Luminous decorative paper and preparation method thereof

Abstract

The present invention discloses luminous decorative paper, a decorative material, and a preparation method thereof. The paper comprises the following components by weight: 5-10 parts of a modified chloroether resin, 6-8 parts of modified cellulose nanocrystals, 3-5 parts of methacrylic acid, 6-10 parts of methyl methacrylate, 8-12 parts of styrene, 15-20 parts of butyl acrylate, 1-2 parts of ammonium persulfate, 0.2-0.5 parts of sodium bicarbonate, 8-11 parts of a composite phosphor, and 12-15 parts of a pigment. The invention adds the silica-modified chloroether resin and modified cellulose nanocrystals to ink to improve the ink's adhesion and durability, thereby increasing the gloss durability and service life of the luminous decorative paper.

Description

Technical Field

[0001] The present invention belongs to the technical field of decorative materials, and in particular relates to luminous decorative paper and a preparation method thereof. Background Art

[0002] As people's requirements for interior decoration become higher and higher, the demand for personalized customization of decorative paper is also growing. However, the existing decorative paper technology has some shortcomings in terms of color. The color stability and durability of traditional decorative paper are limited. Over time, the color may fade or become dim. This color change limits the service life and decorative effect of the decorative paper, and cannot meet people's pursuit of long-lasting bright colors; at the same time, people's demand for luminous effects is also gradually increasing, and traditional decorative paper cannot meet this demand. The development of a new type of wallpaper that has both color durability and luminous effects at night has become a common concern of manufacturers and consumers. This new type of decorative paper needs to be able to display long-lasting bright colors during the day and a luminous effect at night, bringing better effects to interior decoration.

[0003] The existing technology currently has the following main problems: the decorative paper fades and has poor night-time effects. Summary of the Invention

[0004] In view of the above situation and to overcome the defects of the prior art, the present invention provides a luminous decorative paper and a preparation method thereof. In order to solve the problems of fading and poor night effect of decorative paper, the present invention proposes luminous ink, and adds silica-modified chloroether resin and modified cellulose nanocrystals to the ink to improve the adhesion and durability of the ink, thereby increasing the gloss durability and service life of the luminous decorative paper.

[0005] In order to achieve the above-mentioned purpose, the technical solution adopted by the present invention is as follows: The present invention proposes a luminous decorative paper, including a base paper and a luminous ink, wherein the luminous ink includes the following components in parts by weight: 5-10 parts of modified chloroether resin, 6-8 parts of modified cellulose nanocrystals, 3-5 parts of methacrylic acid, 6-10 parts of methyl methacrylate, 8-12 parts of styrene, 15-20 parts of butyl acrylate, 1-2 parts of ammonium persulfate, 0.2-0.5 parts of sodium bicarbonate, 8-11 parts of composite phosphor, and 12-15 parts of pigment.

[0006] Furthermore, the preparation method of the modified cellulose nanocrystals comprises the following steps:

[0007] (1) Mix microcrystalline cellulose and sulfuric acid in a flask, heat in an oil bath to 50-60°C, stir for 30-40 minutes, cool to room temperature, place in a centrifuge tube, wash with deionized water three times, dialyze the suspension to neutrality, and freeze-dry at -50°C in a vacuum freeze-drying machine for 48 hours to obtain cellulose nanocrystals.

[0008] (2) Cellulose nanocrystals were placed in a beaker, 80 mL of anhydrous ethanol and 20 mL of deionized water were added, and ultrasonic treatment was performed for 10-15 min. Then, the mixture was heated to 40 °C, 3-aminopropyltriethoxysilane was added dropwise, and magnetic stirring was performed for 10-12 h at a speed of 300 rpm. The product was collected by centrifugation, washed with deionized water, and dried in an oven at 50-60 °C for 2-4 h to obtain modified cellulose nanocrystals.

[0009] Furthermore, in step (1), the mass fraction of the sulfuric acid is 65%, and the material-liquid ratio of the microcrystalline cellulose to the sulfuric acid is 1:10-15.

[0010] Furthermore, in step (2), the material-liquid ratio of the cellulose nanocrystals to 3-aminopropyltriethoxysilane is 1:5-8.

[0011] Furthermore, the preparation method of the modified chloroether resin comprises the following steps:

[0012] S1. Add nano-silica to anhydrous ethanol and disperse by ultrasonication to obtain a silica dispersion;

[0013] S2. Take a KH-570 aqueous solution and stir and hydrolyze it at 50°C for 5-6 hours, add it to the silica dispersion described in step S1, stir evenly, adjust the pH value to 10 with ammonia water, react at 50°C for 10-12 hours, filter after the reaction, elute the residual reagent with acetone, and dry to obtain modified silica;

[0014] S3. Take the modified silica and add it to the chloroether resin, and perform ultrasonic treatment for 20-30 minutes to obtain the modified chloroether resin.

[0015] Furthermore, in step S1, the mass fraction of the silicon dioxide dispersion is 5%.

[0016] Furthermore, in step S2, the mass fraction of the KH-570 aqueous solution is 5%, and the volume ratio of the KH-570 aqueous solution to the silicon dioxide dispersion is 2:5-7.

[0017] Furthermore, in step S3, the mass ratio of the modified silica to the chloroether resin is 2:20-30.

[0018] Furthermore, the preparation method of the composite phosphor comprises the following steps:

[0019] Take europium nitrate, dysprosium nitrate, strontium nitrate, and aluminum nitrate, add them to deionized water, stir evenly, add oxalic acid and adjust the pH value to 8-9 with ammonia water, let it stand for 24 hours, centrifuge and filter, wash the filter residue with anhydrous ethanol three times, dry and grind to obtain powder, place the powder in a high-temperature furnace, and keep it at 1350°C for 3 hours to obtain a composite phosphor.

[0020] The present invention provides a method for preparing luminous decorative paper, which specifically comprises the following steps:

[0021] ① Take modified chloroether resin, methacrylic acid, methyl methacrylate, styrene, and butyl acrylate, add deionized water twice the total mass, add sodium bicarbonate, and stir for 20-30 minutes to obtain a mixed solution;

[0022] ② Prepare ammonium persulfate into a 5% by mass aqueous solution, place the mixed solution described in step ① in a flask, add modified chloroether resin and modified cellulose nanocrystals, heat to 70°C, add ammonium persulfate solution, heat to 80-85°C, keep warm for 4-5 hours, cool to 40°C after the reaction is completed, adjust the pH value to 8, stir for 20 minutes to obtain a mixed emulsion, add composite phosphor and pigment to obtain luminous ink;

[0023] ③ Apply the luminous ink described in step ② on the bottom paper to obtain luminous decorative paper.

[0024] The beneficial effects achieved by the present invention are as follows:

[0025] The present invention prepares silica-modified chloroether resin and modified cellulose nanocrystals and adds them to ink, thereby improving the adhesion and durability of the ink and increasing the gloss persistence and service life of the luminous decorative paper. KH-570 modified silica is added to the chloroether resin to obtain a modified chloroether resin. The KH-570 modified silica can improve the dispersibility of the silica and improve the stability of the chloroether resin when added to the chloroether resin. The addition of the modified chloroether resin can improve the adhesion and stability of the ink, thereby increasing the gloss persistence of the luminous decorative paper. Surface modification of the cellulose nanocrystals is then performed on the cellulose nanocrystals for an addition reaction with acrylic acid, thereby increasing the mechanical properties of the acrylic acid and improving the adhesion of the ink. Cellulose itself has certain UV resistance and antioxidant properties, thereby slowing down the oxidation rate of other components in the ink layer and extending the service life of the ink layer. In addition, the cellulose can also provide a certain physical barrier effect, reducing direct exposure of light to the ink layer and reducing damage to the ink layer caused by heat and ultraviolet rays. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Graph showing adhesion fastness test results of luminous inks of Examples 1-3 and Comparative Examples 1-2 of the present invention;

[0027] Figure 2 This is a graph showing the anti-blocking test results of luminous inks of Examples 1-3 and Comparative Examples 1-2 of the present invention;

[0028] Figure 3 Graph showing the light aging resistance test results of luminous decorative papers of Examples 1-3 and Comparative Examples 1-2 of the present invention;

[0029] Figure 4 This is a scanning electron microscope image of the modified cellulose nanocrystals described in Example 1 of the present invention.

[0030] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only 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 ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those familiar to those skilled in the art. Furthermore, any methods and materials similar or equivalent to those described herein can be applied to the present invention. The preferred embodiments and materials described herein are for illustrative purposes only and are not intended to limit the scope of this application.

[0033] The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.

[0034] Example 1

[0035] A luminous decorative paper comprises a base paper and luminous ink. The luminous ink comprises the following components in parts by weight: 5 parts of modified chloroether resin, 6 parts of modified cellulose nanocrystals, 3 parts of methacrylic acid, 6 parts of methyl methacrylate, 8 parts of styrene, 15 parts of butyl acrylate, 1 part of ammonium persulfate, 0.2 parts of sodium bicarbonate, 8 parts of composite phosphor, and 12 parts of pigment.

[0036] Furthermore, the preparation method of the modified cellulose nanocrystals comprises the following steps:

[0037] (1) Microcrystalline cellulose and sulfuric acid were mixed in a flask with a mass fraction of sulfuric acid of 65% and a solid-liquid ratio of microcrystalline cellulose to sulfuric acid of 1:10. The mixture was heated to 50°C in an oil bath, stirred for 30 min, cooled to room temperature, placed in a centrifuge tube, and washed three times with deionized water. The suspension was dialyzed to neutrality and freeze-dried at -50°C in a vacuum freeze-drying machine for 48 h to obtain cellulose nanocrystals.

[0038] (2) Take 1 g of cellulose nanocrystals and place them in a beaker. Add 80 mL of anhydrous ethanol and 20 mL of deionized water. Ultrasonicate for 10 min, then heat to 40 °C, add 5 mL of 3-aminopropyltriethoxysilane, and stir magnetically for 10 h at a speed of 300 rpm. Collect the product by centrifugation, wash it with deionized water, and dry it in an oven at 50 °C for 2 h to obtain modified cellulose nanocrystals.

[0039] Furthermore, the preparation method of the modified chloroether resin comprises the following steps:

[0040] S1. Add nano-silica to anhydrous ethanol and disperse by ultrasonication to obtain a silica dispersion with a mass fraction of 5%;

[0041] S2, take 2 mL of KH-570 aqueous solution and stir and hydrolyze at 50°C for 5 hours, the mass fraction of KH-570 aqueous solution is 5%, add 5 mL of the silica dispersion described in step S1, stir evenly, adjust the pH value to 10 with ammonia water, react at 50°C for 10 hours, filter after the reaction, elute the residual reagent with acetone, and dry to obtain modified silica;

[0042] S3. Take modified silica and add it to the chloroether resin, with the mass ratio of modified silica to chloroether resin being 2:20, and perform ultrasonic treatment for 20 minutes to obtain modified chloroether resin.

[0043] Furthermore, the preparation method of the composite phosphor comprises the following steps:

[0044] Take europium nitrate, dysprosium nitrate, strontium nitrate and aluminum nitrate and add them to deionized water, stir evenly, add oxalic acid and adjust the pH value to 8 with ammonia water, let it stand for 24 hours, centrifuge and filter, wash the filter residue with anhydrous ethanol three times, dry and grind to obtain powder, place the powder in a high-temperature furnace, and keep it at 1350°C for 3 hours to obtain a composite phosphor.

[0045] This embodiment provides a method for preparing luminous decorative paper, which specifically includes the following steps:

[0046] ① Take modified chloroether resin, methacrylic acid, methyl methacrylate, styrene, and butyl acrylate, add deionized water twice the total mass, add sodium bicarbonate, and stir for 20 minutes to obtain a mixed solution;

[0047] ② Prepare ammonium persulfate into an aqueous solution with a mass fraction of 5%, place the mixed solution described in step ① in a flask, add modified chloroether resin and modified cellulose nanocrystals, heat to 70°C, add ammonium persulfate solution, heat to 80°C, keep warm for 4 hours, cool to 40°C after the reaction is completed, adjust the pH value to 8, stir for 20 minutes to obtain a mixed emulsion, add composite phosphor and pigment to obtain luminous ink;

[0048] ③ Apply the luminous ink described in step ② on the bottom paper to obtain luminous decorative paper.

[0049] Example 2

[0050] A luminous decorative paper comprises a base paper and luminous ink. The luminous ink comprises the following components in parts by weight: 10 parts of modified chloroether resin, 8 parts of modified cellulose nanocrystals, 5 parts of methacrylic acid, 10 parts of methyl methacrylate, 12 parts of styrene, 20 parts of butyl acrylate, 2 parts of ammonium persulfate, 0.5 part of sodium bicarbonate, 11 parts of composite phosphor, and 15 parts of pigment.

[0051] Furthermore, the preparation method of the modified cellulose nanocrystals comprises the following steps:

[0052] (1) Mix microcrystalline cellulose and sulfuric acid in a flask with a mass fraction of 65% sulfuric acid and a solid-liquid ratio of microcrystalline cellulose to sulfuric acid of 1:15. Heat in an oil bath to 60°C, stir for 40 minutes, cool to room temperature, place in a centrifuge tube, wash three times with deionized water, dialyze the suspension to neutrality, and freeze-dry at -50°C in a vacuum freeze-drying machine for 48 hours to obtain cellulose nanocrystals.

[0053] (2) Take 1 g of cellulose nanocrystals and place them in a beaker. Add 80 mL of anhydrous ethanol and 20 mL of deionized water. Ultrasonic treatment was performed for 15 min. Then, the mixture was heated to 40 °C and 8 mL of 3-aminopropyltriethoxysilane was added dropwise. The mixture was magnetically stirred for 12 h at a speed of 300 rpm. The product was collected by centrifugation, washed with deionized water, and dried in an oven at 60 °C for 4 h to obtain modified cellulose nanocrystals.

[0054] Furthermore, the preparation method of the modified chloroether resin comprises the following steps:

[0055] S1. Add nano-silica to anhydrous ethanol and disperse by ultrasonication to obtain a silica dispersion with a mass fraction of 5%;

[0056] S2, take 2 mL of KH-570 aqueous solution and stir and hydrolyze at 50°C for 6 hours, the mass fraction of KH-570 aqueous solution is 5%, add 7 mL of the silica dispersion described in step S1, stir evenly, adjust the pH value to 10 with ammonia water, react at 50°C for 12 hours, filter after the reaction, elute the residual reagent with acetone, and dry to obtain modified silica;

[0057] S3. Take modified silica and add it to the chloroether resin, with the mass ratio of modified silica to chloroether resin being 2:30, and perform ultrasonic treatment for 30 minutes to obtain modified chloroether resin.

[0058] Furthermore, the preparation method of the composite phosphor comprises the following steps:

[0059] Take europium nitrate, dysprosium nitrate, strontium nitrate and aluminum nitrate, add them to deionized water, stir evenly, add oxalic acid and adjust the pH value to 9 with ammonia water, let it stand for 24 hours, centrifuge and filter, wash the filter residue with anhydrous ethanol three times, dry and grind to obtain powder, place the powder in a high-temperature furnace, and keep it at 1350°C for 3 hours to obtain a composite phosphor.

[0060] This embodiment provides a method for preparing luminous decorative paper, which specifically includes the following steps:

[0061] ① Take modified chloroether resin, methacrylic acid, methyl methacrylate, styrene, and butyl acrylate, add deionized water twice the total mass, add sodium bicarbonate, and stir for 30 minutes to obtain a mixed solution;

[0062] ② Prepare ammonium persulfate into an aqueous solution with a mass fraction of 5%, place the mixed solution described in step ① in a flask, add modified chloroether resin and modified cellulose nanocrystals, heat to 70°C, add ammonium persulfate solution, heat to 85°C, and keep warm for 5 hours. After the reaction is completed, cool to 40°C, adjust the pH value to 8, and stir for 20 minutes to obtain a mixed emulsion. Add composite phosphor and pigment to obtain luminous ink;

[0063] ③ Apply the luminous ink described in step ② on the bottom paper to obtain luminous decorative paper.

[0064] Example 3

[0065] A luminous decorative paper comprises a base paper and luminous ink. The luminous ink comprises the following components in parts by weight: 8 parts of modified chloroether resin, 7 parts of modified cellulose nanocrystals, 4 parts of methacrylic acid, 9 parts of methyl methacrylate, 10 parts of styrene, 17 parts of butyl acrylate, 1.5 parts of ammonium persulfate, 1.3 parts of sodium bicarbonate, 10 parts of composite phosphor, and 13 parts of pigment.

[0066] Furthermore, the preparation method of the modified cellulose nanocrystals comprises the following steps:

[0067] (1) Microcrystalline cellulose and sulfuric acid were mixed in a flask with a mass fraction of sulfuric acid of 65% and a solid-liquid ratio of microcrystalline cellulose to sulfuric acid of 1:13. The mixture was heated to 55°C in an oil bath, stirred for 35 minutes, cooled to room temperature, placed in a centrifuge tube, and washed three times with deionized water. The suspension was dialyzed to neutrality and freeze-dried at -50°C in a vacuum freeze-drying process for 48 hours to obtain cellulose nanocrystals.

[0068] (2) Take 1 g of cellulose nanocrystals and place them in a beaker. Add 80 mL of anhydrous ethanol and 20 mL of deionized water. Ultrasonic treatment was performed for 13 min. Then, the mixture was heated to 40 °C and 7 mL of 3-aminopropyltriethoxysilane was added dropwise. The mixture was magnetically stirred for 11 h at a speed of 300 rpm. The product was collected by centrifugation, washed with deionized water, and dried in an oven at 55 °C for 3 h to obtain modified cellulose nanocrystals.

[0069] Furthermore, the preparation method of the modified chloroether resin comprises the following steps:

[0070] S1. Add nano-silica to anhydrous ethanol and disperse by ultrasonication to obtain a silica dispersion with a mass fraction of 5%;

[0071] S2, take 2 mL of KH-570 aqueous solution and stir and hydrolyze at 50°C for 5 hours, the mass fraction of KH-570 aqueous solution is 5%, add 6 mL of the silica dispersion described in step S1, stir evenly, adjust the pH value to 10 with ammonia water, react at 50°C for 11 hours, filter after the reaction, elute the residual reagent with acetone, and dry to obtain modified silica;

[0072] S3. Take modified silica and add it to the chloroether resin, with the mass ratio of modified silica to chloroether resin being 2:25, and perform ultrasonic treatment for 25 minutes to obtain modified chloroether resin.

[0073] Furthermore, the preparation method of the composite phosphor comprises the following steps:

[0074] Take europium nitrate, dysprosium nitrate, strontium nitrate and aluminum nitrate and add them to deionized water, stir evenly, add oxalic acid and adjust the pH value to 8 with ammonia water, let it stand for 24 hours, centrifuge and filter, wash the filter residue with anhydrous ethanol three times, dry and grind to obtain powder, place the powder in a high-temperature furnace, and keep it at 1350°C for 3 hours to obtain a composite phosphor.

[0075] This embodiment provides a method for preparing luminous decorative paper, which specifically includes the following steps:

[0076] ① Take modified chloroether resin, methacrylic acid, methyl methacrylate, styrene, and butyl acrylate, add deionized water twice the total mass, add sodium bicarbonate, and stir for 25 minutes to obtain a mixed solution;

[0077] ② Prepare ammonium persulfate into an aqueous solution with a mass fraction of 5%, place the mixed solution described in step ① in a flask, add modified chloroether resin and modified cellulose nanocrystals, heat to 70°C, add ammonium persulfate solution, heat to 83°C, and keep warm for 4.5 hours. After the reaction is completed, cool to 40°C, adjust the pH value to 8, and stir for 20 minutes to obtain a mixed emulsion, add composite phosphor and pigment to obtain luminous ink;

[0078] ③ Apply the luminous ink described in step ② on the bottom paper to obtain luminous decorative paper.

[0079] Comparative Example 1

[0080] This comparative example provides a luminous decorative paper and a preparation method thereof. The only difference between the comparative example and Example 1 is that the modified chloroether resin is not included in all components, and the remaining components and component contents are the same as those in Example 1.

[0081] Comparative Example 2

[0082] This comparative example provides a luminous decorative paper and a preparation method thereof, which differs from Example 1 only in that modified cellulose nanocrystals are not included in all components, and the remaining components and component contents are the same as those in Example 1.

[0083] Experimental example

[0084] 1. Adhesion fastness tests were conducted on the luminous inks prepared in Examples 1-3 of the present invention and Comparative Examples 1 and 2. The specific method was based on the national standard GB / T 13217.7-2009. A PET film was used as the test substrate to prepare the ink layer to be tested. After standing at room temperature for 24 hours, adhesive tape was applied to the surface of the ink layer and pressed firmly. The tape was quickly removed while maintaining a right angle to the ink layer. A 2 mm wide grid paper was placed underneath the ink layer. The remaining ink layer and the number of grids removed by the tape were observed. The adhesion fastness of the ink layer was calculated according to the following formula:

[0085] C=C1 / (C1+C2)×100%

[0086] Where: C represents the adhesion strength of the ink, C1 represents the number of grids of the ink layer, and C2 represents the number of grids of the ink layer that has been peeled off.

[0087] 2. The luminous inks prepared in Examples 1-3 of the present invention and Comparative Examples 1 and 2 were subjected to an anti-blocking test. The specific method was based on the national standard GB / T 13217.8-2009. An ink layer sample was prepared according to the adhesion fastness test. The sample was placed for 2 minutes and then transferred to a 60°C high-temperature drying oven for 5 minutes. After cooling, it was folded in half and placed in a 50°C drying oven and pressed with a 2 kg weight for 2 hours. After removal, the folded portion was opened and the adhesion was observed. When a 2 mm grid was used, the number of grids of the ink layer and the removed ink layer was observed. The ink adhesion degree was determined according to the following formula:

[0088] A=A1 / (A1+A2)×100%

[0089] Wherein: A represents the ink adhesion degree of the ink, A1 represents the number of grids of the ink layer, and A2 represents the number of grids of the ink layer that has been peeled off.

[0090] 3. The luminous decorative papers prepared in Examples 1-3 of the present invention and Comparative Examples 1 and 2 were subjected to a light aging resistance test. The specific method is as follows: a xenon lamp was used to irradiate the luminous decorative papers, and the color change was detected every hour. When obvious fading occurred, the papers were removed and the time of color change was recorded.

[0091] 4. The surface morphology of the modified cellulose nanocrystals described in Example 1 was observed using a scanning electron microscope.

[0092] Result Analysis

[0093] Figure 1 The following is a graph showing the adhesion fastness test results of the luminous inks of Examples 1-3 of the present invention and Comparative Examples 1-2. As shown in the figure, the adhesion fastnesses of Examples 1-3 are 100%, 98%, and 100%, respectively, that of Comparative Example 1 is 94%, and that of Comparative Example 2 is 92%. It can be seen that the addition of modified chloroether resin and modified cellulose nanocrystals can improve the adhesion fastness of the ink. The addition of modified chloroether resin can improve the adhesion performance and stability of the ink. The modified cellulose nanocrystals can improve the mechanical properties of acrylic acid, thereby improving the adhesion fastness of the ink.

[0094] Figure 2 This is a graph showing the anti-adhesion test results of the luminous inks of Examples 1-3 of the present invention and Comparative Examples 1-2. As shown in the figure, the adhesion fastnesses of Examples 1-3 are 98%, 98%, and 100%, respectively, that of Comparative Example 1 is 90%, and that of Comparative Example 2 is 92%. It can be seen that the addition of modified chloroether resin and modified cellulose nanocrystals can improve the anti-adhesion properties of the ink.

[0095] Figure 3 The following is a graph showing the light aging resistance test results of the luminous decorative paper of Examples 1-3 and Comparative Examples 1-2 of the present invention. As shown in the figure, the light aging resistance times of Examples 1-3 are 115 hours, 112 hours, and 118 hours, respectively, while that of Comparative Example 1 is 95 hours and that of Comparative Example 2 is 72 hours. Example 1 has better anti-aging effect than Comparative Example 2. This is because cellulose has anti-ultraviolet and antioxidant properties, which can slow down the oxidation rate of other components in the ink layer, thereby extending the service life of the ink layer. Cellulose can also provide a certain physical barrier effect, reducing direct exposure of light to the ink layer, and reducing damage to the ink layer caused by heat and ultraviolet rays.

[0096] Figure 4 This is the microscopic morphology of the modified cellulose nanocrystals described in Example 1 of the present invention. It can be seen that the modified cellulose nanocrystals have a long fiber structure and are evenly dispersed.

[0097] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

[0098] The present invention and its embodiments are described above. Such description is not restrictive. The drawings show only one embodiment of the present invention, and actual applications are not limited thereto. In short, if a person skilled in the art is inspired by the above, and does not deviate from the purpose of the present invention, any method and embodiment similar to the technical solution without creative design shall fall within the scope of protection of the present invention.

Claims

1. A luminous decorative paper, comprising a base paper and luminous ink, characterized in that: The luminous ink comprises the following components in parts by weight: 5-10 parts of modified chloroether resin, 6-8 parts of modified cellulose nanocrystals, 3-5 parts of methacrylic acid, 6-10 parts of methyl methacrylate, 8-12 parts of styrene, 15-20 parts of butyl acrylate, 1-2 parts of ammonium persulfate, 0.2-0.5 parts of sodium bicarbonate, 8-11 parts of composite phosphor, and 12-15 parts of pigment; The method for preparing the luminous decorative paper specifically comprises the following steps: ① Take modified chloroether resin, methacrylic acid, methyl methacrylate, styrene, and butyl acrylate, add deionized water twice the total mass, add sodium bicarbonate, and stir for 20-30 minutes to obtain a mixed solution; ② Prepare ammonium persulfate into a 5% by mass aqueous solution, place the mixed solution described in step ① in a flask, add modified chloroether resin and modified cellulose nanocrystals, heat to 70°C, add ammonium persulfate solution, heat to 80-85°C, keep warm for 4-5 hours, cool to 40°C after the reaction is completed, adjust the pH value to 8, stir for 20 minutes to obtain a mixed emulsion, add composite phosphor and pigment to obtain luminous ink; ③ Apply the luminous ink described in step ② on the bottom paper to obtain luminous decorative paper; The preparation method of the modified cellulose nanocrystals comprises the following steps: (1) Mix microcrystalline cellulose and sulfuric acid in a flask, heat in an oil bath to 50-60°C, stir for 30-40 minutes, cool to room temperature, place in a centrifuge tube, wash with deionized water three times, dialyze the suspension to neutrality, and freeze-dry at -50°C in a vacuum freeze-drying machine for 48 hours to obtain cellulose nanocrystals. (2) Cellulose nanocrystals were placed in a beaker, 80 mL of anhydrous ethanol and 20 mL of deionized water were added, and the mixture was ultrasonically treated for 10-15 min. The mixture was then heated to 40 °C, 3-aminopropyltriethoxysilane was added dropwise, and magnetic stirring was performed for 10-12 h at a speed of 300 rpm. The product was collected by centrifugation, washed with deionized water, and dried in an oven at 50-60 °C for 2-4 h to obtain modified cellulose nanocrystals. The preparation method of the modified chloroether resin comprises the following steps: S1. Add nano-silica to anhydrous ethanol and disperse by ultrasonication to obtain a silica dispersion; S2. Take a KH-570 aqueous solution and stir and hydrolyze it at 50°C for 5-6 hours, add it to the silica dispersion described in step S1, stir evenly, adjust the pH value to 10 with ammonia water, react at 50°C for 10-12 hours, filter after the reaction, elute the residual reagent with acetone, and dry to obtain modified silica; S3. Take the modified silica and add it to the chloroether resin, and perform ultrasonic treatment for 20-30 minutes to obtain the modified chloroether resin.

2. The luminous decorative paper according to claim 1, characterized in that: In step (1), the mass fraction of the sulfuric acid is 65%, and the material-liquid ratio of the microcrystalline cellulose to the sulfuric acid is 1:10-15.

3. The luminous decorative paper according to claim 2, characterized in that: In step (2), the material-liquid ratio of the cellulose nanocrystals to 3-aminopropyltriethoxysilane is 1:5-8.

4. The luminous decorative paper according to claim 3, characterized in that: In step S1, the mass fraction of the silicon dioxide dispersion is 5%.

5. The luminous decorative paper according to claim 4, characterized in that: In step S2, the mass fraction of the KH-570 aqueous solution is 5%, and the volume ratio of the KH-570 aqueous solution to the silicon dioxide dispersion is 2:5-7.

6. The luminous decorative paper according to claim 5, characterized in that: In step S3, the mass ratio of the modified silica to the chloroether resin is 2:20-30.

7. The luminous decorative paper according to claim 6, characterized in that: The preparation method of the composite phosphor comprises the following steps: adding europium nitrate, dysprosium nitrate, strontium nitrate and aluminum nitrate to deionized water, stirring evenly, adding oxalic acid and then adjusting the pH value to 8-9 with ammonia water, standing for 24 hours, centrifuging and filtering, washing the filter residue three times with anhydrous ethanol, drying and grinding to obtain a powder, placing the powder in a high-temperature furnace and keeping it at 1350° C. for 3 hours to obtain the composite phosphor.

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