An antioxidant, waterproof and wear-resistant decorative paper and its preparation method

Abstract

The present invention relates to the technical field of decorative papers, and discloses an antioxidant, waterproof and wear-resistant decorative paper and a preparation method thereof. The method includes: polymerizing sodium carboxymethyl cellulose with acrylate monomers to obtain a cellulose-acrylate prepolymer; re-polymerizing a titanium dioxide-acrylate mixture dispersion with the cellulose-acrylate prepolymer to obtain a modified polyacrylate composite emulsion; mixing and reacting a silica template containing carbon-carbon double bonds, polyvinylpyrrolidone, azobisisobutyronitrile, styrene, divinylbenzene, and trifluoroethyl methacrylate, and obtaining polymer hollow microspheres after etching with an alkali solution; loading the polymer hollow microspheres with styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile to obtain a dispersion of modified polymer composite microspheres; impregnating the decorative paper with the modified polyacrylate composite emulsion, air-drying, and then double-sidedly coating with the dispersion of modified silica composite microspheres, and obtaining the antioxidant, waterproof and wear-resistant decorative paper after thermal initiation reaction.

Description

Technical Field

[0001] The present invention relates to the technical field of decorative papers, and particularly relates to an antioxidant, waterproof and wear-resistant decorative paper and a preparation method thereof. Background Art

[0002] Decorative paper is an important surface finishing material for artificial boards, which plays a role in protecting and beautifying artificial papers and their products. Decorative paper is made by printing and impregnating decorative base paper, but traditional dipping glue will release formaldehyde during production and use, which is harmful to human health.

[0003] With the improvement of people's requirements for the indoor environment, the development of formaldehyde-free impregnating adhesives for decorative papers has become the key to solving the problem. Formaldehyde-free impregnating adhesives mainly include natural adhesives, modified bio-based adhesives, high molecular resin formaldehyde-free impregnating adhesives, etc. In application, decorative paper is inevitably subject to external friction and scratching, resulting in wear of the surface printing surface and affecting the appearance effect. In addition, the surface of decorative paper is easily photo-oxidized, resulting in problems such as oxidation, discoloration and cracking, which affect its decorative effect.

[0004] The prior art such as Chinese Patent Application CN103074814A discloses a moisture-proof wallpaper. By adding bamboo charcoal to the wallpaper absorption layer, the wallpaper has the ability to release natural negative ions on the basis of breathable moisture absorption and odor removal. However, the prepared wallpaper lacks waterproof and wear-resistant performance and poor antioxidant property, which limits the application of the material in the field of decorative paper.

[0005] The prior art such as Chinese Patent Application CN115287943A discloses an antibacterial and wear-resistant decorative paper and a preparation method thereof. By using polystyrene acrylic microspheres as a template to prepare a hollow zinc oxide structure, using alumina as a wear-resistant medium and zinc oxide as an antibacterial material to be mixed and ball-milled together, the antibacterial ability of the material is improved. However, the prepared decorative paper has poor antioxidant property and lacks waterproof property, which limits the application of the material in the field of decorative paper. Summary of the Invention

[0006] The purpose of the present invention is to overcome the deficiencies of the prior art and provide an antioxidant, waterproof and wear-resistant decorative paper and a preparation method thereof. The antioxidant, waterproof and wear-resistant decorative paper has good mechanical properties, excellent antioxidant and weather resistance, and waterproof and wear-resistant properties.

[0007] To achieve the above purpose, the technical scheme adopted by the present invention is as follows:

[0008] A preparation method of an antioxidant, waterproof and wear-resistant decorative paper, comprising the following steps:

[0009] Step (1): Cetyltrimethylammonium bromide, acrylic acid, and methyl methacrylate are mixed evenly. Water is added, and tetrabutyl titanate and silane coupling agent are respectively dropped. After the dropping is completed, a reaction occurs. After the reaction ends, it is mixed with water and dispersed to obtain a titanium dioxide-acrylate mixture dispersion.

[0010] Step (2): Sodium carboxymethyl cellulose is dissolved by mixing with water, and then mixed with a buffer and a second initiator. An acrylate monomer is dropped, and a reaction occurs to obtain a cellulose-acrylate prepolymer. The titanium dioxide-acrylate mixture dispersion is dropped into the cellulose-acrylate prepolymer, and at the same time, a first initiator is dropped. After the dropping is completed, the reaction continues. After the reaction ends, it is cooled and the pH value is adjusted to obtain a modified polyacrylate composite emulsion.

[0011] Step (3): Ethanol and water are mixed evenly, ammonia water and tetraethyl orthosilicate are added, and a reaction occurs. After the reaction ends, vinyltriethoxysilane is added and the reaction continues to obtain a silica template containing carbon-carbon double bonds. The silica template containing carbon-carbon double bonds, polyvinylpyrrolidone, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol are mixed for a polymerization reaction. After the reaction ends, a polymer microsphere dispersion is obtained. The polymer microsphere dispersion is mixed with an aqueous sodium hydroxide solution for an etching reaction. After the reaction ends, it is filtered and washed to obtain polymer hollow microspheres. The polymer hollow microspheres, water, styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile are mixed evenly to obtain a modified polymer composite microsphere dispersion.

[0012] Step (4): The modified polyacrylate composite emulsion, water, and ethanol are mixed to obtain a composite emulsion diluent. Decorative paper is impregnated in the composite emulsion diluent and dried. After drying, the modified polymer composite microsphere dispersion is coated on both surfaces of the decorative paper, and a reaction occurs. After the reaction ends, an antioxidant, waterproof, and wear-resistant decorative paper is obtained.

[0013] Preferably, in step (1): the mass ratio of cetyltrimethylammonium bromide, acrylic acid, methyl methacrylate, water, tetrabutyl titanate, and silane coupling agent is (4 - 10):(6 - 14):(10 - 30):(10 - 15):(2 - 6):(1 - 4); the dropping time of tetrabutyl titanate and silane coupling agent is both 5 - 10 min; the reaction conditions are: stirring reaction at room temperature for 16 - 24 h.

[0014] Preferably, the silane coupling agent includes vinyltrimethoxysilane.

[0015] Preferably, in step (1), the dispersion includes stirring dispersion and ultrasonic dispersion.

[0016] Preferably, in the step (2): the conditions for the reaction to prepare the cellulose-acrylate prepolymer are: reacting in a nitrogen atmosphere at a temperature of 80 °C for 20 - 30 min.

[0017] Preferably, the acrylate monomer is prepared by mixing glycidyl methacrylate, methyl methacrylate, butyl acrylate, and 2-hydroxyethyl methacrylate in a mass ratio of (3 - 5):(3 - 5):(0.5 - 1):(0.5 - 1).

[0018] Preferably, in the step (2): the mass ratio of sodium carboxymethyl cellulose, buffer, first initiator, second initiator, acrylate monomer, and titanium dioxide-acrylate mixture dispersion is (110 - 140):(20 - 30):(5 - 6):(5 - 6):(200 - 300):(1200 - 1500).

[0019] Preferably, in the step (2): the conditions for dropping the titanium dioxide-acrylate mixture dispersion are: dropping for 1 - 2 h in a nitrogen atmosphere at a temperature of 80 °C; the conditions for dropping the first initiator are: dropping for 1.5 - 2.5 h in a nitrogen atmosphere at a temperature of 80 °C; the conditions for continuous reaction are: reacting at a temperature of 80 - 85 °C at a rotation speed of 100 - 120 r / min for 5 - 6 h. Preferably, the buffer includes sodium bicarbonate; both the first initiator and the second initiator are aqueous potassium persulfate solutions, and the aqueous potassium persulfate solution is a 1 - 3 wt% aqueous potassium persulfate solution; the mass ratio of the first initiator to the second initiator is 1:1.

[0020] Preferably, the regulator used to adjust the pH value includes 20 wt% ammonia water, and the pH value of the modified polyacrylate composite emulsion is 7.5 - 8.

[0021] Preferably, in the step (3): when preparing the silica template containing carbon-carbon double bonds, the volume ratio of ethanol, water, ammonia water, tetraethyl orthosilicate, and vinyltriethoxysilane is 100:33:4:10:3; the conditions for the reaction are: reacting at a temperature of 25 - 30 °C for 12 - 14 h; the conditions for continuous reaction are: reacting at a temperature of 25 - 30 °C for 12 - 14 h.

[0022] Further, the ammonia water is 28 wt% ammonia water.

[0023] Preferably, in the step (3): when preparing the polymer microsphere dispersion liquid, the mass ratio of the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol is 3:2:(0.16 - 0.24):4:(1.2 - 1.4):3:(5 - 10):(35 - 40); the conditions for the polymerization reaction are: stirring and reacting at a temperature of 75 - 85°C for 6 - 7 h; the mass ratio of the polymer microsphere dispersion liquid to the sodium hydroxide aqueous solution is 1:(1 - 1.2); the conditions for the etching reaction are: etching and reacting at a temperature of 75 - 80°C for 4 h.

[0024] Preferably, the polyvinylpyrrolidone includes polyvinylpyrrolidone K30.

[0025] Further, the sodium hydroxide aqueous solution is a 2 mol / L sodium hydroxide aqueous solution.

[0026] Preferably, in the step (3): when preparing the modified polymer composite microsphere dispersion liquid, the mass ratio of the polymer hollow microspheres, water, styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile is (0.4 - 0.6):(30 - 50):(0.8 - 1):(0.4 - 0.5):1.

[0027] Preferably, in the step (4): when preparing the composite emulsion diluent, the volume ratio of the modified polyacrylate composite emulsion, water, and ethanol is 2:1:1; the impregnation time is 3 - 5 min; the heating conditions are: reacting at a temperature of 75 - 80°C for 6 - 8 h.

[0028] Preferably, in the step (4): the coating amount of the modified polymer composite microsphere dispersion liquid is 10 - 18 g / m 2 .

[0029] Preferably, an antioxidant, waterproof, and wear-resistant decorative paper prepared by using the preparation method of the antioxidant, waterproof, and wear-resistant decorative paper as described above.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] In the present invention, by grafting and polymerizing carboxymethyl cellulose with acrylate monomers, a cellulose-acrylate prepolymer is obtained; the emulsion prepared from this prepolymer has rich hydroxyl groups on its molecular chain, which can form hydrogen bonds with the hydroxyl groups on the paper fibers, so as to have sufficient adhesion strength to the paper fibers, play a role in strengthening between the paper fibers, and improve the mechanical properties of the decorative paper.

[0032] Nano-titanium dioxide has a photocatalytic effect and can absorb ultraviolet light energy to play an antibacterial and bactericidal role; adding it to the polyacrylate emulsion can improve the anti-aging property of the emulsion and enhance the comprehensive performance of the rubber film.

[0033] In the present invention, the surface of titanium dioxide is organically modified by a silane coupling agent, improving the compatibility between titanium dioxide and the acrylate emulsion, enabling the uniform dispersion of nano-titanium dioxide in the reactive acrylate monomers, and preparing a modified titanium dioxide-acrylate mixture; mixing it with a cellulose-acrylate prepolymer, and preparing a modified polyacrylate composite emulsion by in-situ polymerization, further improving the stability of the acrylate emulsion and the dispersion of titanium dioxide in the emulsion. The decorative paper impregnated with the modified polyacrylate composite emulsion has the advantages of waterproofness, abrasion resistance, antioxidant and weather resistance, etc., while improving its mechanical properties.

[0034] In the present invention, through the template etching method, after styrene and divinylbenzene undergo a polymerization reaction on the surface of a silica template containing carbon-carbon double bonds, the silica is etched away with a strong base to obtain polymer hollow microspheres; according to the principle of similar solubility, the polymer hollow microspheres are loaded with organic prepolymer monomers to obtain modified polymer composite microspheres. The coating liquid made of such composite microspheres is coated on the surface of the decorative paper, and the loaded organic prepolymer monomers are polymerized by thermal initiation and grow on the surface of the polymer composite microspheres to form nano-scale surface protrusions, finally forming a surface of a micro-nano dual-scale structure material with a rough surface structure and hydrophobicity, thereby further improving the waterproofness and abrasion resistance of the decorative paper. Description of the Drawings

[0035] Figure 1 is the process flow chart for preparing the antioxidant, waterproof and wear-resistant decorative paper in the present invention;

[0036] Figure 2 is the process flow chart for preparing the modified polyacrylate composite emulsion in the present invention;

[0037] Figure 3 is the process flow chart for preparing the modified polymer composite microsphere dispersion liquid in the present invention;

[0038] Figure 4 is the reaction schematic diagram for preparing modified titanium dioxide in the preparation of the modified polyacrylate composite emulsion in the present invention;

[0039] Figure 5 is the bar chart of the elongation rate of the antioxidant, waterproof and wear-resistant decorative paper prepared in Examples 1-5 and Comparative Examples 1-3 of the present invention;

[0040] Figure 6 is the bar chart of the tearing degree of the antioxidant, waterproof and wear-resistant decorative paper prepared in Examples 1-5 and Comparative Examples 1-3 of the present invention;

[0041] Figure 7 is the bar chart of the static water contact angle of the antioxidant, waterproof and wear-resistant decorative paper prepared in Examples 1-5 and Comparative Examples 1-3 of the present invention;

[0042] Figure 8 It is a bar chart of the abrasion resistance revolutions of the antioxidant, waterproof and wear-resistant decorative papers prepared in Examples 1-5 and Comparative Examples 1-3 of the present invention. Detailed implementation manners

[0043] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0044] Example 1

[0045] This example discloses a preparation method of an antioxidant, waterproof and wear-resistant decorative paper, including the following steps:

[0046] Step (1): Mix cetyltrimethylammonium bromide, acrylic acid, and methyl methacrylate evenly at room temperature, add water until the mixture becomes clear, and dropwise add tetrabutyl titanate and vinyltrimethoxysilane respectively. The mass ratio of cetyltrimethylammonium bromide, acrylic acid, methyl methacrylate, water, tetrabutyl titanate, and vinyltrimethoxysilane is 10:14:30:15:6:4. The dropping time of tetrabutyl titanate and vinyltrimethoxysilane is 5 minutes each. After the dropping is completed, stir and react at room temperature for 16 hours to obtain a modified titanium dioxide-acrylate mixture; Mix the modified titanium dioxide-acrylate mixture with water at a mass ratio of 2:1, stir and disperse at room temperature and a rotation speed of 2500 r / min for 15 minutes, and then continue ultrasonic dispersion for 30 minutes to obtain a titanium dioxide-acrylate mixture dispersion;

[0047] Step (2): Mix sodium carboxymethyl cellulose with water at a mass ratio of 1:3, stir and dissolve at 70 °C to obtain a sodium carboxymethyl cellulose solution; In a nitrogen atmosphere and at a temperature of 80 °C, mix and stir the sodium carboxymethyl cellulose solution, buffer, and second initiator for 5 minutes, and dropwise add acrylate monomer. The dropping time is 30 minutes. After the dropping is completed, react for 20 minutes to obtain a cellulose-acrylate prepolymer; In a nitrogen atmosphere and at a temperature of 80 °C, dropwise add the titanium dioxide-acrylate mixture dispersion and the first initiator to the cellulose-acrylate prepolymer respectively. The dropping time of the titanium dioxide-acrylate mixture dispersion is 2 hours, and the dropping time of the first initiator is 2.5 hours. After the dropping is completed, continue to stir and react at a rotation speed of 120 r / min and a temperature of 85 °C for 5 hours. After the reaction is completed, cool to room temperature, and add 20 wt% ammonia water to adjust the pH value to 7.5 to obtain a modified polyacrylate composite emulsion;

[0048] Among them, the mass ratio of sodium carboxymethylcellulose, buffer, first initiator, second initiator, acrylate monomer, and titanium dioxide-acrylate mixture dispersion is 140:30:6:6:300:1500;

[0049] The acrylate monomer is prepared by mixing glycidyl methacrylate, methyl methacrylate, butyl acrylate, and 2-hydroxyethyl methacrylate in a mass ratio of 5:5:1:1; the buffer is sodium bicarbonate; both the first initiator and the second initiator are aqueous potassium persulfate solutions, and the aqueous potassium persulfate solution is a 3 wt% aqueous potassium persulfate solution; the mass ratio of the first initiator to the second initiator is 1:1;

[0050] Step (3): Mix ethanol and water evenly, add 28 wt% ammonia water and tetraethyl orthosilicate, react at 30 °C for 12 h. After the reaction, add vinyltriethoxysilane and continue to react at 30 °C for 12 h to obtain a silica template containing carbon-carbon double bonds; mix the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol, and carry out a stirring polymerization reaction at 75 °C for 7 h to obtain a polymer microsphere dispersion. Mix the polymer microsphere dispersion with a 2 mol / L sodium hydroxide aqueous solution in a mass ratio of 1:1.2, carry out an etching reaction at 80 °C for 4 h. After the reaction, filter, add water three times the mass of the filter cake and wash three times to obtain polymer hollow microspheres; mix the polymer hollow microspheres, water, styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile in a mass ratio of 0.6:50:1:0.5:1 and stir for 10 h to obtain a modified polymer composite microsphere dispersion;

[0051] Among them, when preparing the silica template containing carbon-carbon double bonds, the volume ratio of ethanol, water, 28 wt% ammonia water, tetraethyl orthosilicate, and vinyltriethoxysilane is 100:33:4:10:3; when preparing the polymer microsphere dispersion, the mass ratio of the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol is 3:2:0.24:4:1.4:3:10:40;

[0052] Step (4): Mix the modified polyacrylate composite emulsion, water, and ethanol in a volume ratio of 2:1:1 to obtain a composite emulsion dilution. Immerse the decorative paper in the composite emulsion dilution for 5 min, dry at 25 °C for 10 h. After drying, coat the modified polymer composite microsphere dispersion on both surfaces of the decorative paper and heat at 80 °C for 6 h to obtain an antioxidant, waterproof, and wear-resistant decorative paper;

[0053] Among them, the coating amount of the modified polymer composite microsphere dispersion is 18 g / m 2。

[0054] Example 2

[0055] This example discloses a preparation method of an antioxidant, waterproof and wear-resistant decorative paper, comprising the following steps:

[0056] Step (1): Cetyltrimethylammonium bromide, acrylic acid, and methyl methacrylate are mixed evenly at room temperature, and water is added until the mixture becomes clear. Tetrabutyl titanate and vinyltrimethoxysilane are respectively added dropwise. The mass ratio of cetyltrimethylammonium bromide, acrylic acid, methyl methacrylate, water, tetrabutyl titanate, and vinyltrimethoxysilane is 4:6:10:10:2:1. The dropping time of tetrabutyl titanate and vinyltrimethoxysilane is 10 min. After the dropping is completed, the mixture is stirred and reacted at room temperature for 24 h to obtain a modified titanium dioxide-acrylate mixture; the modified titanium dioxide-acrylate mixture and water are mixed at a mass ratio of 2:1, stirred and dispersed at 1500 r / min at room temperature for 20 min, and then ultrasonically dispersed for 15 min to obtain a titanium dioxide-acrylate mixture dispersion;

[0057] Step (2): Sodium carboxymethyl cellulose and water are mixed at a mass ratio of 1:5 and stirred and dissolved at 70 °C to obtain a sodium carboxymethyl cellulose solution; in a nitrogen atmosphere and at 80 °C, the sodium carboxymethyl cellulose solution, a buffer, and a second initiator are mixed and stirred for 10 min, and an acrylate monomer is added dropwise. The dropping time is 30 min. After the dropping is completed, the reaction is carried out for 30 min to obtain a cellulose-acrylate prepolymer; in a nitrogen atmosphere and at 80 °C, the titanium dioxide-acrylate mixture dispersion and a first initiator are respectively added dropwise to the cellulose-acrylate prepolymer. The dropping time of the titanium dioxide-acrylate mixture dispersion is 1 h, and the dropping time of the first initiator is 1.5 h. After the dropping is completed, the mixture is continuously stirred and reacted at 100 r / min and 80 °C for 6 h. After the reaction is completed, it is cooled to room temperature, and 20 wt% ammonia water is added to adjust the pH value to 8 to obtain a modified polyacrylate composite emulsion;

[0058] Among them, the mass ratio of sodium carboxymethyl cellulose, buffer, first initiator, second initiator, acrylate monomer, and titanium dioxide-acrylate mixture dispersion is 135:28:6:6:275:1400;

[0059] The acrylate monomer is prepared by mixing glycidyl methacrylate, methyl methacrylate, butyl acrylate, and 2-hydroxyethyl methacrylate at a mass ratio of 3:3:0.5:0.5; the buffer is sodium bicarbonate; both the first initiator and the second initiator are aqueous potassium persulfate solutions, and the aqueous potassium persulfate solution is a 1 wt% aqueous potassium persulfate solution; the mass ratio of the first initiator to the second initiator is 1:1;

[0060] Step (3): Mix ethanol and water evenly, add 28 wt% ammonia water and tetraethyl orthosilicate, react at 25 °C for 14 h. After the reaction, add vinyltriethoxysilane and continue to react at 25 °C for 14 h to obtain a silica template containing carbon-carbon double bonds; mix the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol, and carry out a stirring polymerization reaction at 85 °C for 6 h to obtain a polymer microsphere dispersion. Mix the polymer microsphere dispersion with 2 mol / L sodium hydroxide aqueous solution at a mass ratio of 1:1, carry out an etching reaction at 75 °C for 4 h. After the reaction, filter, add water 5 times the mass of the filter cake and wash three times to obtain polymer hollow microspheres; mix the polymer hollow microspheres, water, styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile at a mass ratio of 0.4:30:0.8:0.4:1 and stir for 10 h to obtain a modified polymer composite microsphere dispersion;

[0061] Among them, when preparing the silica template containing carbon-carbon double bonds, the volume ratio of ethanol, water, 28 wt% ammonia water, tetraethyl orthosilicate, and vinyltriethoxysilane is 100:33:4:10:3; when preparing the polymer microsphere dispersion, the mass ratio of the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol is 3:2:0.16:4:1.2:3:5:35;

[0062] Step (4): Mix the modified polyacrylate composite emulsion, water, and ethanol at a volume ratio of 2:1:1 to obtain a composite emulsion diluent. Immerse the decorative paper in the composite emulsion diluent for 3 min, dry at 15 °C for 24 h. After drying, coat the modified polymer composite microsphere dispersion on both surfaces of the decorative paper and heat at 75 °C for 8 h to obtain an antioxidant, waterproof, and wear-resistant decorative paper;

[0063] Among them, the coating amount of the modified polymer composite microsphere dispersion is 16 g / m 2 。

[0064] Example 3

[0065] This example discloses a preparation method of an antioxidant, waterproof, and wear-resistant decorative paper, including the following steps:

[0066] Step (1): Cetyltrimethylammonium bromide, acrylic acid, and methyl methacrylate are mixed evenly at room temperature. Water is added until the mixture becomes clear. Tetrabutyl titanate and vinyltrimethoxysilane are added dropwise respectively. The mass ratio of cetyltrimethylammonium bromide, acrylic acid, methyl methacrylate, water, tetrabutyl titanate, and vinyltrimethoxysilane is 8:10:20:12:4:3. The dropping time of both tetrabutyl titanate and vinyltrimethoxysilane is 7 min. After the dropping is completed, the mixture is stirred and reacted at room temperature for 20 h to obtain a modified titanium dioxide-acrylate mixture. The modified titanium dioxide-acrylate mixture and water are mixed at a mass ratio of 2:1, stirred and dispersed at room temperature at a rotation speed of 2000 r / min for 18 min, and then ultrasonically dispersed for 20 min to obtain a titanium dioxide-acrylate mixture dispersion;

[0067] Step (2): Sodium carboxymethyl cellulose and water are mixed at a mass ratio of 1:4 and stirred and dissolved at 70 °C to obtain a sodium carboxymethyl cellulose solution. In a nitrogen atmosphere and at 80 °C, the sodium carboxymethyl cellulose solution, buffer, and second initiator are mixed and stirred for 7 min, and then an acrylate monomer is added dropwise. The dropping time is 30 min. After the dropping is completed, the reaction is carried out for 25 min to obtain a cellulose-acrylate prepolymer. In a nitrogen atmosphere and at 80 °C, the titanium dioxide-acrylate mixture dispersion and the first initiator are added dropwise to the cellulose-acrylate prepolymer respectively. The dropping time of the titanium dioxide-acrylate mixture dispersion is 1.5 h, and the dropping time of the first initiator is 2 h. After the dropping is completed, the mixture is continuously stirred and reacted at a rotation speed of 110 r / min and a temperature of 83 °C for 5.5 h. After the reaction is completed, it is cooled to room temperature, and 20 wt% ammonia water is added to adjust the pH value to 7.5 to obtain a modified polyacrylate composite emulsion;

[0068] Among them, the mass ratio of sodium carboxymethyl cellulose, buffer, first initiator, second initiator, acrylate monomer, and titanium dioxide-acrylate mixture dispersion is 125:25:5:5:250:1350;

[0069] The acrylate monomer is prepared by mixing glycidyl methacrylate, methyl methacrylate, butyl acrylate, and 2-hydroxyethyl methacrylate at a mass ratio of 4:4:0.8:0.8; the buffer is sodium bicarbonate; both the first initiator and the second initiator are aqueous potassium persulfate solutions, and the aqueous potassium persulfate solution is a 2 wt% aqueous potassium persulfate solution; the mass ratio of the first initiator to the second initiator is 1:1;

[0070] Step (3): Mix ethanol and water evenly, add 28 wt% ammonia water and tetraethyl orthosilicate, react at 28 °C for 13 h. After the reaction, add vinyltriethoxysilane and continue to react at 28 °C for 13 h to obtain a silica template containing carbon-carbon double bonds; mix the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol, and carry out a stirring polymerization reaction at 80 °C for 6.5 h to obtain a polymer microsphere dispersion. Mix the polymer microsphere dispersion with 2 mol / L sodium hydroxide aqueous solution at a mass ratio of 1:1.1, carry out an etching reaction at 78 °C for 4 h. After the reaction, filter, add water 4 times the mass of the filter cake and wash three times to obtain polymer hollow microspheres; mix the polymer hollow microspheres, water, styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile at a mass ratio of 0.5:40:0.9:0.4:1 and stir for 10 h to obtain a modified polymer composite microsphere dispersion;

[0071] Among them, when preparing the silica template containing carbon-carbon double bonds, the volume ratio of ethanol, water, 28 wt% ammonia water, tetraethyl orthosilicate, and vinyltriethoxysilane is 100:33:4:10:3; when preparing the polymer microsphere dispersion, the mass ratio of the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol is 3:2:0.20:4:1.3:3:8:38;

[0072] Step (4): Mix the modified polyacrylate composite emulsion, water, and ethanol at a volume ratio of 2:1:1 to obtain a composite emulsion diluent. Immerse the decorative paper in the composite emulsion diluent for 4 min, dry at 20 °C for 18 h. After drying, coat the modified polymer composite microsphere dispersion on both surfaces of the decorative paper and heat at 78 °C for 7 h to obtain an antioxidant, waterproof, and wear-resistant decorative paper;

[0073] Among them, the coating amount of the modified polymer composite microsphere dispersion is 14 g / m 2 。

[0074] Example 4

[0075] This example discloses a preparation method of an antioxidant, waterproof, and wear-resistant decorative paper, including the following steps:

[0076] Step (1): Cetyltrimethylammonium bromide, acrylic acid, and methyl methacrylate are mixed evenly at room temperature. Water is added until the mixture becomes clear. Tetrabutyl titanate and vinyltrimethoxysilane are added dropwise respectively. The mass ratio of cetyltrimethylammonium bromide, acrylic acid, methyl methacrylate, water, tetrabutyl titanate, and vinyltrimethoxysilane is 6:8:20:10:5:3. The dropping time of both tetrabutyl titanate and vinyltrimethoxysilane is 8 min. After the dropping is completed, the mixture is stirred and reacted at room temperature for 20 h to obtain a modified titanium dioxide-acrylate mixture. The modified titanium dioxide-acrylate mixture is mixed with water at a mass ratio of 2:1, stirred and dispersed at room temperature at a rotation speed of 1800 r / min for 17 min, and then ultrasonically dispersed for 25 min to obtain a titanium dioxide-acrylate mixture dispersion;

[0077] Step (2): Sodium carboxymethyl cellulose is mixed with water at a mass ratio of 1:5 and stirred and dissolved at 70 °C to obtain a sodium carboxymethyl cellulose solution. In a nitrogen atmosphere and at 80 °C, the sodium carboxymethyl cellulose solution, buffer, and second initiator are mixed and stirred for 8 min, and then an acrylate monomer is added dropwise. The dropping time is 30 min. After the dropping is completed, the reaction is carried out for 30 min to obtain a cellulose-acrylate prepolymer. In a nitrogen atmosphere and at 80 °C, the titanium dioxide-acrylate mixture dispersion and the first initiator are added dropwise to the cellulose-acrylate prepolymer respectively. The dropping time of the titanium dioxide-acrylate mixture dispersion is 1 h, and the dropping time of the first initiator is 2 h. After the dropping is completed, the mixture is continuously stirred and reacted at 80 °C at a rotation speed of 100 r / min for 6 h. After the reaction is completed, it is cooled to room temperature, and 20 wt% ammonia water is added to adjust the pH value to 7.5 to obtain a modified polyacrylate composite emulsion;

[0078] Among them, the mass ratio of sodium carboxymethyl cellulose, buffer, first initiator, second initiator, acrylate monomer, and titanium dioxide-acrylate mixture dispersion is 115:22:5:5:225:1250;

[0079] The acrylate monomer is prepared by mixing glycidyl methacrylate, methyl methacrylate, butyl acrylate, and 2-hydroxyethyl methacrylate at a mass ratio of 3:3:0.5:0.5; the buffer is sodium bicarbonate; both the first initiator and the second initiator are aqueous potassium persulfate solutions, and the aqueous potassium persulfate solution is a 1.5 wt% aqueous potassium persulfate solution; the mass ratio of the first initiator to the second initiator is 1:1;

[0080] Step (3): Mix ethanol and water evenly, add 28 wt% ammonia water and tetraethyl orthosilicate, react at 25 °C for 14 h. After the reaction, add vinyltriethoxysilane and continue to react at 30 °C for 12 h to obtain a silica template containing carbon-carbon double bonds; mix the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol, and carry out a stirring polymerization reaction at 80 °C for 6 h to obtain a polymer microsphere dispersion. Mix the polymer microsphere dispersion with 2 mol / L sodium hydroxide aqueous solution at a mass ratio of 1:1, carry out an etching reaction at 75 °C for 4 h. After the reaction, filter, add water three times the mass of the filter cake and wash three times to obtain polymer hollow microspheres; mix the polymer hollow microspheres, water, styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile at a mass ratio of 0.6:45:1:0.4:1 and stir for 10 h to obtain a modified polymer composite microsphere dispersion;

[0081] Among them, when preparing the silica template containing carbon-carbon double bonds, the volume ratio of ethanol, water, 28 wt% ammonia water, tetraethyl orthosilicate, and vinyltriethoxysilane is 100:33:4:10:3; when preparing the polymer microsphere dispersion, the mass ratio of the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol is 3:2:0.22:4:1.3:3:8:40;

[0082] Step (4): Mix the modified polyacrylate composite emulsion, water, and ethanol at a volume ratio of 2:1:1 to obtain a composite emulsion diluent. Immerse the decorative paper in the composite emulsion diluent for 3 min, dry at 20 °C for 16 h. After drying, coat the modified polymer composite microsphere dispersion on both surfaces of the decorative paper and heat at 75 °C for 8 h to obtain an antioxidant, waterproof, and wear-resistant decorative paper;

[0083] Among them, the coating amount of the modified polymer composite microsphere dispersion is 12 g / m 2 .

[0084] Example 5

[0085] This example discloses a preparation method of an antioxidant, waterproof, and wear-resistant decorative paper, including the following steps:

[0086] Step (1): Cetyltrimethylammonium bromide, acrylic acid, and methyl methacrylate are mixed evenly at room temperature. Water is added until the mixture becomes clear. Titanium butoxide and vinyltrimethoxysilane are respectively added dropwise. The mass ratio of cetyltrimethylammonium bromide, acrylic acid, methyl methacrylate, water, titanium butoxide, and vinyltrimethoxysilane is 10:14:20:15:5:3. The dropping time of both titanium butoxide and vinyltrimethoxysilane is 10 min. After the dropping is completed, the mixture is stirred and reacted at room temperature for 18 h to obtain a modified titanium dioxide-acrylate mixture. The modified titanium dioxide-acrylate mixture is mixed with water at a mass ratio of 2:1, stirred and dispersed at room temperature at a rotation speed of 2300 r / min for 15 min, and then ultrasonically dispersed for 25 min to obtain a titanium dioxide-acrylate mixture dispersion;

[0087] Step (2): Sodium carboxymethyl cellulose is mixed with water at a mass ratio of 1:5 and stirred and dissolved at 70 °C to obtain a sodium carboxymethyl cellulose solution. In a nitrogen atmosphere and at 80 °C, the sodium carboxymethyl cellulose solution, buffer, and second initiator are mixed and stirred for 10 min. An acrylate monomer is added dropwise, and the dropping time is 30 min. After the dropping is completed, the reaction is carried out for 25 min to obtain a cellulose-acrylate prepolymer. In a nitrogen atmosphere and at 80 °C, the titanium dioxide-acrylate mixture dispersion and the first initiator are respectively added dropwise to the cellulose-acrylate prepolymer. The dropping time of the titanium dioxide-acrylate mixture dispersion is 1.5 h, and the dropping time of the first initiator is 2 h. After the dropping is completed, the mixture is continuously stirred and reacted at 85 °C at a rotation speed of 120 r / min for 5 h. After the reaction is completed, it is cooled to room temperature, and 20 wt% ammonia water is added to adjust the pH value to 8 to obtain a modified polyacrylate composite emulsion;

[0088] Among them, the mass ratio of sodium carboxymethyl cellulose, buffer, first initiator, second initiator, acrylate monomer, and titanium dioxide-acrylate mixture dispersion is 110:20:5:5:200:1200;

[0089] The acrylate monomer is prepared by mixing glycidyl methacrylate, methyl methacrylate, butyl acrylate, and 2-hydroxyethyl methacrylate in a mass ratio of 3:3:0.5:0.5; the buffer is sodium bicarbonate; both the first initiator and the second initiator are aqueous potassium persulfate solutions, and the aqueous potassium persulfate solution is a 1 wt% aqueous potassium persulfate solution; the mass ratio of the first initiator to the second initiator is 1:1;

[0090] Step (3): Mix ethanol and water evenly, add 28 wt% ammonia water and tetraethyl orthosilicate, react at 30 °C for 12 h. After the reaction, add vinyltriethoxysilane and continue to react at 25 °C for 14 h to obtain a silica template containing carbon-carbon double bonds; mix the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol, and carry out a stirring polymerization reaction at 85 °C for 6 h to obtain a polymer microsphere dispersion. Mix the polymer microsphere dispersion with 2 mol / L sodium hydroxide aqueous solution at a mass ratio of 1:1.2, carry out an etching reaction at 75 °C for 4 h. After the reaction, filter, add water 5 times the mass of the filter cake and wash three times to obtain polymer hollow microspheres; mix the polymer hollow microspheres, water, styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile at a mass ratio of 0.4:30:1:0.4:1 and stir for 10 h to obtain a modified polymer composite microsphere dispersion;

[0091] Among them, when preparing the silica template containing carbon-carbon double bonds, the volume ratio of ethanol, water, 28 wt% ammonia water, tetraethyl orthosilicate, and vinyltriethoxysilane is 100:33:4:10:3; when preparing the polymer microsphere dispersion, the mass ratio of the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol is 3:2:0.18:4:1.2:3:6:36;

[0092] Step (4): Mix the modified polyacrylate composite emulsion, water, and ethanol at a volume ratio of 2:1:1 to obtain a composite emulsion diluent. Immerse the decorative paper in the composite emulsion diluent for 5 min, dry at 15 °C for 24 h. After drying, coat the modified polymer composite microsphere dispersion on both surfaces of the decorative paper and heat at 80 °C for 6 h to obtain an antioxidant, waterproof, and wear-resistant decorative paper;

[0093] Among them, the coating amount of the modified polymer composite microsphere dispersion is 10 g / m 2 .

[0094] Comparative Example 1

[0095] This comparative example discloses a preparation method of an antioxidant, waterproof, and wear-resistant decorative paper, including the following steps:

[0096] Step (1): Mix sodium carboxymethyl cellulose and water at a mass ratio of 1:3, stir and dissolve at 70 °C to obtain a sodium carboxymethyl cellulose solution; in a nitrogen atmosphere and at 80 °C, mix and stir the sodium carboxymethyl cellulose solution, buffer, and second initiator for 5 min, add the first portion of acrylate monomer dropwise over 30 min. After the addition is complete, react for 20 min to obtain a cellulose-acrylate prepolymer; add the second portion of acrylate monomer and the first initiator dropwise to the cellulose-acrylate prepolymer. The addition time of the second portion of acrylate monomer is 2 h, and the addition time of the first initiator is 2.5 h. After the addition is complete, continue to stir and react at 120 r / min and 85 °C for 5 h. After the reaction is completed, cool to room temperature and add 20 wt% ammonia water to adjust the pH value to 7.5 to obtain a modified polyacrylate composite emulsion;

[0097] Among them, the mass ratio of sodium carboxymethyl cellulose, buffer, first initiator, second initiator, first portion of acrylate monomer, and second portion of acrylate monomer is 140:30:6:6:300:1000

[0098] The first portion of acrylate monomer and the second portion of acrylate monomer are both prepared by mixing glycidyl methacrylate, methyl methacrylate, butyl acrylate, and 2-hydroxyethyl methacrylate at a mass ratio of 5:5:1:1; the buffer is sodium bicarbonate; both the first initiator and the second initiator are aqueous potassium persulfate solutions, and the aqueous potassium persulfate solution is a 3 wt% aqueous potassium persulfate solution; the mass ratio of the first initiator to the second initiator is 1:1;

[0099] Step (2): Mix ethanol and water evenly, add 28 wt% ammonia water and tetraethyl orthosilicate, react at 30 °C for 12 h. After the reaction is completed, add vinyltriethoxysilane and continue to react at 30 °C for 12 h to obtain a silica template containing carbon-carbon double bonds; mix the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol, and carry out a stirring polymerization reaction at 75 °C for 7 h to obtain a polymer microsphere dispersion. Mix the polymer microsphere dispersion and 2 mol / L sodium hydroxide aqueous solution at a mass ratio of 1:1.2, and carry out an etching reaction at 80 °C for 4 h. After the reaction is completed, filter, add water three times the mass of the filter cake for washing to obtain polymer hollow microspheres; mix the polymer hollow microspheres, water, styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile at a mass ratio of 0.6:50:1:0.5:1 and stir for 10 h to obtain a modified polymer composite microsphere dispersion;

[0100] Among them, when preparing the silica template containing carbon-carbon double bonds, the volume ratio of ethanol, water, 28 wt% ammonia water, tetraethyl orthosilicate, and vinyltriethoxysilane is 100:33:4:10:3; when preparing the polymer microsphere dispersion liquid, the mass ratio of the silica template containing carbon-carbon double bonds, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol is 3:2:0.24:4:1.4:3:10:40;

[0101] Step (3): Mix the modified polyacrylate composite emulsion, water, and ethanol in a volume ratio of 2:1:1 to obtain a composite emulsion dilution liquid. Immerse the decorative paper in the composite emulsion dilution liquid for 5 min, dry it at 25 °C for 10 h. After drying, coat the modified polymer composite microsphere dispersion liquid on both surfaces of the decorative paper, and heat it at 80 °C for 6 h to obtain the antioxidant, waterproof, and wear-resistant decorative paper;

[0102] Among them, the coating amount of the modified polymer composite microsphere dispersion liquid is 18 g / m 2 .

[0103] Comparative Example 2

[0104] This comparative example discloses a preparation method of an antioxidant, waterproof, and wear-resistant decorative paper, including the following steps:

[0105] Step (1): Mix cetyltrimethylammonium bromide, acrylic acid, and methyl methacrylate evenly at room temperature, add water until the mixture becomes clear, and then dropwise add tetrabutyl titanate and vinyltrimethoxysilane respectively. The mass ratio of cetyltrimethylammonium bromide, acrylic acid, methyl methacrylate, water, tetrabutyl titanate, and vinyltrimethoxysilane is 10:14:30:15:6:4. The dropping time of tetrabutyl titanate and vinyltrimethoxysilane is 5 min. After the dropping is completed, stir and react at room temperature for 16 h to obtain a modified titanium dioxide-acrylate mixture; Mix the modified titanium dioxide-acrylate mixture with water in a mass ratio of 2:1, stir and disperse it at room temperature at a rotation speed of 2500 r / min for 15 min, and then continue ultrasonic dispersion for 30 min to obtain a titanium dioxide-acrylate mixture dispersion liquid;

[0106] Step (2): Mix sodium carboxymethylcellulose and water at a mass ratio of 1:3, stir and dissolve at 70 °C to obtain a sodium carboxymethylcellulose solution; in a nitrogen atmosphere and at 80 °C, mix and stir the sodium carboxymethylcellulose solution, buffer, and second initiator for 5 min, then dropwise add the acrylate monomer over 30 min. After the addition is complete, react for 20 min to obtain a cellulose-acrylate prepolymer; in a nitrogen atmosphere and at 80 °C, dropwise add the titanium dioxide-acrylate mixture dispersion and the first initiator to the cellulose-acrylate prepolymer. The dropping time of the titanium dioxide-acrylate mixture dispersion is 2 h, and the dropping time of the first initiator is 2.5 h. After the addition is complete, continue to stir and react at 85 °C and 120 r / min for 5 h. After the reaction is completed, cool to room temperature and add 20 wt% ammonia water to adjust the pH value to 7.5 to obtain a modified polyacrylate composite emulsion;

[0107] Among them, the mass ratio of sodium carboxymethylcellulose, buffer, first initiator, second initiator, acrylate monomer, and titanium dioxide-acrylate mixture dispersion is 140:30:6:6:300:1500;

[0108] The acrylate monomer is prepared by mixing glycidyl methacrylate, methyl methacrylate, butyl acrylate, and 2-hydroxyethyl methacrylate at a mass ratio of 5:5:1:1; the buffer is sodium bicarbonate; both the first initiator and the second initiator are aqueous potassium persulfate solutions, and the aqueous potassium persulfate solution is a 3 wt% aqueous potassium persulfate solution; the mass ratio of the first initiator to the second initiator is 1:1;

[0109] Step (3): Mix the modified polyacrylate composite emulsion, water, and ethanol at a volume ratio of 2:1:1 to obtain a composite emulsion diluent. Immerse the decorative paper in the composite emulsion diluent for 5 min and dry at 25 °C for 10 h to obtain an antioxidant, waterproof, and wear-resistant decorative paper;

[0110] Comparative Example 3

[0111] This comparative example discloses a preparation method of an antioxidant, waterproof, and wear-resistant decorative paper, including the following steps:

[0112] Step (1): Mix ethanol and water evenly, add 28 wt% ammonia water and tetraethyl orthosilicate, react at 30 °C for 12 h. After the reaction, add vinyltriethoxysilane and continue to react at 30 °C for 12 h to obtain a carbon-carbon double bond-containing silica template; mix the carbon-carbon double bond-containing silica template, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol, and carry out a stirring polymerization reaction at 75 °C for 7 h to obtain a polymer microsphere dispersion. Mix the polymer microsphere dispersion with a 2 mol / L sodium hydroxide aqueous solution at a mass ratio of 1:1.2, carry out an etching reaction at 80 °C for 4 h. After the reaction, filter, add water three times the mass of the filter cake for washing to obtain polymer hollow microspheres; mix the polymer hollow microspheres, water, styrene, ethylene glycol dimethacrylate, and azobisisobutyronitrile at a mass ratio of 0.6:50:1:0.5:1 and stir for 10 h to obtain a modified polymer composite microsphere dispersion;

[0113] Among them, when preparing the carbon-carbon double bond-containing silica template, the volume ratio of ethanol, water, 28 wt% ammonia water, tetraethyl orthosilicate, and vinyltriethoxysilane is 100:33:4:10:3; when preparing the polymer microsphere dispersion, the mass ratio of the carbon-carbon double bond-containing silica template, polyvinylpyrrolidone K30, azobisisobutyronitrile, styrene, divinylbenzene, trifluoroethyl methacrylate, water, and ethanol is 3:2:0.24:4:1.4:3:10:40;

[0114] Step (3): Coat the two-side surfaces of the decorative paper with the modified polymer composite microsphere dispersion and heat at 80 °C for 6 h to obtain an antioxidant, waterproof, and wear-resistant decorative paper;

[0115] Among them, the coating amount of the modified polymer composite microsphere dispersion is 18 g / m 2 。

[0116] In the above-mentioned examples and comparative examples: Cetyltrimethylammonium bromide is from Shandong Guohua Chemical Co., Ltd., CAS No.: 57-09-0; acrylic acid is from Shandong Chuangying Chemical Co., Ltd., CAS No.: 79-10-7; methyl methacrylate is from Shandong Yaojia Chemical Co., Ltd., CAS No.: 80-62-6; tetrabutyl titanate is from Mitsui Chemicals (Shandong) Co., Ltd., CAS No.: 85593-70-4; sodium carboxymethyl cellulose is from Hubei Weishi Chemical Reagent Co., Ltd., CAS No.: 9004-32-4; ammonia water is from Beijing Jingtu Hengsheng Trading Co., Ltd., CAS No.: 1336-21-6; vinyltrimethoxysilane is from Nanjing Liansil Chemical Co., Ltd., CAS No.: 2768-02-7; glycidyl methacrylate is from Qianyan Chemical Technology (Wuhan) Co., Ltd., CAS No.: 106-91-2; butyl acrylate is from Jining Sanshi Biotechnology Co., Ltd., CAS No.: 141-32-2; 2-hydroxyethyl methacrylate is from Qianyan Chemical Technology (Wuhan) Co., Ltd., CAS No.: 868-77-9; sodium bicarbonate is from Langfang Qianyao Technology Co., Ltd., CAS No.: 144-55-8; potassium persulfate is from Maoming Xiongda Chemical Industry Co., Ltd., CAS No.: 7727-21-1; ethanol-free is from Guangdong Lin's Chemical Reagent Co., Ltd., CAS No.: 64-17-5; tetraethyl orthosilicate is from Nanjing Chemical Reagent Co., Ltd., CAS No.: 562-90-3; polyvinylpyrrolidone K30 is from the Dongguan Branch of Maoming Xiongda Chemical Industry Co., Ltd., K value 30, model K30, CAS No.: 9003-39-8; azobisisobutyronitrile is from Jinan Sibete Chemical Co., Ltd., CAS No.: 78-67-1; styrene is from Anhui Jinyueguan New Material Technology Co., Ltd., CAS No.: 100-42-5; divinylbenzene is from Maoming Xiongda Chemical Industry Co., Ltd., CAS No.: 1321-74-0; trifluoroethyl methacrylate is from Wuhan Lanabai Pharmaceutical and Chemical Co., Ltd., brand Lanabai, product number DFGEW432, model GTR4535, CAS No.: 352-87-4; sodium hydroxide is from Hubei Shenglun Chemical Technology Co., Ltd., CAS No.: 1310-73-2; ethylene glycol dimethacrylate is from Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS No.: 97-90-5.

[0117] Test Examples

[0118] (1) Mechanical Property Tests

[0119] The mechanical properties of the antioxidant, waterproof and wear-resistant decorative papers prepared in Examples 1-5 and Comparative Examples 1-3 were tested. The specific test results are shown in Table 1:

[0120] Table 1

[0121]

[0122]

[0123] The detection of each index in Table 1 is based on the following standards respectively: The elongation at break is determined by GB / T 12914-2008 "Determination of Tensile Strength of Paper and Board"; The tearing degree is determined by GB / T 455-2002 "Determination of Tear Resistance of Paper and Board"; The number of folding endurance is determined by GB / T 457-2008 "Determination of Folding Endurance of Paper and Board"; The anti-aging performance is determined by GB / T 40278-2021 "Accelerated Aging of Paper and Board (Under the Condition of Light)".

[0124] According to the test results in Table 1, it can be seen that the antioxidant, waterproof and wear-resistant decorative paper prepared by the present invention has good mechanical properties and excellent antioxidant and weather resistance.

[0125] In the present invention, carboxymethyl cellulose is grafted and polymerized with acrylate monomers to obtain a cellulose-acrylate prepolymer; the emulsion prepared by this prepolymer has rich hydroxyl groups on its molecular chain, which can form hydrogen bonds with the hydroxyl groups on the paper fibers, so as to have sufficient adhesion strength to the paper fibers, play a strengthening role between the paper fibers, and improve the mechanical properties of the decorative paper. The nano-titanium dioxide added to the polyacrylate emulsion has a photocatalytic effect, can absorb ultraviolet light energy to play an antibacterial and sterilizing role, thereby improving the antioxidant and weather resistance of the emulsion and enhancing the comprehensive performance of the adhesive film.

[0126] In the present invention, the surface of titanium dioxide is organically modified by a silane coupling agent, which improves the compatibility between titanium dioxide and the acrylate emulsion, enables nano-titanium dioxide to be directly dispersed in the reactive acrylate monomers, and prepares a modified titanium dioxide-acrylate mixture; it is mixed with the cellulose-acrylate prepolymer, and a modified polyacrylate composite emulsion is prepared by in-situ polymerization, further improving the stability of the acrylate emulsion and the dispersibility of titanium dioxide in the emulsion. The decorative paper impregnated with the modified polyacrylate composite emulsion has antioxidant and weather resistance, and at the same time improves its mechanical properties.

[0127] In Comparative Example 1, the modified titanium dioxide-acrylate mixture was not added to the modified polyacrylate composite emulsion, resulting in the lack of anti-aging property of the decorative paper, so the anti-aging performance was lower than that of the example;

[0128] In Comparative Example 3, the modified polyacrylate composite emulsion was not impregnated, there was no carboxymethyl cellulose to play a strengthening role between the paper fibers, and it lacked anti-aging property, so both the mechanical properties and the anti-aging performance were lower than those of the example.

[0129] (2) Waterproof and wear-resistant performance test

[0130] The abrasion resistance revolution number and static water contact angle of the antioxidant, waterproof and wear-resistant decorative papers prepared in Examples 1-5 and Comparative Examples 1-3 were tested; among them, the abrasion resistance revolution number was determined with reference to GB7911.7-87 "Determination of Surface Abrasion Resistance of Thermosetting Resin Decorative Laminates"; the specific test results are shown in Table 2:

[0131] Table 2

[0132]

[0133] It can be seen from the test results in Table 2 that the antioxidant, waterproof and wear-resistant decorative paper prepared by the present invention has excellent waterproof and wear-resistant properties.

[0134] In the present invention, titanium dioxide was surface-organically modified by a silane coupling agent, improving the compatibility between titanium dioxide and acrylate emulsion, enabling nano-titanium dioxide to be directly dispersed in reactive acrylate monomers, and preparing a modified titanium dioxide-acrylate mixture; the prepared modified polyacrylate composite emulsion improved the dispersibility of titanium dioxide in the emulsion. The decorative paper impregnated with the modified polyacrylate composite emulsion has the advantages of waterproofness, wear resistance, antioxidant weather resistance, etc., and at the same time improves its mechanical properties.

[0135] In the present invention, through the template etching method, after styrene and divinylbenzene polymerized on the surface of a silica template containing carbon-carbon double bonds of a silane coupling agent, the silica was etched away with a strong base to obtain polymer hollow microspheres; according to the principle of similar solubility, the polymer hollow microspheres were loaded with organic prepolymers to obtain modified polymer composite microspheres. The coating liquid made of such composite microspheres was coated on the surface of the decorative paper, and through thermal initiation, the loaded organic prepolymers polymerized and grew on the surface of the polymer composite microspheres, forming nano-scale surface protrusions, and finally forming a surface of a micro-nano dual-scale structure material with a rough surface structure and hydrophobicity, thereby further improving the waterproofness and wear resistance of the decorative paper.

[0136] The modified polyacrylate composite emulsion in Comparative Example 1 did not add the modified titanium dioxide-acrylate mixture. Although there was still a rough surface structure of the modified polymer composite microspheres on the surface of the decorative paper, increasing its waterproof and wear resistance, without the synergistic effect of nano-titanium dioxide, its waterproof and wear resistance was slightly lower than that of the examples;

[0137] Comparative Example 2 did not coat the modified polymer composite microsphere dispersion liquid. Although the modified polyacrylate composite emulsion played a certain role in waterproofing and wear resistance, its rough surface structure and hydrophobicity were still inferior to those of the examples, so its waterproof and wear resistance was much lower than that of the examples;

[0138] Comparative Example 3 did not impregnate the modified polyacrylate composite emulsion. Although there was still the rough surface structure of the modified polymer composite microspheres on the surface of the decorative paper, increasing its waterproof and wear resistance, without the synergistic effect of the modified polyacrylate composite emulsion, its waterproof and wear resistance was slightly lower than that of the examples.

[0139] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of an antioxidant, waterproof and wear-resistant decorative paper, characterized in that, it comprises the following steps: Step 1, prepare a modified polyacrylate composite emulsion and a modified polymer composite microsphere dispersion; Among them, the preparation of the modified polyacrylate composite emulsion includes the following steps: By mass, mix 110 - 140 parts of carboxymethyl cellulose with water, dissolve, mix with 20 - 30 parts of a buffer and 5 - 6 parts of a second initiator, dropwise add 200 - 300 parts of acrylate monomers. After the dropping is completed, react in a nitrogen atmosphere at 80 °C for 20 - 30 min to obtain a cellulose-acrylate prepolymer; Mix 4 - 10 parts of cetyltrimethylammonium bromide, 6 - 14 parts of acrylic acid, and 10 - 30 parts of methyl methacrylate, add 10 - 15 parts of water, dropwise add 2 - 6 parts of tetrabutyl titanate and 1 - 4 parts of a silane coupling agent respectively, with the dropping time being 5 - 10 min for both. After the dropping is completed, stir and react at room temperature for 16 - 24 h. After the reaction ends, mix with water and disperse to obtain a titanium dioxide-acrylate mixture dispersion; Dropwise add 1200 - 1500 parts of the titanium dioxide-acrylate mixture dispersion and 5 - 6 parts of a first initiator to the cellulose-acrylate prepolymer respectively. After the dropping is completed, continue the reaction. After the reaction ends, cool and adjust the pH value to obtain a modified polyacrylate composite emulsion; Among them, the preparation of the modified polymer composite microsphere dispersion includes the following steps: Step (1), by volume, mix 100 parts of ethanol with 33 parts of water, add 4 parts of ammonia water and 10 parts of tetraethyl orthosilicate, react at 25 - 30 °C for 12 - 14 h. After the reaction ends, add 3 parts of vinyltriethoxysilane and react at 25 - 30 °C for 12 - 14 h to obtain a silica template containing carbon-carbon double bonds; By mass, mix 3 parts of the silica template containing carbon-carbon double bonds, 2 parts of polyvinylpyrrolidone, 0.16 - 0.24 parts of azobisisobutyronitrile, 4 parts of styrene, 1.2 - 1.4 parts of divinylbenzene, 3 parts of trifluoroethyl methacrylate, 5 - 10 parts of water, and 35 - 40 parts of ethanol, stir and react at 75 - 85 °C for 6 - 7 h. After the reaction ends, obtain a polymer microsphere dispersion; Step (2), by mass, mix 1 part of the polymer microsphere dispersion with 1 - 1.2 parts of an aqueous sodium hydroxide solution, etch and react at 75 - 80 °C for 4 h. After the reaction ends, filter and wash to obtain polymer hollow microspheres. Mix 0.4 - 0.6 parts of the polymer hollow microspheres, 30 - 50 parts of water, 0.8 - 1 part of styrene, 0.4 - 0.5 part of ethylene glycol dimethacrylate, and 1 part of azobisisobutyronitrile evenly to obtain a modified polymer composite microsphere dispersion; Step 2, mix the modified polyacrylate composite emulsion, water, and ethanol to obtain a composite emulsion diluent. Immerse the decorative paper in the composite emulsion diluent, and after immersion, dry. Coat the modified polymer composite microsphere dispersion on both surfaces of the decorative paper and heat to obtain an antioxidant, waterproof and wear-resistant decorative paper.

2. The preparation method of the antioxidant, waterproof and wear-resistant decorative paper according to claim 1, characterized in that, in the process of preparing the modified polyacrylate composite emulsion in step one: the conditions for dropping the titanium dioxide-acrylate mixture dispersion are: dropping for 1-2 h at 80 °C in a nitrogen atmosphere; the conditions for dropping the first initiator are: dropping for 1.5-2.5 h at 80 °C in a nitrogen atmosphere; the conditions for continuous reaction are: reacting at 80-85 °C at a rotation speed of 100-120 r / min for 5-6 h.

3. The preparation method of the antioxidant, waterproof and wear-resistant decorative paper according to claim 1, characterized in that, In Step 2: When preparing the composite emulsion diluent, the volume ratio of the modified polyacrylate composite emulsion, water, and ethanol is 2:1:1; the impregnation time is 3 - 5 min; the heating conditions are: reacting at a temperature of 75 - 80 °C for 6 - 8 h; the coating amount of the modified polymer composite microsphere dispersion is 10 - 18 g / m 2 .

4. An antioxidant, waterproof and wear-resistant decorative paper prepared by using the preparation method of the antioxidant, waterproof and wear-resistant decorative paper according to any one of claims 1-3.

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