CN116003736A - Preparation method of polyurethane binder for low-surface-energy film sandy ink - Google Patents
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Abstract
A preparation method of a polyurethane binder for low-surface-energy film sandy ink comprises the following steps: (1) Adding polyester polyol, polyether polyol, a chain extender, a cross-linking agent and a solvent into a reactor, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 55-75 ℃, dripping diisocyanate into the reactor at a constant speed within 1-2 h, and continuously reacting for 1-3 h to obtain a hydroxyl-terminated prepolymer I; (2) Adding a catalyst and a proper amount of solvent into the hydroxyl-terminated prepolymer I obtained in the step (1), and continuously reacting for 2-6 hours after the temperature is controlled between 75 and 85 ℃ to obtain a hydroxyl-terminated prepolymer II; (3) Cooling the hydroxyl-terminated prepolymer II obtained in the step (2) to 50-55 ℃, adding a solvent to dilute and disperse for 0.5-1 h, cooling to room temperature, uniformly stirring, filtering and discharging to obtain hydroxyl-terminated polyurethane; (4) And mixing and stirring the obtained hydroxyl-terminated polyurethane with a solvent and a curing agent uniformly.
Description
Technical Field
The invention belongs to the technical field of printing ink printing, and particularly relates to a preparation method of a polyurethane binder for low-surface-energy film sand-sensitive printing ink.
Background
With the rapid development of the packaging and printing industry, the gravure ink market of plastic films in China is gradually expanding. The gravure printing ink is widely applied to the plastic packaging fields such as foods, medicines, agricultural feeding products, daily chemical products and the like, along with the sustainable development of the gravure printing market, the requirements of consumers on printing quality are continuously improved, and the matte sand feeling ink product can lead the product to be higher in grade and has soft reflection of light and the effect of protecting vision, so that various ink manufacturers worldwide push out the respective matte sand feeling ink products. However, at present, when the adhesive force of the matte sand feeling ink is tested on a common printing substrate such as PE, PP, PET, the offset ink can be adhered by an adhesive tape, and the offset ink is partially or completely separated from a printing stock, so that poor adhesive force of the matte sand feeling ink brings great trouble to ink manufacturers and printing manufacturers, and particularly the adhesive force and scratch resistance on a low-surface-energy BOPP film, and some matte sand feeling ink products on the market obviously cannot meet the current requirements.
The invention patent with publication number of CN 110845907A provides a preparation method of high-adhesion scratch-resistant matte ink containing a polyurethane system, but does not propose a specific preparation method of polyurethane resin, and only purely introduces the formulation composition of the matte ink.
Disclosure of Invention
Aiming at the problems of the background technology, the invention designs a preparation method of a polyurethane binder for low-surface-energy film sandy ink, which aims at: provides a preparation method of a polyurethane binder for a low-surface-energy film and sand-sensitive ink, which has high bonding strength and high stability.
The technical solution of the invention is as follows:
a preparation method of a polyurethane binder for low-surface-energy film sandy ink comprises the following steps:
(1) Adding polyester polyol, polyether polyol, a chain extender, a cross-linking agent and a solvent into a reactor, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 55-75 ℃, dripping diisocyanate into the reactor at a constant speed within 1-2 h, and continuously reacting for 1-3 h to obtain a hydroxyl-terminated prepolymer I;
(2) Adding a catalyst and a proper amount of solvent into the hydroxyl-terminated prepolymer I obtained in the step (1), and continuously reacting for 2-6 hours after the temperature is controlled between 75 and 85 ℃ to obtain a hydroxyl-terminated prepolymer II;
(3) Cooling the hydroxyl-terminated prepolymer II obtained in the step (2) to 50-55 ℃, adding a solvent to dilute and disperse for 0.5-1 h, cooling to room temperature, uniformly stirring, filtering and discharging to obtain hydroxyl-terminated polyurethane;
(4) And (3) mixing and stirring the hydroxyl-terminated polyurethane obtained in the step (3) with a solvent and a curing agent uniformly to obtain the polyurethane binder for the low-surface-energy film and the sandy ink.
The polyester polyol in the step (1) is one or more of the following: polyethylene glycol adipate glycol with average molecular weight of 1000-2000; a poly (hexanediol adipate) glycol having an average molecular weight of 1000 to 2000; neopentyl glycol adipate diol having an average molecular weight of 1000 to 2000; 1, 4-butanediol polyadipate diol with average molecular weight of 1000-2000; the average molecular weight of the poly (diethylene glycol adipate) glycol is 1000-2000.
The polyether polyol in the step (1) is one or more of the following: polyethylene glycol with average molecular weight of 1000-2000; polypropylene glycol with average molecular weight of 1000-2000; polytetrahydrofuran diol with an average molecular weight of 1000-2000; tetrahydrofuran-propylene oxide copolymer glycol with average molecular weight of 1000-2000.
The chain extender in the step (1) is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, hexanediol and terephthalic acid diethyl glycol.
The cross-linking agent in the step (1) is one or more of glycerol, trimethylolpropane and 3,3 '-dichloro-4, 4' -diaminodiphenyl methane.
The solvent in the steps (1), (2), (3) and (4) is one or more of acetone, butanone, isopropanol, ethyl acetate and butyl acetate.
The diisocyanate in the step (1) is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
The mass ratio of the polyester polyol, the polyether polyol, the chain extender, the cross-linking agent, the solvent and the diisocyanate in the step (1) is 5-15%, 8-18%, 0.2-2%, 1-10% and 5-15% respectively.
The catalyst in the step (2) is one or more of stannous octoate, dibutyl tin dilaurate and organic bismuth.
The mass ratio of the catalyst to the solvent in the step (2) is 0.02-0.1% and 5-20% respectively.
The mass ratio of the solvent in the step (3) is 40% -60%.
The curing agent in the step (4) is one or more of hexamethylene diisocyanate trimer, toluene diisocyanate trimer and hexamethylene diisocyanate-toluene diisocyanate mixed trimer.
The mass ratio of the hydroxyl-terminated polyurethane to the solvent to the curing agent in the step (4) is 55-80%, 20-40% and 1-20% respectively.
The invention has the beneficial effects that: according to the invention, a prepolymer method is adopted to gradually polymerize and synthesize the polyurethane binder for the low-surface-energy film and the sandy ink, and the polyurethane binder has small surface tension of a film formed on the surface of the low-surface-energy film material, good wettability, hydrophobicity and bubble removal property, and can rapidly infiltrate the surface of the low-surface-energy film material, so that the bonding strength with the low-surface-energy film material is greatly improved, and the problems that the traditional resin binder has strong hydrophilicity and large polarity, is easy to migrate to the surface of the film to form a weak interface layer, and causes large surface tension and poor wettability of the film are solved; in addition, the curing agent can effectively crosslink with polyurethane, and the stability of the connecting material is further improved.
Detailed Description
The invention is further described below in connection with specific examples.
Example 1 (amounts of the respective substances in mass percent)
A preparation method of a polyurethane binder for low-surface-energy film sandy ink comprises the following steps:
(1) Adding 5.9% of polyethylene glycol adipate glycol (molecular weight 1000), 12.2% of polyethylene glycol (molecular weight 1000), 0.5% of chain extender glycol, 0.9% of cross-linking agent glycerol and 2.5% of solvent acetone into a reaction vessel, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 55 ℃, uniformly dripping 11.1% of isophorone diisocyanate into the reactor within 1h, and continuing to react for 1.5h to obtain hydroxyl-terminated prepolymer I;
(2) Adding 0.1% of catalyst dibutyltin dilaurate and 15.3% of solvent acetone into the obtained hydroxyl-terminated prepolymer I, and continuously reacting for 2 hours at the temperature of 75 ℃ to obtain a hydroxyl-terminated prepolymer II;
(3) Cooling the obtained hydroxyl-terminated prepolymer II to 55 ℃, adding 51.5% of solvent acetone to dilute and disperse for 0.5h, cooling to room temperature, uniformly stirring, filtering and discharging to obtain hydroxyl-terminated polyurethane;
(4) Mixing the obtained hydroxyl-terminated polyurethane with solvent acetone and curing agent hexamethylene diisocyanate trimer according to the mass ratio of 55%:35%: and (5) uniformly mixing and stirring 10% to obtain the polyurethane binder for the low-surface-energy film and the sandy ink.
The viscosity of the polyurethane binder for the low surface energy film and the sand feeling ink is 700 mPas (25 ℃).
Example 2 (amounts of the respective substances in mass percent)
A preparation method of a polyurethane binder for low-surface-energy film sandy ink comprises the following steps:
(1) Adding 7.6% of poly (neopentyl glycol adipate) glycol (molecular weight 1000), 11.2% of polytetrahydrofuran glycol (molecular weight 1000), 1.0% of chain extender 1, 4-butanediol, 0.5% of crosslinking agent trimethylolpropane and 5.0% of solvent isopropanol into a reaction vessel, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 60 ℃, adding 12.2% of diphenylmethane diisocyanate into the reactor at a constant speed within 1.5h, and continuing to react for 2h to obtain a hydroxyl-terminated prepolymer I;
(2) Adding 0.05% of catalyst stannous octoate and 12.5% of solvent isopropanol into the obtained hydroxyl-terminated prepolymer I, and continuously reacting for 3 hours after controlling the temperature to be 80 ℃ to obtain a hydroxyl-terminated prepolymer II;
(3) Cooling the obtained hydroxyl-terminated prepolymer II to 50 ℃, adding 50.05% solvent isopropanol to dilute and disperse for 0.5h, cooling to room temperature, uniformly stirring, filtering and discharging to obtain hydroxyl-terminated polyurethane;
(4) Mixing the obtained hydroxyl-terminated polyurethane with solvent isopropanol and curing agent toluene diisocyanate trimer according to the mass ratio of 60%:35%: and 5% of the polyurethane binder is mixed and stirred uniformly to obtain the polyurethane binder for the low-surface-energy film and the sandy ink.
The viscosity of the polyurethane binder for the low surface energy film and the sand feeling ink is 600 mPas (25 ℃).
Example 3 (amounts of substances in mass percent)
A preparation method of a polyurethane binder for low-surface-energy film sandy ink comprises the following steps:
(1) Adding 7.8% of poly (diethylene glycol adipate) glycol (molecular weight 1000), 10.9% of polypropylene glycol (molecular weight 1000), 1.5% of chain extender (diethyl terephthalate glycol), 0.8% of cross-linking agent (trimethylolpropane) and 10.0% of solvent (butyl acetate) into a reaction vessel, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 55 ℃, adding 11.4% of isophorone diisocyanate into the reactor at a constant speed within 1h, and continuously reacting for 1.5h to obtain a hydroxyl-terminated prepolymer I;
(2) Adding 0.05% of catalyst organic bismuth and 10.5% of solvent butyl acetate into the hydroxyl-terminated prepolymer I, and continuously reacting for 2 hours at the temperature of 75 ℃ to obtain a hydroxyl-terminated prepolymer II;
(3) Cooling the obtained hydroxyl-terminated prepolymer II to 55 ℃, adding 47.05% solvent butyl acetate to dilute and disperse for 0.5h, cooling to room temperature, uniformly stirring, filtering and discharging to obtain hydroxyl-terminated polyurethane;
(4) Mixing the hydroxyl-terminated polyurethane with solvent butyl acetate, curing agent hexamethylene diisocyanate and toluene diisocyanate to obtain a trimer, wherein the mass ratio of the trimer is 65%:25%: and (5) uniformly mixing and stirring 10% to obtain the polyurethane binder for the low-surface-energy film and the sandy ink.
The viscosity of the polyurethane binder for the low surface energy film and the sand feeling ink is 800 mPas (25 ℃).
Example 4 (amounts of substances in mass percent)
A preparation method of a bi-component polyurethane binder suitable for low-surface-energy film sandy ink comprises the following steps:
adding 8.2% of polyethylene glycol adipate glycol (molecular weight 2000), 12.2% of polytetrahydrofuran glycol (molecular weight 2000), 1.0% of chain extender glycol, 1.5% of cross-linking agent glycerol and 8.0% of solvent butanone into a reaction vessel, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 65 ℃, uniformly dripping 14.6% of isophorone diisocyanate into the reactor within 1h, and continuing to react for 2.0h to obtain hydroxyl-terminated prepolymer I;
(2) Adding 0.04% of catalyst dibutyl tin dilaurate and 14.0% of solvent butanone into the hydroxyl-terminated prepolymer I, and continuously reacting for 3 hours at 80 ℃ to obtain a hydroxyl-terminated prepolymer II;
(3) Cooling the obtained hydroxyl-terminated prepolymer II to 50 ℃, adding 40.46% solvent butanone for diluting and dispersing for 0.5h, cooling to room temperature, uniformly stirring, filtering and discharging to obtain hydroxyl-terminated polyurethane;
(4) Mixing the obtained hydroxyl-terminated polyurethane with solvent butanone and curing agent hexamethylene diisocyanate trimer according to the mass ratio of 70%:25%: and 5% of the polyurethane binder is mixed and stirred uniformly to obtain the polyurethane binder for the low-surface-energy film and the sandy ink.
The viscosity of the polyurethane binder for the low surface energy film and the sand feeling ink is 900 mPas (25 ℃).
Example 5 (amounts of substances in mass percent)
A preparation method of a bi-component polyurethane binder suitable for low-surface-energy film sandy ink comprises the following steps:
(1) Adding 6.7% of poly (neopentyl glycol adipate) glycol (molecular weight 2000), 12.6% of polypropylene glycol (molecular weight 2000), 0.8% of chain extender 1, 4-butanediol, 1.0% of cross-linking agent trimethylolpropane and 5.0% of solvent ethyl acetate into a reaction vessel, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 65 ℃, uniformly dripping 15.4% of diisocyanate into the reactor within 1h, and continuing to react for 3.0h to obtain hydroxyl-terminated prepolymer I;
(2) Adding 0.05% of catalyst dibutyltin dilaurate and 12.5% of solvent ethyl acetate into the obtained hydroxyl-terminated prepolymer I, and continuously reacting for 4 hours at the temperature of 85 ℃ to obtain a hydroxyl-terminated prepolymer II;
(3) Cooling the obtained hydroxyl-terminated prepolymer II to 50 ℃, adding 45.95% ethyl acetate solvent for diluting and dispersing for 0.5h, cooling to room temperature, uniformly stirring, filtering and discharging to obtain hydroxyl-terminated polyurethane;
(4) Mixing the obtained hydroxyl-terminated polyurethane with solvent ethyl acetate and curing agent toluene diisocyanate trimer according to the mass ratio of 60%:25%: and (5) mixing and stirring uniformly to obtain the polyurethane binder for the low-surface-energy film and the sandy ink.
The viscosity of the polyurethane binder for the low surface energy film and the sand feeling ink is 1000 mPas (25 ℃).
Comparative example 1 (amounts of the respective substances in mass percent)
The comparative example provides a process for preparing a polyurethane binder for sandy ink, which is substantially the same as example 1, except that the diisocyanate is added directly, rather than dropwise, as in the case of:
(1) Adding 5.9% of polyethylene glycol adipate glycol (molecular weight 1000), 12.2% of polyethylene glycol (molecular weight 1000), 11.1% of isophorone diisocyanate, 0.5% of chain extender glycol, 0.9% of cross-linking agent glycerol and 2.5% of solvent acetone into a reaction container, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 55 ℃, and continuing to react for 2.5 hours to obtain hydroxyl-terminated prepolymer I;
(2) Adding 0.1% of catalyst dibutyltin dilaurate and 15.3% of solvent acetone into the obtained hydroxyl-terminated prepolymer I, and continuously reacting for 2 hours at the temperature of 75 ℃ to obtain a hydroxyl-terminated prepolymer II;
(3) Cooling the obtained hydroxyl-terminated prepolymer II to 55 ℃, adding 51.5% of solvent acetone to dilute and disperse for 0.5h, cooling to room temperature, uniformly stirring, filtering and discharging to obtain hydroxyl-terminated polyurethane;
(4) Mixing the obtained hydroxyl-terminated polyurethane with solvent acetone and curing agent hexamethylene diisocyanate trimer according to the mass ratio of 55%:35%: and (5) mixing and stirring uniformly 10% to obtain the sandy ink binder.
Comparative example 2 (amounts of the respective substances in mass percent)
This comparative example provides a method for preparing a polyurethane binder for a sandy ink, substantially identical to example 1, except that no curing agent is introduced:
(1) Adding 5.9% of polyethylene glycol adipate glycol (molecular weight 1000), 12.2% of polyethylene glycol (molecular weight 1000), 0.5% of chain extender glycol, 0.9% of cross-linking agent glycerol and 2.5% of solvent acetone into a reaction vessel, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 55 ℃, uniformly dripping 11.1% of isophorone diisocyanate into the reactor within 1h, and continuing to react for 1.5h to obtain hydroxyl-terminated prepolymer I;
(2) Adding 0.1% of catalyst dibutyltin dilaurate and 15.3% of solvent acetone into the obtained hydroxyl-terminated prepolymer I, and continuously reacting for 2 hours at the temperature of 75 ℃ to obtain a hydroxyl-terminated prepolymer II;
(3) And (3) cooling the obtained hydroxyl-terminated prepolymer II to 55 ℃, adding 51.5% of solvent acetone to dilute and disperse for 0.5h, cooling to room temperature, uniformly stirring, and filtering and discharging to obtain the hydroxyl-terminated polyurethane.
The polyurethane resins prepared in examples 1 to 5 and comparative examples 1 to 2 above were formulated into sandy inks according to the formulation of Table 1, and their application properties were tested.
Table 1 formulation for sand feel ink
| Raw materials | Parts by mass |
| Polyurethane binder | 50 |
| Quartz powder | 27.5 |
| Acetic acid ethyl ester | 20 |
| Auxiliary agent | 2.5 |
The application performance of the prepared sandy ink is detected, and the testing method is as follows:
GBT 13217.4-2008 liquid ink viscosity test method; GBT 13217.7-2009 liquid ink attachment fastness testing method; GBT 13217.8-2009 liquid ink anti-blocking test method. GB/T8808-1988 soft composite T-shaped peel strength test method.
Hydrolysis resistance measurement: soaking at 70deg.C and 95% RH for 168-504 hr.
The results of the performance tests of examples 1-5 and comparative examples 1-2 are shown in Table 2:
TABLE 2
As is clear from Table 2, the sand-sensitive inks prepared from the polyurethane binders of examples 1 to 5 of the present invention have high adhesion fastness, blocking resistance, composite strength and hydrolysis resistance, as compared with the sand-sensitive inks prepared from the polyurethane binders of comparative examples 1 to 2. The polyurethane binder obtained by the invention can effectively infiltrate the surface of the low surface energy film material, and can be used as a printing sand feel ink binder for printing low surface energy film materials such as corona-free PET and the like.
The method adopts the mode of dropwise adding isocyanate, because the reaction speed of the hard segment isocyanate and the soft segment polyol is relatively high in the polyurethane synthesis process, if the hard segment isocyanate and the soft segment polyol are directly mixed for reaction, on one hand, the reaction temperature is not easy to control, and on the other hand, the partial hard segment and soft segment polymer is easy to generate a two-phase separation state. According to the invention, a prepolymer method is adopted to gradually polymerize and synthesize the polyurethane binder for the low-surface-energy film and the sandy ink, and the polyurethane binder has small surface tension of a film formed on the surface of the low-surface-energy film material, good wettability, hydrophobicity and bubble removal property, and can rapidly infiltrate the surface of the low-surface-energy film material, so that the bonding strength with the low-surface-energy film material is greatly improved, and the problems that the traditional resin binder has strong hydrophilicity and large polarity, is easy to migrate to the surface of the film to form a weak interface layer, and causes large surface tension and poor wettability of the film are solved; in addition, the curing agent can effectively crosslink with polyurethane, and the stability of the connecting material is further improved.
The above examples merely illustrate specific embodiments of the disclosure, but the embodiments of the disclosure are not limited by the foregoing. Any changes, modifications, substitutions, combinations, and simplifications that may be made without materially departing from the spirit and principles of the inventive concepts of the present disclosure are intended to be equivalent substitutes and are intended to be included within the scope of protection as defined by the claims.
Claims (10)
1. A preparation method of a polyurethane binder for low-surface-energy film sandy ink is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding polyester polyol, polyether polyol, a chain extender, a cross-linking agent and a solvent into a reactor, uniformly mixing, vacuumizing, introducing high-purity nitrogen, heating to 55-75 ℃, dripping diisocyanate into the reactor at a constant speed within 1-2 h, and continuously reacting for 1-3 h to obtain a hydroxyl-terminated prepolymer I;
(2) Adding a catalyst and a proper amount of solvent into the hydroxyl-terminated prepolymer I obtained in the step (1), and continuously reacting for 2-6 hours after the temperature is controlled between 75 and 85 ℃ to obtain a hydroxyl-terminated prepolymer II;
(3) Cooling the hydroxyl-terminated prepolymer II obtained in the step (2) to 50-55 ℃, adding a solvent to dilute and disperse for 0.5-1 h, cooling to room temperature, uniformly stirring, filtering and discharging to obtain hydroxyl-terminated polyurethane;
(4) And (3) mixing and stirring the hydroxyl-terminated polyurethane obtained in the step (3) with a solvent and a curing agent uniformly to obtain the polyurethane binder for the low-surface-energy film and the sandy ink.
2. The method for preparing the polyurethane binder for the low-surface-energy film sandy ink, as claimed in claim 1, wherein the method comprises the following steps: the polyester polyol in the step (1) is one or more of the following: polyethylene glycol adipate glycol with average molecular weight of 1000-2000; a poly (hexanediol adipate) glycol having an average molecular weight of 1000 to 2000; neopentyl glycol adipate diol having an average molecular weight of 1000 to 2000; 1, 4-butanediol polyadipate diol with average molecular weight of 1000-2000; the average molecular weight of the poly (diethylene glycol adipate) glycol is 1000-2000.
3. The method for preparing the polyurethane binder for the low-surface-energy film sandy ink, as claimed in claim 1, wherein the method comprises the following steps: the polyether polyol in the step (1) is one or more of the following: polyethylene glycol with average molecular weight of 1000-2000; polypropylene glycol with average molecular weight of 1000-2000; polytetrahydrofuran diol with an average molecular weight of 1000-2000; tetrahydrofuran-propylene oxide copolymer glycol with average molecular weight of 1000-2000.
4. The method for preparing the polyurethane binder for the low-surface-energy film sandy ink, as claimed in claim 1, wherein the method comprises the following steps: the chain extender in the step (1) is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, hexanediol and terephthalic acid diethyl glycol.
5. The method for preparing the polyurethane binder for the low-surface-energy film sandy ink, as claimed in claim 1, wherein the method comprises the following steps: the cross-linking agent in the step (1) is one or more of glycerol, trimethylolpropane and 3,3 '-dichloro-4, 4' -diaminodiphenyl methane.
6. The method for preparing the polyurethane binder for the low-surface-energy film sandy ink, as claimed in claim 1, wherein the method comprises the following steps: the solvent in the steps (1), (2), (3) and (4) is one or more of acetone, butanone, isopropanol, ethyl acetate and butyl acetate.
7. The method for preparing the polyurethane binder for the low-surface-energy film sandy ink, as claimed in claim 1, wherein the method comprises the following steps: the diisocyanate in the step (1) is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
8. The method for preparing the polyurethane binder for the low-surface-energy film sandy ink, as claimed in claim 1, wherein the method comprises the following steps: the mass ratio of the polyester polyol, the polyether polyol, the chain extender, the cross-linking agent, the solvent and the diisocyanate in the step (1) is 5-15%, 8-18%, 0.2-2%, 1-10% and 5-15% respectively.
9. The method for preparing the polyurethane binder for the low-surface-energy film sandy ink, as claimed in claim 1, wherein the method comprises the following steps: the catalyst in the step (2) is one or more of stannous octoate, dibutyl tin dilaurate and organic bismuth, and the curing agent in the step (4) is one or more of hexamethylene diisocyanate trimer, toluene diisocyanate trimer and hexamethylene diisocyanate-toluene diisocyanate mixed trimer.
10. The method for preparing the polyurethane binder for the low-surface-energy film sandy ink, as claimed in claim 1, wherein the method comprises the following steps: the mass ratio of the catalyst to the solvent in the step (2) is 0.02-0.1% and the mass ratio of the solvent in the step (3) is 40-60%, and the mass ratio of the hydroxyl-terminated polyurethane to the solvent to the curing agent in the step (4) is 55-80%, 20-40% and 1-20%, respectively.
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