A degradable water-based ink and its preparation method

Abstract

The present invention relates to the technical field of inks, and discloses a degradable water-based ink and a preparation method thereof. In the present invention, a DCPD petroleum resin reacts with 4-mercaptohydrocinnamic acid through a thiol-ene addition reaction to obtain a modified petroleum-based resin. Using diallylamine, mercaptopropyltriethoxysilane, 1,6-dibromohexane, epichlorohydrin, etc. as raw materials, through a thiol-ene addition reaction, a substitution reaction, and a quaternization reaction in sequence, a polysilane epoxy-based gemini quaternary ammonium salt is obtained. The epoxy group in the polysilane epoxy-based gemini quaternary ammonium salt undergoes a ring-opening reaction with the hydroxyl group in polyvinyl alcohol to obtain modified polyvinyl alcohol. Finally, the modified petroleum-based resin, modified polyvinyl alcohol, polylactic acid, defoamer, dispersant, etc. are stirred and mixed evenly to obtain a degradable water-based ink. The degradable water-based ink prepared in the present invention is experimentally proven to have good antibacterial properties and adhesion.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, and specifically relates 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 pose harm to the human body, but also cause great environmental pollution. Therefore, in consideration of environmental protection requirements, water-based ink has emerged. Water-based ink, abbreviated as water ink, is mainly composed of water-based polymer resin, pigment, water-based additives, deionized water, etc., and is processed by compound grinding. It is widely used in packaging and printing products such as food, beverages, and pharmaceuticals. At present, the resin used is mainly petroleum-based resin. However, compared with bio-based resin, bio-based resin is more environmentally friendly and 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 from C5 separation as the main raw material, and has advantages such as good solubility, compatibility, and low price. Polyvinyl alcohol is a degradable polymer compound with little environmental pollution and good performance, and is widely used in various fields.

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

[0005] (1) Technical Problems to be Solved

[0006] Aiming at the deficiencies of 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 performance and adhesion.

[0007] (2) Technical Solutions

[0008] A degradable water-based ink, the degradable water-based ink is composed of the following weight components: 100-200 parts by mass of modified petroleum-based resin, 100 parts by mass of bio-based resin, 100-200 parts by mass of modified polyvinyl alcohol, 2-8 parts by mass of pigment, 1-3 parts by mass of defoaming agent, 2-6 parts by mass of dispersant, 1-3 parts by mass of emulsifier, 2-5 parts by mass 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, and its preparation method is as follows: Add DCPD petroleum resin, 4-mercaptohydrocinnamic acid, and benzoyl peroxide initiator into toluene solvent, ultrasonically vibrate, react at 80-90 °C for 1-3 h. After the reaction, precipitate with methanol, filter by suction, and dry to obtain the modified petroleum-based resin;

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

[0012] (1) Add polyvinyl alcohol into deionized water, stir and dissolve at 85-95 °C, then add polysilane epoxy-based gemini quaternary ammonium salt into it, adjust the pH to 9-10 with 10% sodium hydroxide aqueous solution by mass fraction, stir and react at 55-65 °C for 2-4 h. After the reaction, wash with deionized water and dry to obtain modified polyvinyl alcohol;

[0013] (2) Add the modified petroleum-based resin, polylactic acid resin, and modified polyvinyl alcohol into an ethanol aqueous solution with a relative molecular mass of 20%, stir and disperse for 20-40 min, then add pigment, defoamer, dispersant, emulsifier, and wetting agent and stir for 15-30 min to obtain the degradable water-based ink.

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

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

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

[0017] S1. Add diallylamine and mercaptopropyltriethoxysilane into toluene solvent, stir and disperse, then add azobisisobutyronitrile into it, stir and react at 70-80 °C for 30-60 min. After the reaction, perform rotary evaporation, wash with deionized water, and dry to obtain intermediate 1;

[0018] S2. Add intermediate 1 and 1,6-dibromohexane into toluene solvent, stir and mix evenly, then add potassium iodide into it, heat to 100-120 °C under nitrogen protection, stir and react for 20-30 h. After the reaction, cool to room temperature, add deionized water into it, adjust the pH to 9-10 with 50% sodium hydroxide aqueous solution, extract with ether, and perform vacuum distillation on the organic phase to obtain intermediate 2;

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

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

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

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

[0023] (III) Beneficial technical effects

[0024] In the present invention, the DCPD petroleum resin reacts with 4 - mercaptohydrocinnamic acid through a thiol - ene addition reaction to introduce cinnamic acid into the main chain structure of the petroleum resin, obtaining a modified petroleum - based resin. Using diallylamine, mercaptopropyltriethoxysilane, 1,6 - dibromohexane, epichlorohydrin, etc. as raw materials, through a thiol - ene addition reaction, a substitution reaction, and a quaternization reaction in sequence, polysilane epoxy gemini quaternary ammonium salt is obtained. The epoxy group in the polysilane epoxy gemini quaternary ammonium salt undergoes a ring - opening reaction with the hydroxyl group in polyvinyl alcohol to obtain modified polyvinyl alcohol. Finally, the modified petroleum - based resin, modified polyvinyl alcohol, polylactic acid resin, defoaming agent, dispersing agent, etc. are stirred and mixed evenly to obtain a degradable water - based ink.

[0025] Inks mainly using petroleum resin as a binder are difficult to degrade themselves. In the present invention, it is combined with volatile cinnamic acid. On the one hand, it can reduce the volatilization degree of cinnamic acid, and on the other hand, it can improve the degradability of the water - based ink. Then, it is mixed with modified polyvinyl alcohol and polylactic acid. The prepared water - based ink has more excellent degradability compared with the ink solely using petroleum resin as a binder. And because cinnamaldehyde has antibacterial properties and is linked to the petroleum resin by chemical bonds, it can endow the water - based ink with long - term antibacterial properties and can form an auxiliary antibacterial effect with the quaternary ammonium salt antibacterial group, jointly enhancing the antibacterial effect of the ink.

[0026] In addition, the polysilane epoxy gemini quaternary ammonium salt prepared by the present invention contains bis-epoxy groups and a tetrasiloxane structure. When it combines with polyvinyl alcohol, it can not only expand the crosslinking degree, generate more crosslinking sites, reduce the brittleness of polyvinyl alcohol, and thus improve the mechanical properties of the ink, but also due to the easy hydrolysis property of siloxane, the generated silicon-oxygen bonds can condense with the hydroxyl groups on the surface of the matrix material, improving the adhesion of the water-based ink. The water-based ink prepared by the present invention has excellent degradability, antibacterial property, and adhesion. Description of the Drawings

[0027] Figure 1 is the reaction route of the polysilane epoxy gemini quaternary ammonium salt. Detailed Embodiments

[0028] The following further describes the degradable water-based ink and its preparation method of the present invention in combination with some specific embodiments. The specific examples are for further detailed description of the present invention and do not limit the protection scope of the present invention.

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

[0030] Example 1

[0031] (1) Add 20 g of DCPD petroleum resin, 0.4 g of 4-mercaptohydrocinnamic acid, and 0.05 g of dibenzoyl peroxide initiator to toluene solvent, ultrasonically vibrate, react at 90 °C for 2 h. After the reaction, precipitate with methanol, filter by suction, and dry to obtain the modified petroleum-based resin.

[0032] (2) Add 4.9 g of diallylamine and 25 g of mercaptopropyltriethoxysilane to toluene solvent, stir and disperse, then add 0.245 g of azobisisobutyronitrile thereto, react with stirring at 75 °C for 60 min. After the reaction, perform rotary evaporation, wash with deionized water, and dry to obtain Intermediate 1.

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

[0034] (4) Add 12 g of intermediate 2 to an aqueous solution of n-propanol with a mass fraction of 50%, stir and disperse, heat up to 50 °C, add 1.8 g of epichlorohydrin thereto, adjust the pH to 8 with an aqueous sodium hydroxide solution with a mass fraction of 10%, stir and react for 2 h. After the reaction is completed, wash with deionized water and dry to obtain 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 thereto, adjust the pH to 10 with an aqueous sodium hydroxide solution with a mass fraction of 10%, and 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 aqueous ethanol solution with a relative molecular mass of 20%, stir and disperse for 40 min, then add 0.2 g of pigment, 0.2 g of defoamer, 0.5 g of dispersant, 0.1 g of emulsifier, and 0.5 g of wetting agent and stir for 30 min to obtain a degradable water-based ink.

[0037] Example 2

[0038] (1) Add 20 g of DCPD petroleum resin, 0.8 g of 4-mercaptohydrocinnamic acid, and 0.1 g of dibenzoyl peroxide initiator to toluene solvent, ultrasonically oscillate, and react at 80 °C for 3 h. After the reaction is completed, precipitate with methanol, filter by suction, and dry to obtain modified petroleum-based resin.

[0039] (2) Add 4.9 g of diallylamine and 26 g of mercaptopropyltriethoxysilane to toluene solvent, stir and disperse, then add 0.2 g of azobisisobutyronitrile thereto, and stir and react at 80 °C for 40 min. After the reaction is completed, perform rotary evaporation, wash with deionized water, and dry to obtain intermediate 1.

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

[0041] (4) Add 12 g of intermediate 2 to an aqueous solution of n-propanol with a mass fraction of 50%, stir and disperse, heat up to 55 °C, add 2 g of epichlorohydrin thereto, adjust the pH to 9 with an aqueous sodium hydroxide solution with a mass fraction of 10%, stir and react for 5 h. After the reaction is completed, wash with deionized water and dry to obtain 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 thereto, adjust the pH to 9 with an aqueous sodium hydroxide solution with a mass fraction of 10%, and 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) Add 13 g of modified petroleum-based resin, 10 g of polylactic acid resin, and 12 g of modified polyvinyl alcohol to an aqueous ethanol solution with a relative molecular mass of 20%, stir and disperse for 30 min, then add 0.5 g of pigment, 0.3 g of defoamer, 0.2 g of dispersant, 0.3 g of emulsifier, and 0.4 g of wetting agent thereto and stir for 30 min to obtain a degradable water-based ink.

[0044] Example 3

[0045] (1) Add 20 g of DCPD petroleum resin, 1 g of 4-mercaptohydrocinnamic acid, and 0.04 g of dibenzoyl peroxide initiator to toluene solvent, ultrasonically oscillate, react at 85 °C for 1 h. After the reaction is completed, precipitate with methanol, filter by suction, and dry to obtain modified petroleum-based resin.

[0046] (2) Add 4.9 g of diallylamine and 24.5 g of mercaptopropyltriethoxysilane to toluene solvent, stir and disperse, then add 0.245 g of azobisisobutyronitrile thereto, and stir and react at 75 °C for 60 min. After the reaction is completed, perform rotary evaporation, wash with deionized water, and dry to obtain intermediate 1.

[0047] (3) Add 23 g of intermediate 1 and 5 g of 1,6-dibromohexane to toluene solvent, stir and mix evenly, then add 0.05 g of potassium iodide thereto, heat to 100 °C under nitrogen protection, and stir and react for 30 h. After the reaction is completed, cool to room temperature, add deionized water thereto, adjust the pH to 10 with a 50% aqueous sodium hydroxide solution, extract with ether, and perform vacuum distillation on the organic phase to obtain intermediate 2.

[0048] (4) Add 12 g of intermediate 2 to an aqueous solution of n-propanol with a mass fraction of 50%, stir to disperse, heat up to 45 °C, add 2.4 g of epichlorohydrin thereto, adjust the pH to 8 using an aqueous sodium hydroxide solution with a mass fraction of 10%, stir and react for 4 h. After the reaction is completed, wash with deionized water and dry to obtain 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 thereto, adjust the pH to 9 using an aqueous sodium hydroxide solution with a mass fraction of 10%, 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) Add 15 g of modified petroleum-based resin, 10 g of polylactic acid resin, and 15 g of modified polyvinyl alcohol to an aqueous ethanol solution with a relative molecular mass of 20%, stir and disperse for 40 min, then add 0.8 g of pigment, 0.1 g of defoamer, 0.6 g of dispersant, 0.2 g of emulsifier, and 0.2 g of wetting agent thereto and stir for 15 min to obtain a degradable water-based ink.

[0051] Example 4

[0052] (1) Add 20 g of DCPD petroleum resin, 1.5 g of 4-mercaptohydrocinnamic acid, and 0.05 g of dibenzoyl peroxide initiator to toluene solvent, ultrasonically oscillate, react at 90 °C for 2 h. After the reaction is completed, precipitate with methanol, filter by suction, and dry to obtain modified petroleum-based resin.

[0053] (2) Add 4.9 g of diallylamine and 25 g of mercaptopropyltriethoxysilane to toluene solvent, stir and disperse, then add 0.147 g of azobisisobutyronitrile thereto, stir and react at 80 °C for 30 min. After the reaction is completed, perform rotary evaporation, wash with deionized water, and dry to obtain intermediate 1.

[0054] (3) Add 25 g of intermediate 1 and 5 g of 1,6-dibromohexane to toluene solvent, stir and mix evenly, then add 0.025 g of potassium iodide thereto, 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 thereto, adjust the pH to 9 using a 50% aqueous sodium hydroxide solution, extract with ether, and perform vacuum distillation on the organic phase to obtain intermediate 2.

[0055] (4) Add 12 g of intermediate 2 to an aqueous solution of n-propanol with a mass fraction of 50%, stir to disperse, heat up to 50 °C, add 2.2 g of epichlorohydrin thereto, adjust the pH to 9 with an aqueous solution of sodium hydroxide with a mass fraction of 10%, stir and react for 4 h. After the reaction is completed, wash with deionized water and dry to obtain 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 thereto, adjust the pH to 10 with an aqueous solution of sodium hydroxide with a mass fraction of 10%, and 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 aqueous ethanol solution with a relative molecular mass of 20%, stir and disperse for 40 min, then add 0.5 g of pigment, 0.2 g of defoamer, 0.6 g of dispersant, 0.2 g of emulsifier, and 0.5 g of wetting agent thereto and stir for 20 min to obtain a degradable water-based ink.

[0058] Example 5

[0059] (1) Add 20 g of DCPD petroleum resin, 2 g of 4-mercaptohydrocinnamic acid, and 0.1 g of dibenzoyl peroxide initiator to toluene solvent, ultrasonically oscillate, and react at 85 °C for 2 h. After the reaction is completed, precipitate with methanol, filter by suction, and dry to obtain modified petroleum-based resin.

[0060] (2) Add 4.9 g of diallylamine and 27 g of mercaptopropyltriethoxysilane to toluene solvent, stir and disperse, then add 0.2 g of azobisisobutyronitrile thereto, and stir and react at 70 °C for 60 min. After the reaction is completed, perform rotary evaporation, wash with deionized water, and dry to obtain intermediate 1.

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

[0062] (4) Add 12 g of Intermediate 2 to an aqueous solution of n-propanol with a mass fraction of 50%, stir and disperse, heat up to 50 °C, add 2 g of epichlorohydrin thereto, adjust the pH to 9 with an aqueous sodium hydroxide solution with a mass fraction of 10%, stir and react for 4 h. After the reaction is completed, wash with deionized water and dry to obtain 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 thereto, adjust the pH to 10 with an aqueous sodium hydroxide solution with a mass fraction of 10%, and 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 aqueous ethanol solution with a relative molecular mass of 20%, stir and disperse for 40 min, then add 0.2 g of pigment, 0.3 g of defoamer, 0.6 g of dispersant, 0.2 g of emulsifier, and 0.5 g of wetting agent thereto and stir for 30 min to obtain a degradable water-based ink.

[0065] Comparative Example 1

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

[0067] Comparative Example 2

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

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

[0070] Table 1:

[0071]

[0072]

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

[0074] Refer to the method of ISO 22196-2011 to conduct an antibacterial test, and the test bacteria are Staphylococcus aureus and Escherichia coli.

[0075] Table 2:

[0076]

[0077] As can be seen from the table, the antibacterial effect of the modified petroleum-based resin containing cinnamic acid and polyvinyl alcohol containing quaternary ammonium salt assisting each other is better than that 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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