Degradable water-based ink and preparation method thereof

Abstract

The invention relates to the technical field of ink, and discloses degradable water-based ink and a preparation method thereof.The degradable water-based ink is characterized in that DCPD petroleum resin and 4-mercapto hydrocinnamic acid are subjected to a mercapto-ene addition reaction, and modified petroleum-based resin is obtained; diallylamine, mercaptopropyltriethoxysilane, 1, 6-dibromohexane, epichlorohydrin and the like are used as raw materials, a sulfydryl-alkene addition reaction, a substitution reaction and a quaternization reaction are sequentially performed to obtain a polysilane epoxy gemini quaternary ammonium salt, an epoxy group in the polysilane epoxy gemini quaternary ammonium salt and a hydroxyl group in polyvinyl alcohol are subjected to a ring-opening reaction, and the polysilane epoxy gemini quaternary ammonium salt is obtained. The degradable water-based ink is prepared by uniformly stirring and mixing modified petroleum-based resin, modified polyvinyl alcohol and polylactic acid to obtain modified petroleum-based resin, uniformly stirring and mixing the modified petroleum-based resin, the modified polyvinyl alcohol, polylactic acid, a defoaming agent, a dispersing agent and the like to obtain the degradable water-based ink, and tests prove that the degradable water-based ink prepared by the preparation method has relatively good antibacterial performance and adhesive force.

Description

Technical Field

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

[0002] Ink is the most basic raw material in the printing industry, generally composed of resin and organic solvents. However, these organic solvents not only bring harm to the human body, but also greatly pollute the environment. Therefore, in order to consider the needs of environmental protection, water-based ink came into being. Water-based ink is referred to as water-based ink. It is mainly made of water-based polymer resin, pigment, water-based additives, deionized water, etc. through composite grinding and processing. It is widely used in packaging and printing products such as food, beverages, and medicines. The resin used at this stage is mainly petroleum-based resin, but compared with bio-based resin, bio-based resin is more environmentally friendly than petroleum-based resin and is degradable. Therefore, degradable water-based ink has become the focus of current researchers.

[0003] DCPD petroleum resin is a resin produced by thermal polymerization using dicyclopentadiene obtained by separation of C5 as the main raw material. It has the advantages of good solubility, compatibility, low price, etc. Polyvinyl alcohol is a biodegradable polymer compound with low environmental pollution and good performance, and is widely used in various fields.

[0004] For example, the patent with application publication number CN 106519798 A discloses a thermal sublimation transfer ink and a preparation method thereof. The invention uses petroleum resin, polyvinyl alcohol, acrylic resin, etc. as raw materials, and the prepared ink has good adhesion, but does not improve the antibacterial properties of the ink. Summary of the invention

[0005] 1. Technical issues to be resolved

[0006] In view of the deficiencies in the prior art, the present invention provides a degradable water-based ink and a preparation method thereof. The prepared degradable water-based ink has good antibacterial properties and adhesion.

[0007] (II) Technical solution

[0008] A degradable water-based ink, the degradable water-based ink comprising the following weight components: 100-200 parts by weight of modified petroleum-based resin, 100 parts by weight of bio-based resin, 100-200 parts by weight of modified polyvinyl alcohol, 2-8 parts by weight of pigment, 1-3 parts by weight of defoamer, 2-6 parts by weight of dispersant, 1-3 parts by weight of emulsifier, and 2-5 parts by weight of wetting agent;

[0009] The bio-based resin is polylactic acid resin;

[0010] The modified petroleum-based resin is prepared from cinnamic acid and DCPD petroleum resin as raw materials, and the preparation method thereof is as follows: adding DCPD petroleum resin, 4-mercaptohydrocinnamic acid, and dibenzoyl peroxide initiator to toluene solvent, ultrasonically shaking, reacting at 80-90° C. for 1-3 hours, and after the reaction is completed, precipitating with methanol, filtering, and drying to obtain the modified petroleum-based resin;

[0011] The preparation method of the degradable water-based ink is:

[0012] (1) adding polyvinyl alcohol to deionized water, stirring and dissolving at 85-95° C., adding polysilane epoxy gemini quaternary ammonium salt thereto, adjusting the pH to 9-10 with a 10% by mass sodium hydroxide aqueous solution, stirring and reacting at 55-65° C. for 2-4 hours, and after the reaction is completed, washing with deionized water and drying to obtain modified polyvinyl alcohol;

[0013] (2) Adding modified petroleum-based resin, polylactic acid resin and modified polyvinyl alcohol to an ethanol aqueous solution with a relative molecular weight of 20%, stirring and dispersing for 20-40 minutes, and then adding pigment, defoamer, dispersant, emulsifier and wetting agent thereto and stirring for 15-30 minutes to obtain a degradable water-based ink.

[0014] Preferably, in (1), the usage ratio of polyvinyl alcohol to polysilane epoxy gemini quaternary ammonium salt is 1g:(0.1-0.5)g.

[0015] Preferably, the usage ratio of the DCPD petroleum resin, 4-mercaptohydrocinnamic acid and dibenzoyl peroxide is 100 g:(2-10) g:(0.2-0.5) g.

[0016] Preferably, in (1), the preparation method of the polysilane epoxy gemini quaternary ammonium salt is:

[0017] S1, adding diallylamine and mercaptopropyltriethoxysilane to a toluene solvent, stirring and dispersing, then adding azobisisobutyronitrile thereto, stirring and reacting at 70-80° C. for 30-60 min. After the reaction is completed, rotary evaporation, washing with deionized water, and drying to obtain intermediate 1;

[0018] S2, adding intermediate 1 and 1,6-dibromohexane to toluene solvent, stirring and mixing, then adding potassium iodide thereto, heating to 100-120°C under nitrogen protection, stirring and reacting for 20-30 hours, after the reaction is completed, cooling to room temperature, adding deionized water thereto, adjusting the pH to 9-10 with 50% sodium hydroxide aqueous solution, extracting with ether, and distilling the organic phase under reduced pressure to obtain intermediate 2;

[0019] S3. Add intermediate 2 to a 50% by mass aqueous solution of n-propanol, stir and disperse, heat to 45-55°C, add epichlorohydrin, adjust the pH to 8-9 with a 10% by mass aqueous solution of sodium hydroxide, stir and react for 2-5 hours, and after the reaction is completed, wash with deionized water and dry to obtain a polysilane epoxy gemini quaternary ammonium salt.

[0020] Preferably, in S1, the usage ratio of diallylamine, mercaptopropyltriethoxysilane and azobisisobutyronitrile is 1 g:(5-5.5) g:(0.03-0.05) g.

[0021] Preferably, in S2, the usage ratio of the intermediate 1, 1,6-dibromohexane and potassium iodide is (4.5-5) g: 1 g: (0.005-0.01) g.

[0022] Preferably, in S3, the usage ratio of intermediate 2 and epichlorohydrin is 1g:(0.15-0.2)g.

[0023] (III) Beneficial technical effects

[0024] The invention uses DCPD petroleum resin and 4-mercaptohydrocinnamic acid to undergo a mercapto-ene addition reaction, introduces cinnamic acid into the main chain structure of the petroleum resin, and obtains a modified petroleum-based resin. Diallylamine, mercaptopropyltriethoxysilane, 1,6-dibromohexane, epichlorohydrin, etc. are used as raw materials, and a polysilane epoxy gemini quaternary ammonium salt is obtained by sequentially undergoing a mercapto-ene addition reaction, a substitution reaction, and a quaternization reaction. The epoxy group in the polysilane epoxy gemini quaternary ammonium salt is used to undergo a ring-opening reaction with a hydroxyl group in polyvinyl alcohol to obtain a modified polyvinyl alcohol. Finally, the modified petroleum-based resin, the modified polyvinyl alcohol, the polylactic acid resin, a defoamer, a dispersant, etc. are stirred and mixed uniformly to obtain a degradable water-based ink.

[0025] The ink with petroleum resin as the main binder is difficult to degrade itself. The present invention combines it with volatile cinnamic acid, which can reduce the volatility of cinnamic acid on the one hand and improve the degradability of water-based ink on the other hand. It is then mixed with modified polyvinyl alcohol and polylactic acid. The prepared water-based ink has better degradability than the ink with petroleum resin as the binder alone. In addition, since cinnamaldehyde has antibacterial properties and is linked to the petroleum resin by chemical bonds, it can give the water-based ink long-term antibacterial properties and can form an auxiliary antibacterial effect with the quaternary ammonium salt antibacterial group. The two together improve the antibacterial effect of the ink.

[0026] In addition, the polysilane epoxy gemini quaternary ammonium salt prepared by the present invention contains diepoxy groups and tetrasiloxane structures, which, when combined with polyvinyl alcohol, can not only expand the degree of crosslinking, generate more crosslinking sites, reduce the brittleness of polyvinyl alcohol, and thus improve the mechanical properties of ink, but also, due to the easy hydrolysis of siloxane, the generated silicon oxygen bonds can condense with the hydroxyl groups on the surface of the matrix material, thereby improving the adhesion of the water-based ink. The water-based ink prepared by the present invention has excellent degradability, antibacterial properties and adhesion. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is the reaction route of polysilane epoxy gemini quaternary ammonium salt. DETAILED DESCRIPTION

[0028] The following further describes the degradable water-based ink and its preparation method in combination with some specific embodiments. The specific embodiments are for further illustrating the present invention in detail, but not for limiting the protection scope of the present invention.

[0029] The pigment is 24033 red, the defoamer is defoamer DEGO 822, the dispersant is dispersant DEGO 760W, the emulsifier is sodium lauryl sulfate, and the wetting agent is wetting agent DEGO 500.

[0030] Example 1

[0031] (1) 20 g of DCPD petroleum resin, 0.4 g of 4-mercaptohydrocinnamic acid, and 0.05 g of dibenzoyl peroxide initiator were added to toluene solvent, ultrasonically shaken, and reacted at 90° C. for 2 h. After the reaction was completed, methanol was precipitated, filtered, and dried to obtain a modified petroleum-based resin.

[0032] (2) 4.9 g of diallylamine and 25 g of mercaptopropyltriethoxysilane were added to a toluene solvent and dispersed with stirring. Then, 0.245 g of azobisisobutyronitrile was added thereto. The mixture was stirred and reacted at 75° C. for 60 min. After the reaction was completed, the mixture was rotary evaporated, washed with deionized water, and dried to obtain an intermediate 1.

[0033] (3) Add 22 g of intermediate 1 and 5 g of 1,6-dibromohexane to toluene solvent, stir and mix well, then add 0.025 g of potassium iodide, heat to 105° C. under nitrogen protection, stir and react for 26 h. After the reaction is completed, cool to room temperature, add deionized water, adjust the pH to 10 with 50% sodium hydroxide aqueous solution, extract with ether, and distill the organic phase under reduced pressure to obtain intermediate 2.

[0034] (4) Add 12 g of intermediate 2 to a 50% by mass aqueous solution of n-propanol, stir and disperse, heat to 50° C., add 1.8 g of epichlorohydrin, adjust the pH to 8 with a 10% by mass aqueous solution of sodium hydroxide, stir and react for 2 h, and after the reaction is completed, wash with deionized water and dry to obtain a polysilane epoxy gemini quaternary ammonium salt.

[0035] (5) Add 20 g of polyvinyl alcohol to deionized water, stir and dissolve at 85° C., then add 2 g of polysilane epoxy gemini quaternary ammonium salt, adjust the pH to 10 with a 10% by mass sodium hydroxide aqueous solution, stir and react at 65° C. for 2 h. After the reaction is completed, wash with deionized water and dry to obtain modified polyvinyl alcohol.

[0036] (6) Add 10 g of modified petroleum-based resin, 10 g of polylactic acid resin, and 10 g of modified polyvinyl alcohol to an ethanol aqueous solution with a relative molecular mass of 20%, stir and disperse for 40 minutes, then add 0.2 g of pigment, 0.2 g of defoaming agent, 0.5 g of dispersant, 0.1 g of emulsifier, and 0.5 g of wetting agent and stir for 30 minutes to obtain a degradable water-based ink.

[0037] Example 2

[0038] (1) 20 g of DCPD petroleum resin, 0.8 g of 4-mercaptohydrocinnamic acid, and 0.1 g of dibenzoyl peroxide initiator were added to toluene solvent, ultrasonically shaken, and reacted at 80° C. for 3 h. After the reaction was completed, methanol was precipitated, filtered, and dried to obtain a modified petroleum-based resin.

[0039] (2) 4.9 g of diallylamine and 26 g of mercaptopropyltriethoxysilane were added to a toluene solvent and dispersed with stirring. Then, 0.2 g of azobisisobutyronitrile was added thereto. The mixture was stirred and reacted at 80° C. for 40 min. After the reaction was completed, the mixture was rotary evaporated, washed with deionized water, and dried to obtain an intermediate 1.

[0040] (3) Add 24 g of intermediate 1 and 5 g of 1,6-dibromohexane to toluene solvent, stir and mix well, then add 0.03 g of potassium iodide, heat to 120° C. under nitrogen protection, stir and react for 24 h. After the reaction is completed, cool to room temperature, add deionized water, adjust the pH to 10 with 50% sodium hydroxide aqueous solution, extract with ether, and distill the organic phase under reduced pressure to obtain intermediate 2.

[0041] (4) Add 12 g of intermediate 2 to a 50% by mass aqueous solution of n-propanol, stir and disperse, heat to 55° C., add 2 g of epichlorohydrin, adjust the pH to 9 with a 10% by mass aqueous solution of sodium hydroxide, stir and react for 5 h, and after the reaction is completed, wash with deionized water and dry to obtain a polysilane epoxy gemini quaternary ammonium salt.

[0042] (5) Add 20 g of polyvinyl alcohol to deionized water, stir and dissolve at 95° C., then add 4 g of polysilane epoxy gemini quaternary ammonium salt, adjust the pH to 9 with a 10% by mass sodium hydroxide aqueous solution, stir and react at 55° C. for 4 h. After the reaction is completed, wash with deionized water and dry to obtain modified polyvinyl alcohol.

[0043] (6) 13 g of modified petroleum-based resin, 10 g of polylactic acid resin, and 12 g of modified polyvinyl alcohol were added to an ethanol aqueous solution with a relative molecular mass of 20%, and stirred and dispersed for 30 minutes. Then, 0.5 g of pigment, 0.3 g of defoaming agent, 0.2 g of dispersant, 0.3 g of emulsifier, and 0.4 g of wetting agent were added and stirred for 30 minutes to obtain a degradable water-based ink.

[0044] Example 3

[0045] (1) 20 g of DCPD petroleum resin, 1 g of 4-mercaptohydrocinnamic acid, and 0.04 g of dibenzoyl peroxide initiator were added to a toluene solvent, and ultrasonically vibrated at 85° C. for 1 h. After the reaction was completed, methanol was precipitated, filtered, and dried to obtain a modified petroleum-based resin.

[0046] (2) 4.9 g of diallylamine and 24.5 g of mercaptopropyltriethoxysilane were added to a toluene solvent and dispersed with stirring. Then, 0.245 g of azobisisobutyronitrile was added thereto. The mixture was stirred and reacted at 75° C. for 60 min. After the reaction was completed, the mixture was rotary evaporated, washed with deionized water, and dried to obtain an intermediate 1.

[0047] (3) 23 g of intermediate 1 and 5 g of 1,6-dibromohexane were added to toluene solvent and stirred to mix evenly. Then, 0.05 g of potassium iodide was added thereto. Under nitrogen protection, the mixture was heated to 100° C. and stirred for reaction for 30 h. After the reaction was completed, the mixture was cooled to room temperature. Deionized water was added thereto. The pH was adjusted to 10 using a 50% aqueous sodium hydroxide solution. The mixture was extracted with ether and the organic phase was distilled under reduced pressure to obtain intermediate 2.

[0048] (4) Add 12 g of intermediate 2 to a 50% by mass aqueous solution of n-propanol, stir and disperse, heat to 45° C., add 2.4 g of epichlorohydrin, adjust the pH to 8 with a 10% by mass aqueous solution of sodium hydroxide, stir and react for 4 h, and after the reaction is completed, wash with deionized water and dry to obtain a polysilane epoxy gemini quaternary ammonium salt.

[0049] (5) Add 20 g of polyvinyl alcohol to deionized water, stir and dissolve at 90° C., then add 6 g of polysilane epoxy gemini quaternary ammonium salt, adjust the pH to 9 with a 10% by mass sodium hydroxide aqueous solution, stir and react at 60° C. for 4 h. After the reaction is completed, wash with deionized water and dry to obtain modified polyvinyl alcohol.

[0050] (6) 15 g of modified petroleum-based resin, 10 g of polylactic acid resin, and 15 g of modified polyvinyl alcohol were added to an ethanol aqueous solution with a relative molecular mass of 20%, and stirred and dispersed for 40 minutes. Then, 0.8 g of pigment, 0.1 g of defoaming agent, 0.6 g of dispersant, 0.2 g of emulsifier, and 0.2 g of wetting agent were added thereto and stirred for 15 minutes to obtain a degradable water-based ink.

[0051] Example 4

[0052] (1) 20 g of DCPD petroleum resin, 1.5 g of 4-mercaptohydrocinnamic acid, and 0.05 g of dibenzoyl peroxide initiator were added to toluene solvent, ultrasonically shaken, and reacted at 90° C. for 2 h. After the reaction was completed, methanol was precipitated, filtered, and dried to obtain a modified petroleum-based resin.

[0053] (2) 4.9 g of diallylamine and 25 g of mercaptopropyltriethoxysilane were added to a toluene solvent and dispersed with stirring. Then, 0.147 g of azobisisobutyronitrile was added thereto. The mixture was stirred and reacted at 80° C. for 30 min. After the reaction was completed, the mixture was rotary evaporated, washed with deionized water, and dried to obtain an intermediate 1.

[0054] (3) Add 25 g of intermediate 1 and 5 g of 1,6-dibromohexane to toluene solvent, stir and mix well, then add 0.025 g of potassium iodide, heat to 120° C. under nitrogen protection, stir and react for 20 h. After the reaction is completed, cool to room temperature, add deionized water, adjust the pH to 9 with 50% sodium hydroxide aqueous solution, extract with ether, and distill the organic phase under reduced pressure to obtain intermediate 2.

[0055] (4) Add 12 g of intermediate 2 to a 50% by mass aqueous solution of n-propanol, stir and disperse, heat to 50° C., add 2.2 g of epichlorohydrin, adjust the pH to 9 with a 10% by mass aqueous solution of sodium hydroxide, stir and react for 4 h, and after the reaction is completed, wash with deionized water and dry to obtain a polysilane epoxy gemini quaternary ammonium salt.

[0056] (5) Add 20 g of polyvinyl alcohol to deionized water, stir and dissolve at 90° C., then add 8 g of polysilane epoxy gemini quaternary ammonium salt, adjust the pH to 10 with a 10% by mass sodium hydroxide aqueous solution, stir and react at 60° C. for 3 h. After the reaction is completed, wash with deionized water and dry to obtain modified polyvinyl alcohol.

[0057] (6) Add 18 g of modified petroleum-based resin, 10 g of polylactic acid resin, and 18 g of modified polyvinyl alcohol to an ethanol aqueous solution with a relative molecular mass of 20%, stir and disperse for 40 minutes, then add 0.5 g of pigment, 0.2 g of defoaming agent, 0.6 g of dispersant, 0.2 g of emulsifier, and 0.5 g of wetting agent and stir for 20 minutes to obtain a degradable water-based ink.

[0058] Example 5

[0059] (1) 20 g of DCPD petroleum resin, 2 g of 4-mercaptohydrocinnamic acid, and 0.1 g of dibenzoyl peroxide initiator were added to a toluene solvent, and ultrasonically vibrated at 85° C. for 2 h. After the reaction was completed, methanol was precipitated, filtered, and dried to obtain a modified petroleum-based resin.

[0060] (2) 4.9 g of diallylamine and 27 g of mercaptopropyltriethoxysilane were added to a toluene solvent and dispersed with stirring. Then, 0.2 g of azobisisobutyronitrile was added thereto. The mixture was stirred and reacted at 70° C. for 60 min. After the reaction was completed, the mixture was rotary evaporated, washed with deionized water, and dried to obtain an intermediate 1.

[0061] (3) Add 22.5 g of intermediate 1 and 5 g of 1,6-dibromohexane to toluene solvent, stir and mix well, then add 0.05 g of potassium iodide, heat to 110° C. under nitrogen protection, stir and react for 24 h. After the reaction is completed, cool to room temperature, add deionized water, adjust the pH to 10 with 50% sodium hydroxide aqueous solution, extract with ether, and distill the organic phase under reduced pressure to obtain intermediate 2.

[0062] (4) Add 12 g of intermediate 2 to a 50% by mass aqueous solution of n-propanol, stir and disperse, heat to 50° C., add 2 g of epichlorohydrin, adjust the pH to 9 with a 10% by mass aqueous solution of sodium hydroxide, stir and react for 4 h, and after the reaction is completed, wash with deionized water and dry to obtain a polysilane epoxy gemini quaternary ammonium salt.

[0063] (5) Add 20 g of polyvinyl alcohol to deionized water, stir and dissolve at 90° C., then add 10 g of polysilane epoxy gemini quaternary ammonium salt, adjust the pH to 10 with a 10% by mass sodium hydroxide aqueous solution, stir and react at 65° C. for 3 h. After the reaction is completed, wash with deionized water and dry to obtain modified polyvinyl alcohol.

[0064] (6) Add 20 g of modified petroleum-based resin, 10 g of polylactic acid resin, and 20 g of modified polyvinyl alcohol to an ethanol aqueous solution with a relative molecular mass of 20%, stir and disperse for 40 minutes, then add 0.2 g of pigment, 0.3 g of defoaming agent, 0.6 g of dispersant, 0.2 g of emulsifier, and 0.5 g of wetting agent and stir for 30 minutes to obtain a degradable water-based ink.

[0065] Comparative Example 1

[0066] The difference between this comparative example and Example 1 is that DCPD petroleum resin is used in step (6) instead of modified petroleum-based resin.

[0067] Comparative Example 2

[0068] The difference between this comparative example and Example 1 is that polyvinyl alcohol is used instead of modified polyvinyl alcohol in step (6).

[0069] Adhesion test: Use a wire rod to print a water-based ink on a BOPP film, dry it at 80°C, stick a tape on the printed film, rub it evenly and peel it off quickly, and examine the surface state of the printed film after peeling. The visual measurement standard is good, qualified, and unqualified. More than 90% of the printed film residue is good, 60-90% of the printed film residue is qualified, and less than 60% of the printed film residue is unqualified.

[0070] Table 1:

[0071]

[0072]

[0073] It can be seen from the table that the degradable water-based ink prepared by the present invention has good adhesion.

[0074] The antibacterial test was carried out according to the ISO 22196-2011 method, and the test bacteria were Staphylococcus aureus and Escherichia coli.

[0075] Table 2:

[0076]

[0077] It can be seen from the table that the antibacterial effect of the modified petroleum-based resin containing cinnamic acid and the polyvinyl alcohol containing quaternary ammonium salt that assists each other is better than the antibacterial effect of a single antibacterial component, and the ink prepared by the present invention has good antibacterial properties.

Claims

1. A degradable water-based ink, characterized in that: The degradable water-based ink is composed of the following components by weight: 100-200 parts by weight of modified petroleum-based resin, 100 parts by weight of bio-based resin, 100-200 parts by weight of modified polyvinyl alcohol, 2-8 parts by weight of pigment, 1-3 parts by weight of defoamer, 2-6 parts by weight of dispersant, 1-3 parts by weight of emulsifier, and 2-5 parts by weight of wetting agent; The bio-based resin is polylactic acid resin; The modified petroleum-based resin is prepared from cinnamic acid and DCPD petroleum resin as raw materials, and the preparation method thereof is as follows: adding DCPD petroleum resin, 4-mercaptohydrocinnamic acid, and dibenzoyl peroxide initiator to toluene solvent, ultrasonically shaking, reacting at 80-90° C. for 1-3 hours, and after the reaction is completed, precipitating with methanol, filtering, and drying to obtain the modified petroleum-based resin; The preparation method of the degradable water-based ink is: (1) adding polyvinyl alcohol to deionized water, stirring and dissolving at 85-95° C., adding polysilane epoxy gemini quaternary ammonium salt thereto, adjusting the pH to 9-10 with a 10% by mass sodium hydroxide aqueous solution, stirring and reacting at 55-65° C. for 2-4 hours, and after the reaction is completed, washing with deionized water and drying to obtain modified polyvinyl alcohol; (2) Adding modified petroleum-based resin, polylactic acid resin and modified polyvinyl alcohol to an ethanol aqueous solution with a relative molecular weight of 20%, stirring and dispersing for 20-40 minutes, and then adding pigment, defoamer, dispersant, emulsifier and wetting agent thereto and stirring for 15-30 minutes to obtain a degradable water-based ink.

2. The degradable water-based ink according to claim 1, characterized in that: In the above (1), the usage ratio of polyvinyl alcohol and polysilane epoxy gemini quaternary ammonium salt is 1g:(0.1-0.5)g.

3. The degradable water-based ink according to claim 1, characterized in that: The usage ratio of the DCPD petroleum resin, 4-mercaptohydrocinnamic acid and dibenzoyl peroxide is 100g:(2-10)g:(0.2-0.5)g.

4. The degradable water-based ink according to claim 1, characterized in that: In the above (1), the preparation method of polysilane epoxy gemini quaternary ammonium salt is: S1, adding diallylamine and mercaptopropyltriethoxysilane to a toluene solvent, stirring and dispersing, then adding azobisisobutyronitrile thereto, stirring and reacting at 70-80° C. for 30-60 min. After the reaction is completed, rotary evaporation, washing with deionized water, and drying to obtain intermediate 1; S2, adding intermediate 1 and 1,6-dibromohexane to toluene solvent, stirring and mixing, then adding potassium iodide thereto, heating to 100-120°C under nitrogen protection, stirring and reacting for 20-30 hours, after the reaction is completed, cooling to room temperature, adding deionized water thereto, adjusting the pH to 9-10 with 50% sodium hydroxide aqueous solution, extracting with ether, and distilling the organic phase under reduced pressure to obtain intermediate 2; S3. Add intermediate 2 to a 50% by mass aqueous solution of n-propanol, stir and disperse, heat to 45-55°C, add epichlorohydrin, adjust the pH to 8-9 with a 10% by mass aqueous solution of sodium hydroxide, stir and react for 2-5 hours, and after the reaction is completed, wash with deionized water and dry to obtain a polysilane epoxy gemini quaternary ammonium salt.

5. The degradable water-based ink according to claim 4, characterized in that: In the S1, the usage ratio of diallylamine, mercaptopropyltriethoxysilane and azobisisobutyronitrile is 1 g:(5-5.5) g:(0.03-0.05) g.

6. The degradable water-based ink according to claim 4, characterized in that: In S2, the usage ratio of the intermediate 1, 1,6-dibromohexane and potassium iodide is (4.5-5) g: 1 g: (0.005-0.01) g.

7. The degradable water-based ink according to claim 4, characterized in that: In S3, the usage ratio of intermediate 2 and epichlorohydrin is 1g:(0.15-0.2)g.

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