A kind of water-based bio-based decorative paper ink and preparation method thereof

Abstract

The invention relates to the technical field of decorative paper ink, and discloses a water-based bio-based decorative paper ink and a preparation method thereof. The invention adds water-based bio-based epoxy acrylate resin, quaternary ammonium salt modified triazole, boric acid modified nano-alumina, ethylene glycol, and a wetting agent BYK348 into a reactor, stirs, and obtains water-based bio-based decorative paper ink after completion. The sodium sulfonate group, boron element, and nano-alumina contained in the quaternary ammonium salt modified triazole and the boric acid modified nano-alumina all have good flame retardant effects, and together constitute a flame retardant system; the ammonium salt can be adsorbed onto negatively charged bacteria, forming a high concentration of ion groups on the surface of the bacteria, which directly affects the normal function of the bacterial cells, and at the same time destroys the permeability of the cell wall, causing the cell to dissolve and die, and plays an antibacterial role; the triazole group causes the cell membrane to die by destroying its structure, and also has a good antibacterial effect; the nano-alumina itself has a good antibacterial effect.

Description

Technical Field

[0001] The invention relates to the technical field of decorative paper ink, and in particular to a water-based bio-based decorative paper ink and a preparation method thereof. Background Art

[0002] Decorative paper ink is a special ink used to decorate base paper. It gives the base paper various colors and patterns. Decorative paper ink is a special ink used to decorate base paper. The ink is transferred to the base paper through the printing process to form rich colors and patterns. It is widely used in the printing of indoor decorative materials such as furniture, floors, and walls. However, long-term exposure to the air will cause bacteria to erode it, thus affecting its appearance. At the same time, when encountering a fire, the ink on the furniture is flammable, which will affect its normal use. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, patent CN111320892A discloses an ink and its preparation method. The ink of the invention has the characteristics of low viscosity, good dispersibility, and easy drying, but its flame retardant and antibacterial properties have not been improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a water-based bio-based decorative paper ink and a preparation method thereof, which has good antibacterial and flame retardant effects.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a water-based bio-based decorative paper ink, comprising the following components by weight: 16-25 parts by weight of water-based bio-based epoxy acrylate resin, 6-9 parts by weight of quaternary ammonium salt-modified triazole, 3-5 parts by weight of boric acid-modified nano-alumina, 1-2 parts by weight of ethylene glycol, and 0.8-1 parts by weight of wetting agent BYK348.

[0007] Preferably, the preparation method of the quaternary ammonium salt modified triazole is:

[0008] (1) Add 2-chloroethyldimethylamine and 1,3-propane sultone to acetone solvent for dissolution, then dropwise add 2-4% sodium hydroxide solution, react at 65-90°C for 6-12h, and after the reaction, concentrate under reduced pressure to remove the solvent, and recrystallize the crude product in ethanol to obtain intermediate 1;

[0009] (2) Add intermediate 1 and sodium azide to N,N-dimethylformamide solvent, stir to dissolve, and react at 60-75°C for 10-12 hours. After the reaction is completed, add the reaction solution to n-hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent in vacuo to obtain intermediate 2;

[0010] (3) 6-14 parts by weight of 1-methylpropargylamine and 4-8 parts by weight of intermediate 2 are added to anhydrous N,N-dimethylformamide, and then 0.1-0.2 parts by weight of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.1-0.15 parts by weight of cuprous bromide are added, nitrogen is introduced for protection, and the reaction is carried out at 40-65°C. After the reaction is completed, the reaction solution is passed through an alumina chromatography column and eluted with tetrahydrofuran as an eluent to remove copper salts in the system. The reaction is then concentrated by rotary evaporation and dialyzed with water for 2-4 days to remove N,N-dimethylformamide to obtain a quaternary ammonium salt modified triazole.

[0011] Preferably, the mass ratio of 2-chloroethyldimethylamine to 1,3-propane sultone in (1) is 1:0.9-1.1.

[0012] Preferably, the mass ratio of the intermediate 1 to sodium azide in (2) is 1:1.3-1.5.

[0013] Preferably, the reaction time in (3) is 4-7 hours.

[0014] Preferably, the preparation method of the boric acid modified nano-alumina is:

[0015] S1. Add nano-alumina to a mixed solvent of ethanol and deionized water, disperse by ultrasonication, stir evenly, then continue to add γ-aminopropyltriethoxysilane, react at 70-95°C for 10-14h, centrifuge after the reaction, wash and dry to obtain amino-alumina nano-alumina;

[0016] S2. Add 4-8 parts by weight of amino-modified nano-alumina and 5-10 parts by weight of 2-aminophenylboric acid into a reactor filled with N,N-dimethylformamide solvent, react at 70-80°C for 6-8h, and then perform reduced pressure distillation, washing, and recrystallization of the crude product to obtain boric acid-modified nano-alumina.

[0017] Preferably, the mass ratio of nano-alumina to γ-aminopropyltriethoxysilane in S1 is 1:1.3-1.4.

[0018] Preferably, the preparation method of the water-based bio-based decorative paper ink is: adding water-based bio-based epoxy acrylate resin, quaternary ammonium salt-modified triazole, boric acid-modified nano-alumina, ethylene glycol, and wetting agent BYK348 into a reactor, stirring for 20-25 minutes, and then obtaining the water-based bio-based decorative paper ink. (III) Beneficial technical effects

[0019] The invention provides a method for obtaining water-based bio-based decorative paper ink by adding water-based bio-based epoxy acrylate resin, quaternary ammonium salt-modified triazole, boric acid-modified nano-alumina, ethylene glycol and wetting agent BYK348 into a reactor and stirring the mixture.

[0020] The sodium sulfonate groups, boron elements, and nano-alumina contained in the quaternary ammonium salt-modified triazole and boric acid-modified nano-alumina all have good flame retardant effects and together constitute a flame retardant system; ammonium salts can be adsorbed onto negatively charged bacteria, forming high-concentration ion groups on the bacterial surface, which directly affect the normal function of bacterial cells, while destroying the permeability of the cell wall, leading to cell lysis and death, and playing an antibacterial role; the triazole group also has a good antibacterial effect by destroying the structure of the cell membrane and causing its death; the nano-alumina itself has a good antibacterial effect. During the stirring process, the quaternary ammonium salt groups in the quaternary ammonium salt-modified triazole and the amino groups in the boric acid-modified nano-alumina will form hydrogen bonds with the acid esters in the water-based bio-based epoxy acrylate resin, making them cross-linked with each other and improving their compatibility with each other. DETAILED DESCRIPTION Example 1

[0021] (1) 2-chloroethyldimethylamine and 1,3-propane sultone were added to acetone solvent for dissolution, wherein the mass ratio of 2-chloroethyldimethylamine to 1,3-propane sultone was 1:0.9, and then a 2% sodium hydroxide solution was added dropwise, and the reaction was carried out at 65° C. for 6 h. After the reaction, the solvent was removed by concentration under reduced pressure, and the crude product was recrystallized in ethanol to obtain intermediate 1;

[0022] (2) Add intermediate 1 and sodium azide to N,N-dimethylformamide solvent, wherein the mass ratio of intermediate 1 to sodium azide is 1:1.3, stir and dissolve, react at 60°C for 10 hours, and after the reaction is completed, add n-hexane to dissolve the solution after the reaction, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent in vacuo to obtain intermediate 2;

[0023] (3) 6 parts by weight of 1-methylpropargylamine and 4 parts by weight of intermediate 2 were added to anhydrous N,N-dimethylformamide, and then 0.1 parts by weight of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.1 parts by weight of cuprous bromide were added, nitrogen was introduced for protection, and the reaction was carried out at 40°C for 4 hours. After the reaction was completed, the reaction solution was passed through an alumina chromatography column and eluted with tetrahydrofuran as an eluent to remove the copper salt in the system. After rotary evaporation and concentration, the reaction was dialyzed with water for 2 days to remove N,N-dimethylformamide to obtain a quaternary ammonium salt modified triazole;

[0024] (4) adding nano-alumina to a mixed solvent of ethanol and deionized water, dispersing by ultrasonication, stirring evenly, and then adding γ-aminopropyltriethoxysilane, wherein the mass ratio of nano-alumina to γ-aminopropyltriethoxysilane is 1:1.3, reacting at 70° C. for 10 h, centrifuging after the reaction, washing and drying to obtain amino-treated nano-alumina;

[0025] (5) adding 4 parts by weight of amino-modified nano-alumina and 5 parts by weight of 2-aminophenylboric acid into a reactor filled with N,N-dimethylformamide solvent, reacting at 70° C. for 6 hours, and then distilling under reduced pressure, washing, and recrystallizing the crude product to obtain boric acid-modified nano-alumina;

[0026] (6) 16 parts by weight of water-based bio-based epoxy acrylate resin, 6 parts by weight of quaternary ammonium salt-modified triazole, 3 parts by weight of boric acid-modified nano-alumina, 1 part by weight of ethylene glycol, and 0.8 parts by weight of wetting agent BYK348 were added into a reactor and stirred for 20 minutes to obtain water-based bio-based decorative paper ink. Example 2

[0027] (1) 2-chloroethyldimethylamine and 1,3-propane sultone were added to an acetone solvent for dissolution, wherein the mass ratio of 2-chloroethyldimethylamine to 1,3-propane sultone was 1:1.1, and then a 4% sodium hydroxide solution was added dropwise, and the reaction was carried out at 90° C. for 12 h. After the reaction, the solvent was removed by concentration under reduced pressure, and the crude product was recrystallized in ethanol to obtain intermediate 1;

[0028] (2) Add intermediate 1 and sodium azide to N,N-dimethylformamide solvent, wherein the mass ratio of intermediate 1 to sodium azide is 1:1.5, stir and dissolve, react at 75°C for 12 hours, and after the reaction is completed, add the reaction solution into n-hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent in vacuo to obtain intermediate 2;

[0029] (3) 14 parts by weight of 1-methylpropargylamine and 8 parts by weight of intermediate 2 were added to anhydrous N,N-dimethylformamide, and then 0.2 parts by weight of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.15 parts by weight of cuprous bromide were added, nitrogen was introduced for protection, and the reaction was carried out at 65°C for 7 hours. After the reaction was completed, the reaction solution was passed through an alumina chromatography column and eluted with tetrahydrofuran as an eluent to remove the copper salt in the system. After rotary evaporation and concentration, the N,N-dimethylformamide was removed by dialyzing with water for 4 days to obtain a quaternary ammonium salt modified triazole;

[0030] (4) adding nano-alumina to a mixed solvent of ethanol and deionized water, dispersing by ultrasonication, stirring evenly, and then adding γ-aminopropyltriethoxysilane, wherein the mass ratio of nano-alumina to γ-aminopropyltriethoxysilane is 1:1.4, reacting at 95° C. for 14 h, centrifuging after the reaction, washing and drying to obtain amino-treated nano-alumina;

[0031] (5) adding 8 parts by weight of amino-modified nano-alumina and 10 parts by weight of 2-aminophenylboric acid into a reactor filled with N,N-dimethylformamide solvent, reacting at 80° C. for 8 h, and then distilling under reduced pressure, washing, and recrystallizing the crude product to obtain boric acid-modified nano-alumina;

[0032] (6) 25 parts by weight of water-based bio-based epoxy acrylate resin, 9 parts by weight of quaternary ammonium salt-modified triazole, 5 parts by weight of boric acid-modified nano-alumina, 2 parts by weight of ethylene glycol, and 1 part by weight of wetting agent BYK348 were added into a reactor and stirred for 25 minutes to obtain water-based bio-based decorative paper ink. Example 3

[0033] (1) 2-chloroethyldimethylamine and 1,3-propane sultone were added to an acetone solvent for dissolution, wherein the mass ratio of 2-chloroethyldimethylamine to 1,3-propane sultone was 1:1.0, and then a 3% sodium hydroxide solution was added dropwise, and the mixture was reacted at 75°C for 9 hours. After the reaction, the solvent was removed by concentration under reduced pressure, and the crude product was recrystallized in ethanol to obtain intermediate 1;

[0034] (2) Add intermediate 1 and sodium azide to N,N-dimethylformamide solvent, wherein the mass ratio of intermediate 1 to sodium azide is 1:1.4, stir and dissolve, react at 65°C for 11 hours, and after the reaction is completed, add n-hexane to dissolve the solution after the reaction, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent in vacuo to obtain intermediate 2;

[0035] (3) 10 parts by weight of 1-methylpropargylamine and 6 parts by weight of intermediate 2 were added to anhydrous N,N-dimethylformamide, and then 0.15 parts by weight of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.12 parts by weight of cuprous bromide were added, nitrogen was introduced for protection, and the reaction was carried out at 55°C for 5 hours. After the reaction was completed, the reaction solution was passed through an alumina chromatography column and washed with tetrahydrofuran as the eluent to remove the copper salt in the system. After rotary evaporation and concentration, the N,N-dimethylformamide was removed by dialyzing with water for 3 days to obtain a quaternary ammonium salt modified triazole;

[0036] (4) adding nano-alumina to a mixed solvent of ethanol and deionized water, dispersing by ultrasonication, stirring evenly, and then adding γ-aminopropyltriethoxysilane, wherein the mass ratio of nano-alumina to γ-aminopropyltriethoxysilane is 1:1.35, reacting at 80° C. for 12 h, centrifuging after the reaction, washing and drying to obtain amino-treated nano-alumina;

[0037] (5) adding 6 parts by weight of amino-modified nano-alumina and 8 parts by weight of 2-aminophenylboric acid into a reactor filled with N,N-dimethylformamide solvent, reacting at 75° C. for 7 h, and then distilling under reduced pressure, washing, and recrystallizing the crude product to obtain boric acid-modified nano-alumina;

[0038] (6) 22 parts by weight of water-based bio-based epoxy acrylate resin, 8 parts by weight of quaternary ammonium salt-modified triazole, 4 parts by weight of boric acid-modified nano-alumina, 1 part by weight of ethylene glycol, and 1 part by weight of wetting agent BYK348 were added into a reactor and stirred for 22 minutes to obtain water-based bio-based decorative paper ink. Example 4

[0039] (1) 2-chloroethyldimethylamine and 1,3-propane sultone were added to acetone solvent for dissolution, wherein the mass ratio of 2-chloroethyldimethylamine to 1,3-propane sultone was 1:0.9, and then a 2% sodium hydroxide solution was added dropwise, and the reaction was carried out at 65° C. for 6 h. After the reaction, the solvent was removed by concentration under reduced pressure, and the crude product was recrystallized in ethanol to obtain intermediate 1;

[0040] (2) Add intermediate 1 and sodium azide to N,N-dimethylformamide solvent, wherein the mass ratio of intermediate 1 to sodium azide is 1:1.3, stir and dissolve, react at 60°C for 10 hours, and after the reaction is completed, add n-hexane to dissolve the solution after the reaction, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent in vacuo to obtain intermediate 2;

[0041] (3) 14 parts by weight of 1-methylpropargylamine and 8 parts by weight of intermediate 2 were added to anhydrous N,N-dimethylformamide, and then 0.2 parts by weight of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.15 parts by weight of cuprous bromide were added, nitrogen was introduced for protection, and the reaction was carried out at 65°C for 7 hours. After the reaction was completed, the reaction solution was passed through an alumina chromatography column and eluted with tetrahydrofuran as an eluent to remove the copper salt in the system. After rotary evaporation and concentration, the N,N-dimethylformamide was removed by dialyzing with water for 4 days to obtain a quaternary ammonium salt modified triazole;

[0042] (4) adding nano-alumina to a mixed solvent of ethanol and deionized water, dispersing by ultrasonication, stirring evenly, and then adding γ-aminopropyltriethoxysilane, wherein the mass ratio of nano-alumina to γ-aminopropyltriethoxysilane is 1:1.4, reacting at 95° C. for 14 h, centrifuging after the reaction, washing and drying to obtain amino-treated nano-alumina;

[0043] (5) adding 6 parts by weight of amino-modified nano-alumina and 8 parts by weight of 2-aminophenylboric acid into a reactor filled with N,N-dimethylformamide solvent, reacting at 75° C. for 7 h, and then distilling under reduced pressure, washing, and recrystallizing the crude product to obtain boric acid-modified nano-alumina;

[0044] (6) 22 parts by weight of water-based bio-based epoxy acrylate resin, 8 parts by weight of quaternary ammonium salt-modified triazole, 4 parts by weight of boric acid-modified nano-alumina, 1 part by weight of ethylene glycol, and 1 part by weight of wetting agent BYK348 were added into a reactor and stirred for 22 minutes to obtain water-based bio-based decorative paper ink.

[0045] Comparative Example 1

[0046] This comparative example is different from Example 4 in that no quaternary ammonium salt is added to modify the triazole.

[0047] Comparative Example 2

[0048] The difference between this comparative example and Example 4 is that no boric acid-modified nano-alumina is added.

[0049] A Staphylococcus aureus liquid with a concentration of 2×108 CFU / mL was added to a sterilized culture dish as a test strain, and then a solid agar medium was added and dissolved, cooled to 45°C, and then poured into a culture dish, 20 mL was poured into each plate with an inner diameter of 10 cm, and then the water-based bio-based decorative paper ink (with a diameter of 3 cm and a thickness of 1 mm) of the embodiment of the present invention and the comparative example was placed on the culture plate, and cultured in a constant temperature incubator for 12 hours at a temperature of 37°C. After culture, the diameter of the inhibition zone was measured. The test results are shown in Table 1.

[0050] Table 1: Antimicrobial testing.

[0051] project Diameter of inhibition zone (mm) Example 1 16.7 Example 2 15.8 Example 3 16.9 Example 4 15.4 Comparative Example 1 11.7 Comparative Example 2 11.2

[0052] It can be seen from Table 1 that the diameter of the inhibition zone of the embodiments of the present invention reaches 15.4-16.9 mm, indicating that it has a good antibacterial effect.

[0053] The oxygen index of water-based bio-based decorative paper ink was tested using an oxygen index tester, and the combustion grade of water-based bio-based decorative paper ink was tested using a horizontal and vertical combustion tester.

[0054] Table 2: Flame retardancy tests.

[0055] project Oxygen index (%) UL-94 Example 1 32 V-0 Example 2 33 V-0 Example 3 32 V-0 Example 4 31 V-0 Comparative Example 1 20 V-1 Comparative Example 2 21 V-1

[0056] It can be seen from Table 2 that Examples 1-4 of the present invention have better flame retardant effects than Comparative Examples 1-2.

[0057] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A water-based bio-based decorative paper ink, characterized in that: The invention comprises the following components by weight: 16-25 parts by weight of water-based bio-based epoxy acrylate resin, 6-9 parts by weight of quaternary ammonium salt-modified triazole, 3-5 parts by weight of boric acid-modified nano-alumina, 1-2 parts by weight of ethylene glycol, and 0.8-1 parts by weight of wetting agent BYK348; The preparation method of the quaternary ammonium salt modified triazole is: (1) Add 2-chloroethyldimethylamine and 1,3-propane sultone to acetone solvent for dissolution, then dropwise add 2-4% sodium hydroxide solution, react at 65-90°C for 6-12h, and after the reaction, concentrate under reduced pressure to remove the solvent, and recrystallize the crude product in ethanol to obtain intermediate 1; (2) Add intermediate 1 and sodium azide to N,N-dimethylformamide solvent, stir to dissolve, and react at 60-75°C for 10-12 hours. After the reaction is completed, add the reaction solution to n-hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent in vacuo to obtain intermediate 2; (3) 6-14 parts by weight of 1-methylpropargylamine and 4-8 parts by weight of intermediate 2 are added to anhydrous N,N-dimethylformamide, and then 0.1-0.2 parts by weight of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.1-0.15 parts by weight of cuprous bromide are added, nitrogen is introduced for protection, and the reaction is carried out at 40-65° C. After the reaction is completed, the reaction solution is passed through an alumina chromatography column and washed with tetrahydrofuran as an eluent to remove copper salts in the system, and then concentrated by rotary evaporation, and dialyzed with water for 2-4 days to remove N,N-dimethylformamide to obtain a quaternary ammonium salt modified triazole; The preparation method of the boric acid modified nano-alumina is as follows: S1. Add nano-alumina to a mixed solvent of ethanol and deionized water, disperse by ultrasonication, stir evenly, then continue to add γ-aminopropyltriethoxysilane, react at 70-95°C for 10-14h, centrifuge after the reaction, wash and dry to obtain amino-alumina nano-alumina; S2. Add 4-8 parts by weight of amino-modified nano-alumina and 5-10 parts by weight of 2-aminophenylboric acid into a reactor filled with N,N-dimethylformamide solvent, react at 70-80°C for 6-8h, and then perform reduced pressure distillation, washing, and recrystallization of the crude product to obtain boric acid-modified nano-alumina.

2. The water-based bio-based decorative paper ink according to claim 1, characterized in that: The mass ratio of 2-chloroethyldimethylamine to 1,3-propane sultone in (1) is 1:0.9-1.

1.

3. The water-based bio-based decorative paper ink according to claim 1, characterized in that: The mass ratio of the intermediate 1 to sodium azide in (2) is 1:1.3-1.

5.

4. The water-based bio-based decorative paper ink according to claim 1, characterized in that: The reaction time in (3) is 4-7h.

5. The water-based bio-based decorative paper ink according to claim 1, characterized in that: The mass ratio of nano-alumina to γ-aminopropyltriethoxysilane in S1 is 1:1.3-1.

4.

6. A method for preparing the water-based bio-based decorative paper ink according to any one of claims 1 to 5, characterized in that: The preparation method of the water-based bio-based decorative paper ink comprises: adding water-based bio-based epoxy acrylate resin, quaternary ammonium salt-modified triazole, boric acid-modified nano-alumina, ethylene glycol, and wetting agent BYK348 into a reactor, stirring for 20-25 minutes, and obtaining the water-based bio-based decorative paper ink.