After filtration and washing with water until neutral, the mixture was dried to obtain modified titanium dioxide.

[0058] Preparation Example 2-4, a modified titanium dioxide, differs from Preparation Example 2-1 in that it uses tri-tert-butoxyvinylsilane to replace γ-glycidyl ether propyltrimethoxysilane in an equal amount.

[0059] Preparation Example 2-5, a modified titanium dioxide, differs from Preparation Example 2-1 in that γ-mercaptopropyltrimethoxysilane is replaced by an equal amount of γ-glycidyl ether propyltrimethoxysilane. Example

[0060] Example 1: A method for preparing wear-resistant decorative paper, comprising the following preparation steps:

[0061] Preparation of primer coating: Add the raw materials for primer coating (as shown in Table 1) to a mixing tank and stir for 15 minutes at 600 r / min to prepare primer coating.

[0062] Preparation of primer layer: The primer coating is applied to the surface of the base paper and then placed at 130±5℃ for 1.0±0.5h to form a primer layer with a thickness of 0.2±0.05mm.

[0063] Preparation of wear-resistant coating: Divinylbenzene, styrene, vinyl silicone oil, glycidyl acrylate, ethyl acrylate, methyl methacrylate, hydroxyl acrylate, xylene, polyoxypropylene glycerol ether, modified silica, fluorinated acrylic acid, cationic unsaturated substances, dibutyltin disilicate and azobisisobutyronitrile are added to a reaction vessel and stirred for 1.5 h at 800 r / min and 90℃ to prepare wear-resistant coating.

[0064] Preparation of wear-resistant decorative paper: A wear-resistant coating is applied to the surface of the primer layer of the base paper and placed at 120±5℃ for 1.0±0.5h to form a wear-resistant coating with a thickness of 0.4±0.05mm, thus obtaining wear-resistant decorative paper.

[0065] Examples 2 and 3 describe a method for preparing wear-resistant decorative paper. The difference between this method and Example 1 lies in the types and weights of raw materials used in the primer and wear-resistant coating, as well as the different process parameters for preparing the primer. Please refer to Tables 1 and 2 for details.

[0066] Table 1 lists the types and weights of raw materials used in the preparation methods of wear-resistant decorative paper in Examples 1-3, as well as the settings of the preparation process parameters for the wear-resistant coatings.

[0067]

[0068] Table 2 lists the types and weights of raw materials used in the primer coating in the preparation methods of wear-resistant decorative paper in Examples 1-3.

[0069]

[0070] Examples 4 and 5 describe a method for preparing wear-resistant decorative paper, which differs from Example 1 in that the modified silica in the wear-resistant coating is the same as that used in Examples 1-4 to 1-5.

[0071] Examples 6 and 7 describe a method for preparing wear-resistant decorative paper, which differs from Example 1 in that the modified titanium dioxide in the primer coating is sequentially the modified titanium dioxide from Preparation Examples 2-4 to Preparation Examples 2-5.

[0072] Example 8, a method for preparing wear-resistant decorative paper, differs from Example 1 in that the modified titanium dioxide of Preparation Example 2-1 is used to replace the modified silicon dioxide in an equal amount in the wear-resistant coating; and the modified silicon dioxide of Preparation Example 1-1 is used to replace the modified titanium dioxide in an equal amount in the primer coating.

[0073] Example 9, a method for preparing wear-resistant decorative paper, differs from Example 1 in that modified silica is not used in the wear-resistant coating.

[0074] Example 10, a method for preparing wear-resistant decorative paper, differs from Example 1 in that glycidyl acrylate is not used in the wear-resistant coating.

[0075] Example 11, a method for preparing wear-resistant decorative paper, differs from Example 1 in that the wear-resistant coating does not use glycidyl acrylate, modified silica, and dibutyltin disilicate.

[0076] Example 12, a method for preparing wear-resistant decorative paper, differs from Example 1 in that modified titanium dioxide is not used in the primer coating.

[0077] Example 13, a method for preparing wear-resistant decorative paper, differs from Example 1 in that glycidyl acrylate and modified silica are not used in the wear-resistant coating; and modified titanium dioxide is not used in the primer coating.

[0078] Example 14, a method for preparing wear-resistant decorative paper, differs from Example 1 in that the vinyl silicone oil used is a vinyl silicone oil with a viscosity of 20000 mPa·s at 25°C and a vinyl content of 0.30%

[0079] Example 15, a method for preparing wear-resistant decorative paper, differs from Example 1 in that the wear-resistant coating does not use fluorooctyl ethyl acrylate.

[0080] Example 16, a method for preparing wear-resistant decorative paper, differs from Example 1 in that 1-allyl-3-vinylimidazolium chloride is not used in the wear-resistant coating.

[0081] Example 17, a method for preparing wear-resistant decorative paper, differs from Example 1 in that 1-allyl-3-vinylimidazolium chloride and fluoctyl ethyl acrylate are not used in the wear-resistant coating.

[0082] Example 18, a method for preparing wear-resistant decorative paper, differs from Example 1 in that carboxymethyl cellulose is not used in the primer coating.

[0083] Example 19, a method for preparing wear-resistant decorative paper, differs from Example 1 in that 1-allyl-3-vinylimidazolium chloride and fluoctyl ethyl acrylate are not used in the wear-resistant coating; and carboxymethyl cellulose is not used in the primer coating.

[0084] Example 20, a method for preparing wear-resistant decorative paper, differs from Example 1 in that carboxymethyl cellulose is used to replace triglycerides in an equal amount in the primer coating.

[0085] Example 21, a method for preparing wear-resistant decorative paper, differs from Example 1 in that titanium dioxide (D50 particle size of 20nm) is used to replace modified titanium dioxide in an equal amount in the primer coating; and silicon dioxide (D50 particle size of 20nm) is used to replace modified silicon dioxide in an equal amount in the wear-resistant coating.

[0086] Example 22, a method for preparing wear-resistant decorative paper, differs from Example 1 in that the wear-resistant coating does not use glycidyl acrylate, modified silica, fluorinated acrylic acid, dibutyltin dibutylsilicate and 1-allyl-3-vinylimidazolium chloride; and no primer coating is provided. Comparative Example

[0087] Comparative Example 1, a method for preparing wear-resistant decorative paper, differs from Example 22 in that styrene is used to replace divinylbenzene in an equal amount in the wear-resistant coating; and methyl methacrylate is used to replace hydroxyl acrylate in an equal amount.

[0088] Comparative Example 2, a method for preparing wear-resistant decorative paper, differs from Example 22 in that styrene is used to replace divinylbenzene in an equal amount in the wear-resistant coating; and ethyl acrylate is used to replace vinyl silicone oil in an equal amount in the wear-resistant coating.

[0089] Comparative Example 3, a method for preparing wear-resistant decorative paper, differs from Example 22 in that styrene is used to replace divinylbenzene in an equal amount in the wear-resistant coating; methyl methacrylate is used to replace hydroxyl acrylate in an equal amount; and ethyl acrylate is used to replace vinyl silicone oil in an equal amount.

[0090] Comparative Example 4, a method for preparing wear-resistant decorative paper, differs from Example 22 in that the wear-resistant coating uses 4 kg of divinylbenzene, 8 kg of styrene, 8 kg of vinyl silicone oil, and 2 kg of hydroxyl acrylate.

[0091] Test 1: Abrasion resistance

[0092] The abrasion resistance of the test samples was tested according to Method A in GB / T 9966.4.

[0093] Experimental steps:

[0094] The test sample is fixed onto the plate, and the mass of the plate with the test sample attached (M0) is weighed to an accuracy of 0.01g. The plate with the test sample attached is then mounted on an abrasion testing machine. Each fixture weighs 1250g, and a rotary abrasion test is performed on it for 1000 revolutions to complete one test.

[0095] Remove the sample, brush off the powder, and weigh the plate with the test sample fixed after grinding (M1), accurate to 0.01g.

[0096] Measure the two mutually perpendicular diameters at the abraded end of the test sample using vernier calipers, accurate to 0.1 cm. Calculate the abraded area (A) using the average of the two diameters.

[0097] Wear calculation:

[0098] M = (M0 - M1)A

[0099] Where: M - wear amount, g / cm 2 ;

[0100] M0: Sample mass before test (g); M1: Sample mass after test (g); A: Abrasion area of ​​the sample (cm²) 2 .

[0101] Experiment 2: Water contact angle

[0102] The water contact angle of the test sample was tested using a contact angle water droplet angle measuring instrument in accordance with GB / T 30693-2014.

[0103] Water contact angle decrease rate = (water contact angle before friction - water contact angle after friction) / water contact angle before friction.

[0104] Test 3: Oil Repellency Rating

[0105] The oil repellency rating of the test samples was tested according to the AATCC-118 test method. The oil repellency effect was the worst when the rating was 1 and the best when the rating was 8.

[0106] Test samples: The wear-resistant decorative paper prepared by the preparation method of wear-resistant decorative paper in Examples 1 to 22 is used as the example sample; the wear-resistant decorative paper prepared by the preparation method of wear-resistant decorative paper in Comparative Examples 1 to 4 is used as the comparative example sample.

[0107] The decrease in oil repellency level = oil repellency level before friction - oil repellency level after friction.

[0108] The friction conditions were conducted according to the test conditions in the wear resistance test of Experiment 1.

[0109] Experimental results: The test results of the abrasion resistance, water contact angle and oil repellency of the abrasion-resistant decorative paper prepared by the preparation methods of Examples 1 to 22 and Comparative Examples 1 to 4 are shown in Table 3.

[0110] Table 3. Test results of abrasion resistance, water contact angle, and oil repellency of the abrasion-resistant decorative papers prepared using the methods described in Examples 1 to 22 and Comparative Examples 1 to 4.

[0111]

[0112] Combining Examples 1 to 22 and Comparative Examples 1 to 4 with Table 3, it can be seen that:

[0113] The wear-resistant decorative paper prepared by the methods described in Examples 1 to 22 showed lower wear amount, water contact angle reduction rate, and oil repellency grade reduction than Comparative Examples 1 to 4. This indicates that the use of hydroxyl acrylate, ethyl acrylate, methyl methacrylate, divinylbenzene, styrene, and vinyl silicone oil in the wear-resistant coating results in a wear-resistant decorative paper with excellent wear resistance.

[0114] The reasons for this may be as follows: the use of hydroxyl acrylate, ethyl acrylate, and methyl methacrylate in the wear-resistant coating gives it good adhesion; the use of divinylbenzene and styrene in the wear-resistant coating improves the hardness and strength of the film formed by the coating; the use of vinyl silicone oil in the wear-resistant coating improves the flexibility and water and oil repellency of the film formed by the coating; and the use of hydroxyl acrylate, ethyl acrylate, methyl methacrylate, divinylbenzene, styrene, and vinyl silicone oil in the wear-resistant coating results in excellent wear resistance in the prepared wear-resistant decorative paper.

[0115] The wear-resistant decorative paper prepared by the methods described in Examples 1 to 3 showed lower wear amount and water contact angle reduction rate than that of Examples 4 to 7. This indicates that the modified silica in the wear-resistant coating uses vinyl silane and the modified titanium dioxide in the primer coating uses epoxy silane coupling agent, which makes the prepared wear-resistant decorative paper have better wear resistance.

[0116] The reason may be that: the use of vinyl silane coupling agents to modify the surface of silica allows the vinyl groups in the vinyl silane coupling agents to polymerize with the unsaturated bonds in the raw materials of the wear-resistant coating, improving the dispersion performance of silica and its bonding force with other raw materials in the coating, thereby improving the wear resistance of the wear-resistant decorative paper; the photosensitive modified titanium dioxide surface contains epoxy groups, which react with the hydroxyl groups of melamine-formaldehyde resin and the hydroxyl groups on the raw materials in the wear-resistant coating, thereby improving the toughness, strength and adhesion of the primer coating, further improving the wear resistance of the wear-resistant decorative paper.

[0117] The wear-resistant decorative paper prepared by the methods described in Examples 1 to 3 showed lower wear and water contact angle reduction rates than that of Examples 8 to 13. This indicates that the use of modified silica and glycidyl acrylate in the wear-resistant coating and the use of modified titanium dioxide in the primer coating resulted in the prepared wear-resistant decorative paper having better wear resistance and water and oil repellency.

[0118] The reasons for this may be as follows: Firstly, modified titanium dioxide has small particle size, large specific surface area, high surface energy, and insufficient surface atomic coordination, resulting in strong surface activity and adsorption capacity. Secondly, when modified titanium dioxide is added to primer coatings, the hydroxyl active groups on its surface easily bond with the polar groups in the primer coating, and can react with the epoxy groups in the glycidyl acrylate in the wear-resistant coating. The epoxy groups on the surface of modified titanium dioxide can also react with the hydroxyl groups contained in the raw materials of the primer coating and the wear-resistant coating. Compared with modified silica, modified titanium dioxide has a better compatibility with melamine-formaldehyde resin, improving the adhesion, strength, toughness of the primer coating, and the bonding force between it and the wear-resistant coating.

[0119] Compared to modified titanium dioxide, modified silica can better improve the hardness, strength, and waterproof and seepage-proof performance of the coating film. Furthermore, the vinyl groups in modified silica participate in the polymerization reaction that occurs in the wear-resistant coating, resulting in a better synergistic effect between modified silica and other components in the wear-resistant coating. By using glycidyl acrylate and modified silica in the wear-resistant coating and modified titanium dioxide in the primer coating, the prepared wear-resistant decorative paper has good wear resistance and water and oil repellency.

[0120] The wear resistance and water contact angle reduction rate of the wear-resistant decorative paper prepared by the methods of Examples 1 to 3 are lower than those of Example 14. This indicates that the wear-resistant coating uses styrene, divinylbenzene and vinyl silicone oil in combination and the type of vinyl silicone oil is optimized, which improves the wear resistance and water and oil repellency of the prepared wear-resistant decorative paper.

[0121] The reason for this may be that the use of styrene and divinylbenzene in combination effectively improves the hardness and strength of the wear-resistant coating; vinyl silicone oil enhances the flexibility and hydrophobic and oleophobic properties of the wear-resistant coating; and optimizing the type of vinyl silicone oil results in a more uniform distribution of siloxane groups in the wear-resistant coating. The use of styrene, divinylbenzene, and vinyl silicone oil in combination, and the optimization of the type of vinyl silicone oil, thereby improves the wear resistance and water and oil repellency of the prepared wear-resistant decorative paper.

[0122] The wear resistance and water contact angle reduction rate of the wear-resistant decorative paper prepared by the preparation methods of Examples 1 to 3 are lower than those of Examples 15 to 19. This indicates that the use of 1-allyl-3-vinylimidazolium chloride and fluoctyl ethyl acrylate in the wear-resistant coating and the use of carboxymethyl cellulose in the primer coating further improve the wear resistance and water and oil repellency of the prepared wear-resistant decorative paper.

[0123] The reasons may be as follows: the use of fluorooctyl ethyl acrylate in the wear-resistant coating improves the adhesion, wear resistance, and water and oil repellency of the wear-resistant coating; the use of cationic 1-allyl-3-vinylimidazolium chloride in the wear-resistant coating not only improves the hardness of the wear-resistant coating, but also has a good compatibility with anionic carboxymethyl cellulose in the primer coating, further improving the wear resistance of the prepared wear-resistant decorative paper.

[0124] The wear resistance and water contact angle reduction rate of the wear-resistant decorative paper prepared by the methods of Examples 1 to 3 are lower than those of Example 20, indicating that the use of carboxymethyl cellulose and triglycerides in the primer coating improves the wear resistance of the prepared wear-resistant decorative paper.

[0125] The reason for this may be that triglycerides have good wetting, penetrating and adhesive properties, which can penetrate into the base paper, not only improving the strength and toughness of the base paper, but also improving the bonding force between the primer coating and the base paper when combined with carboxymethyl cellulose, thereby improving the wear resistance of the wear-resistant decorative paper.

[0126] The wear resistance and water contact angle reduction rate of the wear-resistant decorative paper prepared by the preparation method of Example 21 are higher than those of Examples 1 to 3. This may be because a larger amount of titanium dioxide is directly used in the primer coating; a larger amount of silica is used in the wear-resistant coating. The unmodified silica and titanium dioxide have poor dispersion properties, resulting in internal defects in the coating and poor synergistic effect with other raw materials in the coating, which in turn leads to a decrease in the wear resistance of the wear-resistant decorative paper.

[0127] The wear resistance and water contact angle reduction rate of the wear-resistant decorative paper prepared by the methods of Examples 1 to 3 are lower than those of Example 22. This indicates that the use of glycidyl acrylate, modified silica, dibutyltin disilicate and 1-allyl-3-vinylimidazolium chloride in the wear-resistant coating, along with the addition of a primer coating, improves the wear resistance of the prepared wear-resistant decorative paper.

[0128] The reason for this may be that the use of glycidyl acrylate, modified silica, dibutyltin disilicate, and 1-allyl-3-vinylimidazolium chloride in the wear-resistant coating, along with the addition of a primer coating, not only enhances the interaction between the raw material components in the wear-resistant coating and the primer coating, but also improves the cohesiveness and strength of the wear-resistant coating and the primer coating, and enhances the bonding force between the wear-resistant coating and the primer coating, thereby improving the wear resistance of the prepared wear-resistant decorative paper.

[0129] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A method for producing a wear-resistant decorative paper, characterized by The preparation method comprises the following steps: Preparation of the wear-resistant decorative paper: applying wear-resistant coating on the surface of the base paper, and drying to form a wear-resistant coating layer, thereby obtaining the wear-resistant decorative paper; The wear-resistant coating is prepared by mixing 5-8 parts by mass of divinylbenzene, 4-6 parts by mass of styrene, 10-15 parts by mass of vinyl silicone oil, 3-10 parts by mass of ethyl acrylate, 3-6 parts by mass of methyl methacrylate, 3-8 parts by mass of hydroxy acrylate, 15-20 parts by mass of dimethylbenzene, 1-2 parts by mass of polyoxypropylene glycerol ether, and 0.001-0.01 parts by mass of azobisisobutyronitrile, and then stirring and reacting at 70-90°C for 1.5-4 hours. In the preparation process of the wear-resistant coating, 1-5 parts by mass of modified silicon dioxide, 0.001-0.01 parts by mass of dibutyltin dimetasilicate, and 3-8 parts by mass of glycidyl acrylate are further added, wherein the modified silicon dioxide is prepared by modifying the surface of nano silicon dioxide with a vinyl silane coupling agent. In the preparation process of the wear-resistant coating, 3-6 parts by mass of fluorine-containing acrylic acid are further added; the fluorine-containing acrylic acid is at least one of fluoro-octyl ethyl acrylate, methyl methacrylate dodecafluoroheptyl ester, fluoro-octanol acrylate, methyl methacrylate hexafluorobutyl ester, and perfluorodecyl acrylate. In the preparation process of the wear-resistant coating, 2-4 parts by mass of cationic unsaturated substances are further added; the cationic unsaturated substances are 1-allyl-3-vinylimidazole chloride and / or 1-allyl-3-methyl imidazole chloride. A primer layer is arranged between the base paper and the wear-resistant coating layer. The primer layer is prepared by applying primer coating on the surface of the base paper, and then drying to form the primer layer; the wear-resistant coating is applied on the primer layer on the surface of the base paper to form the wear-resistant coating layer. The raw materials of the primer coating include, in parts by mass, 25-35 parts of melamine formaldehyde resin, 0.1-0.6 parts of ammonium chloride, 6-12 parts of modified titanium dioxide, 0.3-0.6 parts of polysorbate-40, 0.5-1 part of sodium dodecylbenzenesulfonate, 3-5 parts of triglycerol, and 0.2-0.6 parts of polyoxypropylene glycerol ether; the modified titanium dioxide is prepared by modifying the surface of nano titanium dioxide with a silane coupling agent; the silane coupling agent is an epoxy-based silane coupling agent; the raw materials of the primer coating further include 0.5-1.5 parts by mass of carboxymethyl cellulose.

2. A method of preparing a wear-resistant decorative paper according to claim 1, characterized in that, The hydroxy acrylate is at least one of hydroxyethyl methacrylate, caprolactone acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate phosphate, and N-hydroxymethyl acrylamide.

3. A method of preparing a wear resistant decorative paper according to claim 1, characterized in that, The viscosity of the vinyl silicone oil is 1000-10000 mPa·s, and the vinyl content is 0.35-0.8%.

4. A wear-resistant decorative paper prepared by the preparation method of any one of claims 1-3.

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