Rosin modified resin, preparation process thereof and low-odor printing ink

Abstract

The invention relates to rosin modified resin and a preparation process thereof and low-odor printing ink, the rosin modified resin is prepared from maleic anhydride, sulfonate alkyd resin, rosin and a metal organic framework, and the sulfonate alkyd resin is prepared from neopentyl glycol, dibutyltin dilaurate, m-phthalic acid-5-sodium sulfonate, phthalic anhydride and pentaerythritol. The printing ink has the effect of improving the strength and smell of the printing ink.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of ink, in particular to a rosin modified resin and its preparation process and low odor ink. BACKGROUND

[0002] Ink is an important material for printing, which transfers patterns, characters and other information to paper, plastic, metal, fabric and other various printing materials by printing or spraying.

[0003] Resin is one of the main components of ink binder, which can uniformly disperse and bond solid components such as pigments together, and at the same time enable the ink to be transferred and adhered to the surface of the printing material during printing. Resin has good adhesion and film forming properties, which can form a continuous film after printing, firmly fixing the pigments on the printing material, so that the printed matter has certain gloss, wear resistance and water resistance.

[0004] Phenolic resin is often added to ink to improve the performance of ink due to its good thermal stability and mechanical strength. However, phenolic resin is usually made from phenol and formaldehyde and other raw materials by condensation polymerization, and a small amount of unreacted phenol, formaldehyde and other raw materials remain in the system, which has a smell and will gradually release in the ink, resulting in odor of the ink. SUMMARY

[0005] In order to improve the above problems, the present application provides a rosin modified resin and its preparation process and low odor ink.

[0006] In a first aspect, the present application provides a rosin modified resin, which adopts the following technical solution: A rosin modified resin, the raw materials include maleic anhydride, sulfonate alkyd resin, rosin and metal organic framework, the sulfonate alkyd resin raw materials include neopentyl glycol, dibutyltin dilaurate, sodium 5-sulfonate isophthalic acid, phthalic anhydride, pentaerythritol.

[0007] By adopting the above technical solution, the rosin is grafted with the sulfonate alkyd resin by maleic anhydride, so that the rosin is combined with the sulfonate alkyd resin, without phenolic resin, which can effectively reduce the odor, and the metal framework is also added as a filler of the resin system, which can effectively improve the strength of the whole resin system, thereby improving the stability of the resin.

[0008] As a preferred, the sulfonate alkyd resin is prepared by the following method: The new pentaerythritol is mixed with dibutyltin dilaurate, after warming, sodium 5-sulfoisophthalate is added for reaction, after the reactants are transparent, cooling is performed to obtain the sulfonate monomer; the aqueous monomer, phthalic anhydride, pentaerythritol, soybean oil acid and dimethylbenzene are mixed with the sulfonate monomer, warming is performed for reaction, then cooling is performed, dimethylbenzene is extracted, continuous cooling is performed, then ethylene glycol butyl ether is added, after stirring, the product is discharged to obtain the sulfonate alkyd resin.

[0009] By adopting the technical scheme, the sulfonate monomer is prepared from sodium 5-sulfoisophthalate and new pentaerythritol, the sulfonate monomer is compounded with polyethylene glycol acrylate, soybean oil acid, phthalic anhydride and pentaerythritol to prepare the sulfonate alkyd resin, the sulfonate alkyd resin is synthesized by embedding the monomer in the alkyd resin chain, and the sulfonate alkyd resin has good stability and dispersibility, good dryness, viscosity and stability, and further improves the stability of the resin as a whole.

[0010] Preferably, the aqueous monomer comprises hydroxypropyl methacrylate.

[0011] By adopting the technical scheme, the hydroxypropyl methacrylate is used as the aqueous monomer to prepare the sulfonate alkyd resin, the stability of the prepared alkyd resin is further improved, and the sulfonate alkyd resin has good compatibility and dispersibility, so that the stability of the system is improved when the system is applied, and the stratification phenomenon is reduced, and the introduction of the sulfonate group can further improve the viscosity of the system as a whole, so that the bonding performance of the system as a whole is further improved.

[0012] Preferably, the mass ratio between the sulfonate monomer, the hydroxypropyl methacrylate and the ethylene glycol butyl ether is (0.54-0.58):0.4:1.

[0013] By adopting the technical scheme, the mass ratio between the sulfonate monomer, the hydroxypropyl methacrylate and the ethylene glycol butyl ether is within the above range, so that the stability of the sulfonate alkyd resin as a whole is further improved.

[0014] Preferably, the metal organic framework raw material comprises cobalt nitrate hexahydrate, trimesic acid and N,N-dimethylformamide; the metal organic framework is prepared by the following method: The cobalt nitrate hexahydrate and the N,N-dimethylformamide are mixed, then the trimesic acid is added for stirring to obtain a mixture, the mixture is heated for reaction, the reaction is cooled and washed, and then dried to obtain the metal organic framework.

[0015] By adopting the technical scheme, the metal organic framework prepared by the cobalt nitrate hexahydrate, trimesic acid and N,N-dimethylformamide is added in the resin system, so that the overall corrosion resistance of the resin system can be effectively improved, and the resin system has good protection performance. The metal organic framework can fill the voids in the resin system, and the strength of the overall resin system is improved. The metal organic framework is prepared by solvothermal synthesis with the cobalt nitrate hexahydrate as the metal source and the trimesic acid as the embryo. The metal organic framework has many active sites, which improves the contact area with the resin system and improves the density of the resin system, thereby improving the corrosion resistance of the system.

[0016] Preferably, the reaction temperature is 140-160 DEG C, and the reaction time is 110-130 min.

[0017] By adopting the technical scheme, the reaction temperature is preferably within the above range, and the reaction time is preferably within the above range, so that the stability of the overall metal organic framework prepared can be further improved.

[0018] In a second aspect, the application provides a preparation method of rosin modified resin, which adopts the following technical scheme: A preparation method of rosin modified resin comprises the following steps: The rosin is heated to melt, then rosin is continuously added, maleic anhydride is added while stirring, glycerol is added after reaction, and the temperature is continuously raised for reaction to obtain a rosin compound. The rosin compound, sulfonate alkyd resin and metal framework mixture are heated and reacted to obtain the rosin modified resin.

[0019] Preferably, the mass ratio of the rosin, maleic anhydride and glycerol is 1:(0.13-0.14):0.17.

[0020] By adopting the technical scheme, the mass ratio of the rosin, maleic anhydride and glycerol is preferably within the above range, so that the stability of the prepared rosin modified resin can be further improved.

[0021] Preferably, the mass ratio of the rosin compound, sulfonate alkyd resin and metal organic framework is 1:0.22:(0.06-0.08).

[0022] By adopting the technical scheme, the mass ratio of the rosin compound, sulfonate alkyd resin and metal organic framework is preferably within the above range, so that the stability of the prepared rosin modified resin can be further improved.

[0023] In a third aspect, the application provides a low odor ink, which adopts the following technical scheme: A low odor ink comprises the rosin modified resin as described above.

[0024] In summary, the present application includes at least one of the following beneficial technical effects: 1. The rosin is grafted with the sulfonate alkyd resin by maleic anhydride, so that the rosin is combined with the sulfonate alkyd resin, the prepared rosin modified resin has no smell of raw materials such as phenol and formaldehyde, and the application to the ink can effectively reduce the smell of the ink, and the maleic anhydride connecting system can improve the strength of the whole resin; 2. The sulfonate monomer is prepared by sodium 5-sulfonate isophthalic acid and neopentyl glycol, and then the sulfonate monomer is combined with acrylic acid polyethylene glycol ester, soybean oil acid, phthalic acid and pentaerythritol to prepare a sulfonate alkyd resin, so that the resin alkyd resin has good stability and dispersibility, and the hydroxypropyl methacrylate is a water-based material, so that the prepared alkyd resin has good water solubility, thereby further improving the compatibility of the prepared rosin modified resin, to further improve the stability of the whole system; 3. The metal organic framework is prepared by complexing cobalt nitrate hexahydrate, trimesic acid and N,N-dimethylformamide through solvothermal synthesis, which has many active sites and can further combine with the resin system, so that the metal organic framework is filled into the voids of the resin, thereby improving the strength of the whole system, and improving the density of the resin system and the corrosion resistance of the whole system. DETAILED DESCRIPTION

[0025] The present application is further described below in combination with examples: Raw material description: all raw materials in the examples can be obtained by market purchase; Among them, the red yellow blue organic dye is obtained by mixing acid red G (CAS number: 3734-67-6), acid yellow 220 (CAS number: 71603-79-7) and acid blue 9 (CAS number: 2650-18-2) in a mass ratio of 1:1:1; the vegetable oil is obtained by mixing soybean oil and castor oil in a mass ratio of 1:1; the drying agent is cobalt naphthenate (CAS number: 61789-51-3); the friction powder is polyethylene wax (CAS number: 9002-88-4); and the water repellent agent is methacrylate (CAS number: 922-67-8).

[0026] Example 1 Preparation of metal organic framework: Add 45 g of cobalt nitrate hexahydrate to 72 g of N,N-dimethylformamide (CAS No.: 68-12-2) and stir until completely dissolved, then add 33 g of trimesic acid (CAS No.: 554-95-0) and continue stirring for 1 h to obtain a mixture, transfer the mixture to a stainless steel reaction kettle with a polytetrafluoroethylene liner, heat to 140°C under sealed conditions, and react for 130 min, then naturally cool to 25°C after the reaction, wash with N,N-dimethylformamide and anhydrous ethanol alternately, and dry the washed product in a vacuum drying oven at a temperature of 60°C for 24 h to obtain an organic metal framework.

[0027] Preparation of sulfonate alkyd resin: Mix 35 g of neopentyl glycol (CAS No.: 126-30-7) with 7 g of dibutyltin dilaurate (CAS No.: 77-58-7), warm to 120°C, then add 45 g of sodium 5-sulfonate isophthalic acid (CAS No.: 6362-79-4), and warm to 200°C at a warming rate of 20°C / h while removing water generated in the system in a timely manner, and obtain a sulfonate monomer after the reactants become transparent and the temperature is lowered to 140°C; mix 16.49 g of aqueous monomer, 43 g of phthalic anhydride (CAS No.: 85-44-9), 30 g of pentaerythritol (CAS No.: 115-77-5), 86 g of soybean oil acid (CAS No.: 68308-53-2), and 30 g of xylene (CAS No.: 1330-20-7) with 22.27 g of sulfonate monomer, then warm to 140°C and maintain for 2 h while removing water in the system in a timely manner, then lower the temperature to 160°C, remove xylene, lower the temperature to 100°C, then add 41.24 g of ethylene glycol butyl ether (CAS No.: 111-76-2), stir for 0.5 h, then lower the temperature to 50°C to discharge, and obtain a sulfonate alkyd resin; The aqueous monomer is hydroxypropyl methacrylate (CAS No.: 27813-02-1).

[0028] Preparation of rosin modified resin: Warm 144 g of rosin (CAS No.: 8050-09-7) to 150°C in a nitrogen-protected environment, stir until the rosin is melted, then add 96 g of rosin, add 31.2 g of maleic anhydride (CAS No.: 108-31-6) while stirring, warm to 200°C and react for 1 h, then add 40.8 g of glycerol, warm to 270°C, and continue to react for 7 h while removing water in a timely manner, and obtain a rosin compound after vacuuming.

[0029] Preparation of ink: After 50 g of rosin modified resin is mixed with 45 g of vegetable oil, a connecting agent is obtained; After red and blue organic dyes are mixed with carbon black at a mass ratio of 1:1, a pigment is obtained; After a drying agent, a friction powder and a water repellent agent are mixed at a mass ratio of 1:1:1, an auxiliary agent is obtained; After 10 g of the pigment, 89 g of the connecting agent and 1 g of the auxiliary agent are mixed and stirred, an ink is obtained.

[0030] Example 2 Preparation of a metal organic framework: 45 g of cobalt nitrate hexahydrate is added to 72 g of N,N-dimethylformamide and stirred until completely dissolved, then 33 g of trimesic acid is added and stirring is continued for 1 h to obtain a mixture, the mixture is transferred to a stainless steel reaction kettle with a polytetrafluoroethylene liner, and heated to 160°C under sealed conditions for 110 min, after reaction, it is naturally cooled to 25°C, washed with N,N-dimethylformamide and anhydrous ethanol alternately, and the washed product is dried in a vacuum drying oven at a temperature of 60°C for 24 h to obtain a metal organic framework.

[0031] Preparation of a sulfonate alkyd resin: 35 g of neopentyl glycol is mixed with 7 g of dibutyltin dilaurate, heated to 120°C, then 45 g of m-phthalic acid-5-sodium sulfonate is added, and heated to 200°C at a heating rate of 20°C / h, and the generated water is discharged from the system in a timely manner during the reaction, after the reaction material becomes transparent, the temperature is lowered to 140°C to obtain a sulfonate monomer; 23.44 g of the aqueous monomer, 43 g of phthalic anhydride, 30 g of pentaerythritol, 86 g of soybean oil acid and 30 g of dimethylbenzene are mixed with 16.16 g of the sulfonate monomer, then heated to 140°C and kept for 2 h, and the water is discharged in a timely manner, then the temperature is lowered to 160°C, the dimethylbenzene is extracted, the temperature is lowered to 100°C, then 41.24 g of ethylene glycol butyl ether is added, stirred for 0.5 h, then the temperature is lowered to 50°C to discharge, and a sulfonate alkyd resin is obtained; The aqueous monomer is hydroxypropyl methacrylate.

[0032] Preparation of a rosin modified resin: 144 g of rosin is heated to 150°C under nitrogen protection, stirred until the rosin is melted, then 96 g of rosin is added, 33.6 g of maleic anhydride is added while stirring, heated to 200°C and reacted for 1 h, then 40.8 g of glycerol is added, heated to 270°C and reacted for 7 h, and the water is discharged in a timely manner during the reaction, and a rosin compound is obtained after vacuum extraction; 120 g of the rosin compound, 33 g of the sulfonate alkyd resin and 7.2 g of the metal framework mixture are heated to 200°C and reacted for 1 h to obtain a rosin modified resin.

[0033] Preparation of ink: After mixing 80 g of rosin modified resin with 38 g of vegetable oil, a connecting agent is obtained; After mixing red and blue organic dyes with carbon black in a mass ratio of 1:1, a pigment is obtained; After mixing a drying agent, a friction powder and a water repellent agent in a mass ratio of 1:1:1, an auxiliary agent is obtained; After mixing 30 g of pigment, 65 g of connecting agent and 5 g of auxiliary agent, the ink is obtained by stirring.

[0034] Example 3 Preparation of metal organic framework: After 45 g of cobalt nitrate hexahydrate is added to 72 g of N,N-dimethylformamide and stirred until completely dissolved, 33 g of trimesic acid is added, and stirring is continued for 1 h to obtain a mixture. The mixture is transferred to a stainless steel reaction kettle with a polytetrafluoroethylene liner, and heated to 150℃ under sealed conditions for 120 min. After reaction, it is naturally cooled to 25℃, and washed with N,N-dimethylformamide and anhydrous ethanol alternately. The washed product is dried in a vacuum drying box at a temperature of 60℃ for 24 h to obtain a metal organic framework.

[0035] Preparation of sulfonate alkyd resin: After 35 g of neopentyl glycol is mixed with 7 g of dibutyltin dilaurate, and heated to 120℃, 45 g of sodium 5-sulfonate isophthalic acid is added, and heated to 200℃ at a heating rate of 20℃ / h. Water generated during the reaction is timely removed from the system. After the reactants become transparent, the temperature is lowered to 140℃ to obtain a sulfonate monomer. 22.85 g of aqueous monomer, 43 g of phthalic anhydride, 30 g of pentaerythritol, 86 g of soybean oil acid and 30 g of xylene are mixed with 16.33 g of sulfonate monomer, and then heated to 140℃ and kept for 2 h. Water is timely removed from the system, and then the temperature is lowered to 160℃. Xylene is removed, and the temperature is lowered to 100℃. Then 40.82 g of ethylene glycol butyl ether is added, and stirred for 0.5 h. The temperature is lowered to 50℃ to discharge the product, and a sulfonate alkyd resin is obtained. The aqueous monomer is hydroxypropyl methacrylate.

[0036] Preparation of rosin modified resin: The 144g of rosin is heated to 150°C under nitrogen protection, and stirred until the rosin is melted, then 96g of rosin is added, 32.4g of maleic anhydride is added while stirring, heated to 200°C for 1h, then 40.8g of glycerol is added, heated to 270°C, and continue to react for 7h, and water is discharged in time during the reaction, and the rosin compound is obtained after vacuuming.

[0037] Preparation of ink: The 65g of rosin modified resin is mixed with 42g of vegetable oil to obtain the connecting agent; The red and blue organic dyes are mixed with carbon black at a mass ratio of 1:1 to obtain the pigment; The drying agent, friction powder and water repellent are mixed at a mass ratio of 1:1:1 to obtain the auxiliary agent; The 20g of pigment, 77g of connecting agent and 3g of auxiliary agent are mixed and stirred to obtain the ink.

[0038] Example 4 Example 4 is based on Example 3, and in Example 4, the amount of sulfonate monomer used in the preparation of sulfonate alkyd resin is 21.36g, the amount of hydroxypropyl methacrylate used is 16.76g, and the amount of ethylene glycol butyl ether used is 41.88g.

[0039] Example 5 Example 5 is based on Example 3, and in Example 5, the amount of sulfonate monomer used in the preparation of sulfonate alkyd resin is 24.28g, the amount of hydroxypropyl methacrylate used is 15.92g, and the amount of ethylene glycol butyl ether used is 39.8g.

[0040] Example 6 Example 6 is based on Example 3, and in Example 6, the monomer hydroxypropyl methacrylate is replaced by polyethylene glycol (CAS No.: 25322-68-3) in the preparation of sulfonate alkyd resin.

[0041] Example 7 Example 7 is based on Example 3, and in Example 7, the reaction temperature in the preparation of metal framework is 110°C.

[0042] Example 8 Example 8 is based on Example 3, and in Example 8, the reaction temperature in the preparation of metal framework is 180°C.

[0043] Example 9 Example 9 is based on Example 3, and in Example 9, the reaction time in the preparation of metal framework is 90min.

[0044] Example 10 Example 10 is based on Example 3, and in Example 10, the reaction time is 150 min when preparing the metal skeleton.

[0045] Example 11 Example 11 is based on Example 3, and in Example 11, the maleic anhydride used is 28.8 g when preparing the rosin modified resin.

[0046] Example 12 Example 12 is based on Example 3, and in Example 12, the maleic anhydride used is 36 g when preparing the rosin modified resin.

[0047] Example 13 Example 13 is based on Example 3, and in Example 13, the metal skeleton added is 3.6 g when preparing the rosin modified resin.

[0048] Example 14 Example 14 is based on Example 3, and in Example 14, the metal skeleton added is 8.4 g when preparing the rosin modified resin.

[0049] Comparative Example 1 Comparative Example 1 is based on Example 3, and in Comparative Example 1, the sulfonate alkyd resin is replaced by a common alkyd resin when preparing the rosin modified resin.

[0050] Comparative Example 2 Comparative Example 2 is based on Example 3, and in Comparative Example 2, the metal skeleton is replaced by an equal amount of nano cobalt powder when preparing the rosin modified resin.

[0051] Comparative Example 3 Comparative Example 3 is based on Example 3, and in Comparative Example 3, no maleic anhydride is added to the rosin modified resin when preparing the ink.

[0052] Comparative Example 4 Comparative Example 4 is based on Example 3, and in Comparative Example 4, the rosin modified resin is replaced by a phenolic resin when preparing the ink.

[0053] Performance Test The samples of Examples 1-14 and Comparative Examples 1-4 were tested for the following performances: (1) Impact strength test The impact performance of the samples was tested according to GB / T 1732, and each sample was tested three times to take the average value, and the test results were filled in Table 1.

[0054] (2) Odor The odor of the sample was rated according to GB / T 35773-2017, each sample was tested 3 times, the average value was taken, and the test results were filled in Table 1.

[0055] (3) Corrosion resistance A sodium chloride solution with a mass concentration of 5% was configured, and a salt spray corrosion test box FQY 015 from Shanghai Experimental Instrument Factory was used for testing, the test temperature was 35°C, each sample was tested 3 times, the average value was taken, and the test results were filled in Table 1.

[0056] Table 1 Performance test results of examples 1-14 and comparative examples 1-4 As can be seen from Table 1, the impact strength of examples 1-3 is all above 4.24 J, which shows that the ink prepared by the application has good strength; the odor of examples 1-3 is all 1 / 1, which shows that the odor of the ink prepared by the application is improved; the current density of examples 1-3 is all below 1.83 μA / cm 2 , which shows that the ink prepared by the application has good corrosion resistance.

[0057] In examples 4 and 5, the mass ratio of sulfonate monomer, hydroxypropyl methacrylate and ethylene glycol butyl ether in the preparation of sulfonate alkyd resin is not within the range defined by the application. When the amount of sulfonate monomer is too small, the water solubility of the prepared sulfonate alkyd resin is poor, and the viscosity is too large, which affects the overall stability of the system; when the content of sulfonate monomer is too high, the number of polar groups in the molecular chain of the prepared sulfonate resin increases, thereby increasing the viscosity of the sulfonate resin, which affects the overall stability of the system, so the performance of examples 4 and 5 is decreased.

[0058] In example 6, polyethylene glycol is used instead of monomer hydroxypropyl methacrylate in the preparation of sulfonate alkyd resin. The reactivity of polyethylene glycol is poor, and the stability of the prepared sulfonate alkyd resin is decreased, which affects the overall performance of the system, so the performance of example 6 is decreased.

[0059] In examples 7 and 8, the reaction temperature in the preparation of metal skeleton is not within the range defined by the application, and in examples 9 and 10, the reaction time in the preparation of metal skeleton is not within the range defined by the application. When the reaction temperature is too high or too low, or the reaction time is too short or too long, it is difficult to form a metal skeleton with stable morphology, and it is difficult to further improve the active site of the metal skeleton. The combination performance with the resin system is decreased, so the performance of examples 7-10 is decreased.

[0060] The mass ratio between the rosin, the maleic anhydride and the glycerol in the preparation of the rosin modified resin in the embodiments 11 and 12 is not within the range defined in the present application, when the amount of the maleic anhydride is too small, the softening point of the rosin is reduced, thereby affecting the stability of the rosin modified resin prepared subsequently; when the amount of the maleic anhydride is too high, the softening point of the rosin is too high, the rigidity of the rosin modified resin prepared subsequently is too large, and the strength is reduced.

[0061] The mass ratio between the rosin compound, the sulfonate alkyd resin and the metal skeleton in the preparation of the rosin modified resin in the embodiments 13 and 14 is not within the range defined in the present application, when the amount of the metal skeleton is too small, the reinforcing effect on the resin system is difficult to further promote, thereby affecting the strength of the rosin modified resin, and the corrosion resistance is also reduced; when the amount of the metal skeleton is too high, the dispersibility of the metal skeleton in the system is reduced, and the metal skeleton is aggregated, thereby affecting the overall comprehensive performance of the system.

[0062] In the comparative example 1, the sulfonate alkyd resin is replaced by the ordinary alkyd resin, the water solubility of the ordinary alkyd resin is poor, the dispersibility of the rosin modified resin prepared is difficult to improve, and the stability of the overall system is affected.

[0063] In the comparative example 2, the metal skeleton is replaced by the same amount of nano cobalt powder, the dispersibility of the nano cobalt powder in the system is difficult to further improve, the nano cobalt powder is aggregated in the system, and the overall corrosion resistance of the system is difficult to further improve.

[0064] In the comparative example 3, the maleic anhydride is not added, the polar group is difficult to be introduced, the combination between the rosin and the alkyd resin is reduced, the molecular force is reduced, and the stability is reduced, so the performance of the comparative example 3 is reduced.

[0065] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application, through the above description, the relevant staff can make various changes and modifications without deviating from the technical idea of the present application. The technical scope of the present application is not limited to the content in the specification, and the technical scope of the present application must be determined according to the scope of the claims.

Claims

1. A rosin-modified resin, characterized in that: The raw materials include maleic anhydride, sulfonate alkyd resin, rosin and metal organic framework. The sulfonate alkyd resin raw materials include neopentyl glycol, dibutyltin dilaurate, 5-sodium sulfoisophthalate, phthalic anhydride and pentaerythritol.

2. A rosin-modified resin according to claim 1, characterized in that: The sulfonate alkyd resin is prepared by the following method: Neopentyl glycol and dibutyltin dilaurate are mixed, and after heating, sodium 5-sulfoisophthalate is added for reaction. After the reactant becomes transparent, the temperature is lowered to obtain a sulfonate monomer. A water-based monomer, phthalic anhydride, pentaerythritol, soybean oil acid, and xylene are mixed with the sulfonate monomer, heated for reaction, and then cooled. The xylene is extracted, the temperature is further lowered, and then ethylene glycol butyl ether is added. The mixture is stirred and discharged to obtain a sulfonate alkyd resin.

3. A rosin-modified resin according to claim 2, characterized in that: The waterborne monomer includes hydroxypropyl methacrylate.

4. A rosin-modified resin according to claim 3, characterized in that: The mass ratio of the sulfonate monomer, hydroxypropyl methacrylate and ethylene glycol butyl ether is (0.54-0.58):0.4:

1.

5. A rosin-modified resin according to claim 1, characterized in that: The metal organic framework raw materials include cobalt nitrate hexahydrate, trimesic acid and N,N-dimethylformamide; the metal organic framework is prepared by the following method: Cobalt nitrate hexahydrate and N,N-dimethylformamide are mixed, and then trimesic acid is added and stirred to obtain a mixture. The mixture is heated to react, cooled, washed, and dried to obtain an organic metal framework.

6. A rosin-modified resin according to claim 5, characterized in that: The reaction temperature is 140-160° C., and the reaction time is 110-130 min.

7. A method for preparing the rosin-modified resin according to any one of claims 1 to 6, characterized in that: The steps include: The rosin is heated until it is melted, and then more rosin is added, maleic anhydride is added while stirring, glycerin is added after the reaction, and the temperature is raised to continue the reaction to obtain a rosin complex; the rosin complex, sulfonate alkyd resin and metal skeleton mixture are heated to react to obtain a rosin modified resin.

8. The method for preparing a rosin-modified resin according to claim 7, wherein: The mass ratio of the rosin, maleic anhydride and glycerol is 1:(0.13-0.14):0.

17.

9. The method for preparing a rosin-modified resin according to claim 7, wherein: The mass ratio of the rosin composite, the sulfonate alkyd resin and the metal organic framework is 1:0.22:(0.06-0.08).

10. A low-odor ink, characterized in that: The invention comprises the rosin modified resin according to any one of claims 1 to 6.

Images