High-solid-content quick-drying ink resin and preparation method thereof
By preparing a high-solid content, fast-drying ink resin, the problems of slow drying and poor adhesion of traditional water-based inks were solved, fast drying and excellent adhesion were achieved, and its application in packaging and electronics fields was expanded.
Patent Information
- Application Number
- CN202510930278.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-07
- Publication Date
- 2025-09-16
AI Technical Summary
Traditional water-based inks have slow drying speed, poor adhesion to non-polar substrates, and insufficient weather resistance after film formation, which limits their application in packaging and electronics.
It uses a high-solid, quick-drying ink resin composed of polyester monomers, MOF-silicone-containing acrylate composite monomers, vinyl ether monomers, etc. It is prepared through a specific process and added with thermal initiators, photoinitiators, leveling agents, defoaming agents and adhesion promoters to form excellent adhesion and weather resistance.
The rapid drying, good adhesion and weather resistance of the ink resin are achieved, which improves the quality and application range of the ink.
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of ink materials, in particular to a high-solid content quick-drying ink resin and a preparation method thereof. Background Art
[0002] With the improvement of living standards, the packaging industry has grown rapidly, which has also promoted the continuous development of gravure ink technology and market. Ink resin is the main material used in plastic packaging printing ink. Its properties determine the ink's adhesion and fastness.
[0003] Traditional water-based inks use water as a solvent, which significantly improves environmental friendliness. However, they dry slowly, have poor adhesion to non-polar substrates (such as PP and PE films), and lack weather resistance after film formation, limiting their application in packaging, electronics and other fields.
[0004] Based on this, the present invention provides a high-solid content quick-drying ink resin and a preparation method thereof to solve the above-mentioned technical problems. Summary of the Invention
[0005] The purpose of the present invention is to provide a high-solid content quick-drying ink resin and a preparation method thereof. The prepared high-solid content quick-drying ink resin not only has good high solid content and fixing speed performance, but also has excellent adhesion and weather resistance, effectively ensuring its quality.
[0006] To achieve the above object, the present invention provides the following technical solutions: A first aspect of the present invention provides a high-solid content, fast-drying ink resin, which is composed of the following raw materials in parts by weight: 30 to 35 parts of a polyester monomer, 15 to 20 parts of a MOF-silicon-containing acrylate composite monomer, 12 to 15 parts of a vinyl ether monomer, 8 to 10 parts of trimethylolpropane triacrylate, 6 to 10 parts of ethoxylated trimethylolpropane triacrylate, 2 to 4 parts of a thermal initiator, 2 to 4 parts of a photoinitiator, 0.3 to 0.6 parts of a leveling agent, 0.3 to 0.5 parts of a defoaming agent, and 1 to 2 parts of an adhesion promoter; The polyester monomer is a hyperbranched polyester macromonomer; The preparation process of the MOF-silicon-containing acrylate composite monomer is as follows: The ZIF-8 was placed in the monomer solution and ultrasonically dispersed; The obtained dispersion was centrifuged, and the precipitate was collected, washed with anhydrous ethanol, and then vacuum-dried to prepare a MOF-silicon-containing acrylate composite monomer.
[0007] The present invention is further configured as follows: the preparation process of the polyester monomer is as follows: The composite material and anhydrous dimethyl sulfoxide are magnetically stirred at a volume ratio of 1:3-4 for 20-30 minutes; 8-10% of the mass of the composite material in the amount of CALB enzyme powder is added thereto, and stirring is continued for 4-7 minutes to obtain a pre-mixed solution; Add modified mesoporous silica nanoparticles to the obtained pre-formulated solution, perform ultrasonic dispersion treatment for 20 to 30 minutes, and then place in a constant temperature oscillating water bath at 50° C. for 42 to 44 hours; After the reaction is complete, ethanol is immediately added to the reaction system to terminate the enzyme-catalyzed reaction, and the reaction mixture is centrifuged to collect the precipitate; A hydrofluoric acid solution with a mass fraction of 5.1 to 5.4% is added to the precipitate, and the precipitate is treated at room temperature for 100 to 130 minutes. The precipitate is then dialyzed in deionized water using a dialysis membrane with a molecular weight cutoff of 3500 to 4500 Da. After the dialysis, the solution in the dialysis bag is vacuum freeze-dried to prepare a polyester monomer.
[0008] The present invention is further configured as follows: the composite material is prepared by compounding pentaerythritol tetraacrylate and dimer acid in a molar ratio of 1:3.
[0009] The present invention is further configured as follows: the amount of the modified mesoporous silica nanoparticles added is 10-11% of the mass of the pre-prepared solution; the preparation process of the modified mesoporous silica nanoparticles is as follows: The mesoporous silica nanoparticles are placed in a muffle furnace and calcined at 500° C. for 4 to 6 hours; after cooling, the calcined product is ultrasonically dispersed in anhydrous toluene at a dosage ratio of 0.01 to 0.02 g / mL for 20 to 30 minutes to obtain a dispersed solution; The dispersed solution and γ-methacryloxypropyltrimethoxysilane are mixed in a mass ratio of 0.15 to 0.2:1, and the temperature is raised to 78 to 80°C under nitrogen protection, and magnetic stirring is performed for 10 to 12 hours. The mixture is cooled to room temperature, and the modified nanoparticles are separated by centrifugation. The modified nanoparticles are washed with anhydrous toluene and ethanol for 2 to 3 times, respectively, and vacuum dried to obtain modified mesoporous silica nanoparticles.
[0010] The present invention is further configured such that the added mass of the hydrofluoric acid solution is 5 to 10 times the mass of the precipitate.
[0011] The present invention is further configured as follows: the monomer solution is prepared by compounding γ-methacryloxypropyltrimethoxysilane and ethanol in a volume ratio of 1:3 to 5, and the added amount of ZIF-8 is 20 to 25% of the mass of the monomer solution.
[0012] The present invention is further configured as follows: the preparation process of the vinyl ether monomer is as follows: Vinyl acrylate and 1,4-dioxane are stirred and mixed in a volume ratio of 1.41 to 1.45:1 under a nitrogen atmosphere, and then sodium glycerophosphate is added thereto at a volume ratio of 72 to 74% by weight of vinyl acrylate to obtain a preformulation; then, antarctic Candida lipase B is added at a volume ratio of 4.5 to 5% by weight of the preformulation, and the mixture is treated at a constant temperature of 35° C. for 10 to 12 hours, the Antarctic Candida lipase B is separated by centrifugation, and 1,4-dioxane is removed by distillation under reduced pressure to obtain a first precursor; The first precursor is placed in dichloromethane at a mass ratio of 0.6 to 0.8:1, and then 25 to 28% of the mass of the first precursor and 42 to 45% of potassium carbonate are added thereto. The mixture is stirred at room temperature for 8 to 10 hours. After the mixture is completed, the mixture is filtered, and the filtrate is washed with distilled water 2 to 3 times and distilled under reduced pressure to obtain a second precursor. The second precursor, ethyl vinyl ether, copper sulfate pentahydrate, sodium ascorbate and dichloromethane are stirred at room temperature for 20 to 24 hours under nitrogen protection in a mass ratio of 1:0.021 to 0.024:0.005 to 0.008:0.012 to 0.14:0.042 to 0.046. After the reaction is completed, the mixture is separated by silica gel column chromatography, wherein the eluent is a mixture of n-hexane and ethyl acetate in a volume ratio of 3:1, to obtain a vinyl ether monomer.
[0013] The present invention is further configured such that the adhesion promoter is selected from any one of silane coupling agent KH-550 and silane coupling agent KH-560.
[0014] The second aspect of the present invention is to provide a method for preparing the high-solid content quick-drying ink resin, comprising the following steps: Step 1: Accurately weigh polyester monomer, MOF-silicon-containing acrylate composite monomer, vinyl ether monomer, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, thermal initiator, photoinitiator, leveling agent, defoaming agent and adhesion promoter, and add polyester monomer, MOF-silicon-containing acrylate composite monomer and vinyl ether monomer into a reactor, and stir at a constant temperature of 50° C. for 20 to 30 minutes; Step 2: After stirring is completed, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate are added in sequence at intervals of 8 to 10 minutes, and then the temperature is lowered to 35 to 38°C, and a thermal initiator, a photoinitiator, a leveling agent, a defoaming agent and an adhesion promoter are added, and stirring is continued for 50 to 60 minutes; Step three: filter through a 100-mesh filter, then degas for 25 to 30 minutes at a vacuum degree of -0.092 MPa, and then undergo quality inspection and filling to obtain a high-solid content quick-drying ink resin product.
[0015] Compared with the prior art, the present invention has the following beneficial effects: In the present invention, polyester monomer, MOF-silicon-containing acrylate composite monomer, vinyl ether monomer, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, etc. are used as raw materials. The polyester monomer, MOF-silicon-containing acrylate composite monomer, and vinyl ether monomer are added to a reactor and stirred at a constant temperature. Then, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate are added in sequence and at intervals. After cooling, a thermal initiator, a photoinitiator, a leveling agent, a defoaming agent, and an adhesion promoter are added. The mixture is stirred continuously, filtered, and vacuum degassed to prepare a high-solid content fast-drying ink resin product. The prepared high-solid content fast-drying ink resin not only has good high solid content and fixing speed performance, but also has excellent adhesion and weather resistance, effectively ensuring its quality. The high-solid content fast-drying ink resin and its preparation method provided by the present invention have a broader market prospect and are more suitable for promotion. DETAILED DESCRIPTION
[0016] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.
[0017] Example 1 This embodiment provides a high-solid content, quick-drying ink resin, which is composed of the following raw materials in parts by weight: 30 parts of polyester monomer, 15 parts of MOF-silicon-containing acrylate composite monomer, 12 parts of vinyl ether monomer, 8 parts of trimethylolpropane triacrylate, 6 parts of ethoxylated trimethylolpropane triacrylate, 2 parts of thermal initiator, 2 parts of photoinitiator, 0.3 parts of leveling agent, 0.3 parts of defoaming agent and 1 part of adhesion promoter.
[0018] In this embodiment, it should be noted that the thermal initiator is benzoyl peroxide (BPO), the photoinitiator is photoinitiator 184, the leveling agent is leveling agent BYK-333, and the defoaming agent is defoaming agent BYK-066N.
[0019] The adhesion promoter is silane coupling agent KH-550.
[0020] The polyester monomer is a hyperbranched polyester macromonomer.
[0021] The preparation process of polyester monomer is as follows: The composite and anhydrous dimethyl sulfoxide were magnetically stirred at a volume ratio of 1:3 for 20 minutes; CALB enzyme powder (8% by weight of the composite) was added thereto, and stirring was continued for 4 minutes to obtain a pre-formulated solution; modified mesoporous silica nanoparticles were added to the obtained pre-formulated solution, ultrasonically dispersed for 20 minutes, and then placed in a constant temperature oscillating water bath at 50°C for 42 hours; after completion, ethanol was immediately added to the reaction system to terminate the enzyme-catalyzed reaction, and the reaction mixture was centrifuged to collect the precipitate; a 5.1% mass fraction hydrofluoric acid solution was added to the precipitate, treated at room temperature for 100 minutes, and then dialyzed in deionized water using a dialysis membrane with a molecular weight cutoff of 3500 Da. After dialysis, the solution in the dialysis bag was vacuum freeze-dried to prepare a polyester monomer.
[0022] Furthermore, the composite material is prepared by compounding pentaerythritol tetraacrylate and dimer acid in a molar ratio of 1:3.
[0023] The amount of modified mesoporous silica nanoparticles added is 10% of the mass of the pre-mixed solution; the preparation process of modified mesoporous silica nanoparticles is as follows: Mesoporous silica nanoparticles were placed in a muffle furnace and calcined at 500°C for 4 hours. After cooling, the calcined product was ultrasonically dispersed in anhydrous toluene at a dosage ratio of 0.01 g / mL for 20 minutes to obtain a dispersed solution. The dispersed solution and γ-methacryloxypropyltrimethoxysilane were mixed at a mass ratio of 0.15:1, and the temperature was raised to 78°C under nitrogen protection and magnetically stirred for 10 hours. The modified nanoparticles were cooled to room temperature and separated by centrifugation. The modified nanoparticles were washed twice with anhydrous toluene and ethanol respectively, and vacuum dried to obtain modified mesoporous silica nanoparticles.
[0024] Furthermore, the added mass of the hydrofluoric acid solution is 5 times the mass of the precipitate.
[0025] In this embodiment, it should be noted that the mesoporous silica nanoparticles were purchased from Suzhou Beike Nanotechnology Co., Ltd.
[0026] The preparation process of MOF-silicon-containing acrylate composite monomer is as follows: The ZIF-8 is placed in a monomer solution and ultrasonically dispersed; the obtained dispersion is centrifuged, and the precipitate is collected, washed with anhydrous ethanol, and vacuum dried to prepare a MOF-silicon-containing acrylate composite monomer.
[0027] The monomer solution is prepared by compounding γ-methacryloxypropyltrimethoxysilane and ethanol in a volume ratio of 1:3, and the added amount of ZIF-8 is 20% of the mass of the monomer solution.
[0028] In this embodiment, it should be noted that ZIF-8 was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
[0029] The preparation process of vinyl ether monomer is as follows: Vinyl acrylate and 1,4-dioxane were stirred and mixed in a nitrogen atmosphere at a volume ratio of 1.41:1, and then sodium glycerophosphate (72% by weight of vinyl acrylate) was added thereto to obtain a preformulation; then, antarctic Candida lipase B (4.5% by weight of the preformulation) was added, and the mixture was treated at a constant temperature of 35°C for 10 hours. Antarctic Candida lipase B was separated by centrifugation, and 1,4-dioxane was removed by vacuum distillation to obtain a first precursor; the first precursor was placed in dichloromethane at a mass ratio of 0.6:1, and then 25% by weight of the first precursor was added thereto. propargyl bromide and 42% potassium carbonate were stirred at room temperature for 8 hours. After the reaction, the mixture was filtered, and the filtrate was washed twice with distilled water and distilled under reduced pressure to obtain a second precursor. The second precursor, ethyl vinyl ether, copper sulfate pentahydrate, sodium ascorbate and dichloromethane were added in a mass ratio of 1:0.021:0.005:0.012:0.042 under nitrogen protection and stirred at room temperature for 20 hours. After the reaction was completed, the mixture was separated by silica gel column chromatography, wherein the eluent was a mixture of n-hexane and ethyl acetate in a volume ratio of 3:1, to obtain a vinyl ether monomer.
[0030] In addition, this embodiment also provides a method for preparing the high-solid content quick-drying ink resin, comprising the following steps: Step 1: Accurately weigh polyester monomer, MOF-silicon-containing acrylate composite monomer, vinyl ether monomer, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, thermal initiator, photoinitiator, leveling agent, defoamer and adhesion promoter, and add polyester monomer, MOF-silicon-containing acrylate composite monomer and vinyl ether monomer into the reactor, and stir at a constant temperature of 50°C for 20 minutes; Step 2: After stirring, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate are added in sequence at intervals of 8 minutes, and then the temperature is lowered to 35°C, and a thermal initiator, a photoinitiator, a leveling agent, a defoaming agent and an adhesion promoter are added, and stirring is continued for 50 to 60 minutes; Step three: filter through a 100-mesh filter, then degas for 250 minutes at a vacuum degree of -0.092 MPa, and then undergo quality inspection and filling to obtain a high-solid content fast-drying ink resin product. Example 2
[0031] The preparation method of the high-solid content quick-drying ink resin provided in this embodiment is basically the same as that of Example 1, except that the specific raw material composition and specific preparation method of the high-solid content quick-drying ink resin in this embodiment are different; the specific raw material composition and specific preparation method of the high-solid content quick-drying ink resin in this embodiment are as follows: A high-solid content, quick-drying ink resin is composed of the following raw materials in parts by weight: 32 parts of polyester monomer, 17 parts of MOF-silicon-containing acrylate composite monomer, 13 parts of vinyl ether monomer, 9 parts of trimethylolpropane triacrylate, 8 parts of ethoxylated trimethylolpropane triacrylate, 3 parts of thermal initiator, 3 parts of photoinitiator, 0.5 parts of leveling agent, 0.4 parts of defoaming agent and 2 parts of adhesion promoter.
[0032] In this embodiment, it should be noted that the thermal initiator is benzoyl peroxide (BPO), the photoinitiator is photoinitiator 184, the leveling agent is leveling agent BYK-333, and the defoaming agent is defoaming agent BYK-066N.
[0033] The adhesion promoter is silane coupling agent KH-560.
[0034] The polyester monomer is a hyperbranched polyester macromonomer.
[0035] The preparation process of polyester monomer is as follows: The composite and anhydrous dimethyl sulfoxide were magnetically stirred at a volume ratio of 1:4 for 25 minutes; CALB enzyme powder (9% by weight of the composite) was added thereto, and stirring was continued for 5 minutes to obtain a pre-formulated solution; modified mesoporous silica nanoparticles were added to the obtained pre-formulated solution, ultrasonically dispersed for 25 minutes, and then placed in a constant temperature oscillating water bath at 50°C for 43 hours; after completion, ethanol was immediately added to the reaction system to terminate the enzyme-catalyzed reaction, and the reaction mixture was centrifuged to collect the precipitate; a 5.2% by mass hydrofluoric acid solution was added to the precipitate, treated at room temperature for 115 minutes, and then dialyzed in deionized water using a dialysis membrane with a molecular weight cutoff of 4000 Da. After dialysis, the solution in the dialysis bag was vacuum freeze-dried to prepare a polyester monomer.
[0036] Furthermore, the composite material is prepared by compounding pentaerythritol tetraacrylate and dimer acid in a molar ratio of 1:3.
[0037] The amount of modified mesoporous silica nanoparticles added is 11% of the mass of the pre-mixed solution; the preparation process of modified mesoporous silica nanoparticles is as follows: Mesoporous silica nanoparticles were placed in a muffle furnace and calcined at 500°C for 5 hours. After cooling, the calcined product was ultrasonically dispersed in anhydrous toluene at a dosage ratio of 0.02 g / mL for 25 minutes to obtain a dispersed solution. The dispersed solution and γ-methacryloxypropyltrimethoxysilane were mixed at a mass ratio of 0.17:1, and under nitrogen protection, the temperature was raised to 79°C and magnetically stirred for 11 hours. The modified nanoparticles were cooled to room temperature and separated by centrifugation. The modified nanoparticles were washed twice with anhydrous toluene and ethanol respectively, and vacuum dried to obtain modified mesoporous silica nanoparticles.
[0038] Furthermore, the added mass of the hydrofluoric acid solution is 7 times the mass of the precipitate.
[0039] In this embodiment, it should be noted that the mesoporous silica nanoparticles were purchased from Suzhou Beike Nanotechnology Co., Ltd.
[0040] The preparation process of MOF-silicon-containing acrylate composite monomer is as follows: The ZIF-8 is placed in a monomer solution and ultrasonically dispersed; the obtained dispersion is centrifuged, and the precipitate is collected, washed with anhydrous ethanol, and vacuum dried to prepare a MOF-silicon-containing acrylate composite monomer.
[0041] The monomer solution is prepared by compounding γ-methacryloxypropyltrimethoxysilane and ethanol in a volume ratio of 1:4, and the added amount of ZIF-8 is 22% of the mass of the monomer solution.
[0042] In this embodiment, it should be noted that ZIF-8 was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
[0043] The preparation process of vinyl ether monomer is as follows: Vinyl acrylate and 1,4-dioxane were stirred and mixed in a nitrogen atmosphere at a volume ratio of 1.43:1, and then sodium glycerophosphate (73% by weight of vinyl acrylate) was added thereto to obtain a preformulation; then, antarctic Candida lipase B (4.7% by weight of the preformulation) was added, and the mixture was treated at a constant temperature of 35°C for 11 hours, and the Antarctic Candida lipase B was separated by centrifugation, and 1,4-dioxane was removed by vacuum distillation to obtain a first precursor; the first precursor was placed in dichloromethane at a mass ratio of 0.7:1, and then 26% by weight of the first precursor was added thereto. propargyl bromide and 43% potassium carbonate were stirred at room temperature for 9 hours. After the reaction, the mixture was filtered, and the filtrate was washed with distilled water three times and distilled under reduced pressure to obtain a second precursor. The second precursor, ethyl vinyl ether, copper sulfate pentahydrate, sodium ascorbate and dichloromethane were added in a mass ratio of 1:0.022:0.006:0.013:0.044 under nitrogen protection and stirred at room temperature for 22 hours. After the reaction was completed, the mixture was separated by silica gel column chromatography, wherein the eluent was a mixture of n-hexane and ethyl acetate in a volume ratio of 3:1, to obtain a vinyl ether monomer.
[0044] In addition, this embodiment also provides a method for preparing the high-solid content quick-drying ink resin, comprising the following steps: Step 1: Accurately weigh polyester monomer, MOF-silicon-containing acrylate composite monomer, vinyl ether monomer, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, thermal initiator, photoinitiator, leveling agent, defoamer and adhesion promoter, and add polyester monomer, MOF-silicon-containing acrylate composite monomer and vinyl ether monomer into the reactor, and stir at a constant temperature of 50° C. for 25 minutes; Step 2: After stirring, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate were added in sequence at intervals of 9 minutes, and then the temperature was lowered to 37°C, and a thermal initiator, a photoinitiator, a leveling agent, a defoaming agent and an adhesion promoter were added, and stirring was continued for 50 to 60 minutes; Step three: filter through a 100-mesh filter, then degas for 27 minutes at a vacuum degree of -0.092 MPa, and then undergo quality inspection and filling to obtain a high-solid content fast-drying ink resin product.
[0045] Example 3
[0046] The preparation method of the high-solid content quick-drying ink resin provided in this embodiment is basically the same as that of Example 1, except that the specific raw material composition and specific preparation method of the high-solid content quick-drying ink resin in this embodiment are different; the specific raw material composition and specific preparation method of the high-solid content quick-drying ink resin in this embodiment are as follows: A high-solid content, fast-drying ink resin is composed of the following raw materials in parts by weight: 35 parts of polyester monomer, 20 parts of MOF-silicon-containing acrylate composite monomer, 15 parts of vinyl ether monomer, 10 parts of trimethylolpropane triacrylate, 10 parts of ethoxylated trimethylolpropane triacrylate, 4 parts of thermal initiator, 4 parts of photoinitiator, 0.6 parts of leveling agent, 0.5 parts of defoaming agent and 2 parts of adhesion promoter.
[0047] In this embodiment, it should be noted that the thermal initiator is benzoyl peroxide (BPO), the photoinitiator is photoinitiator 184, the leveling agent is leveling agent BYK-333, and the defoaming agent is defoaming agent BYK-066N.
[0048] The adhesion promoter is silane coupling agent KH-550.
[0049] The polyester monomer is a hyperbranched polyester macromonomer.
[0050] The preparation process of polyester monomer is as follows: The composite material and anhydrous dimethyl sulfoxide were magnetically stirred at a volume ratio of 1:4 for 30 minutes; CALB enzyme powder (10% by weight of the composite material) was added thereto, and stirring was continued for 7 minutes to obtain a pre-formulated solution; modified mesoporous silica nanoparticles were added to the obtained pre-formulated solution, ultrasonically dispersed for 30 minutes, and then placed in a constant temperature oscillating water bath at 50°C for 44 hours; after completion, ethanol was immediately added to the reaction system to terminate the enzyme catalytic reaction, and the reaction mixture was centrifuged to collect the precipitate; a hydrofluoric acid solution with a mass fraction of 5.4% was added to the precipitate, and the mixture was treated at room temperature for 130 minutes, and then dialyzed in deionized water using a dialysis membrane with a molecular weight cutoff of 4500Da. After the dialysis, the solution in the dialysis bag was vacuum freeze-dried to prepare a polyester monomer.
[0051] Furthermore, the composite material is prepared by compounding pentaerythritol tetraacrylate and dimer acid in a molar ratio of 1:3.
[0052] The amount of modified mesoporous silica nanoparticles added is 11% of the mass of the pre-mixed solution; the preparation process of modified mesoporous silica nanoparticles is as follows: Mesoporous silica nanoparticles were placed in a muffle furnace and calcined at 500°C for 6 hours. After cooling, the calcined product was ultrasonically dispersed in anhydrous toluene at a dosage ratio of 0.02 g / mL for 30 minutes to obtain a dispersed solution. The dispersed solution and γ-methacryloxypropyltrimethoxysilane were mixed at a mass ratio of 0.2:1, and the temperature was raised to 80°C under nitrogen protection, and magnetically stirred for 12 hours. The modified nanoparticles were cooled to room temperature, centrifuged, and washed with anhydrous toluene and ethanol for 2 to 3 times respectively. After vacuum drying, modified mesoporous silica nanoparticles were obtained.
[0053] Furthermore, the added mass of the hydrofluoric acid solution is 10 times the mass of the precipitate.
[0054] In this embodiment, it should be noted that the mesoporous silica nanoparticles were purchased from Suzhou Beike Nanotechnology Co., Ltd.
[0055] The preparation process of MOF-silicon-containing acrylate composite monomer is as follows: The ZIF-8 is placed in a monomer solution and ultrasonically dispersed; the obtained dispersion is centrifuged, and the precipitate is collected, washed with anhydrous ethanol, and vacuum dried to prepare a MOF-silicon-containing acrylate composite monomer.
[0056] The monomer solution is prepared by compounding γ-methacryloxypropyltrimethoxysilane and ethanol in a volume ratio of 1:5, and the added amount of ZIF-8 is 25% of the mass of the monomer solution.
[0057] In this embodiment, it should be noted that ZIF-8 was purchased from Xi'an Qiyue Biotechnology Co., Ltd.
[0058] The preparation process of vinyl ether monomer is as follows: Vinyl acrylate and 1,4-dioxane were stirred and mixed in a nitrogen atmosphere at a volume ratio of 1.45:1, and then sodium glycerophosphate (74% by weight of vinyl acrylate) was added thereto to obtain a preformulation; then 5% by weight of the preformulation of Candida antarctica lipase B was added, and the mixture was treated at a constant temperature of 35°C for 12 hours, and Candida antarctica lipase B was centrifuged and filtered out, and 1,4-dioxane was removed by vacuum distillation to obtain a first precursor; the first precursor was placed in dichloromethane at a mass ratio of 0.8:1, and then 28% by weight of the first precursor was added thereto. Propargyl bromide and 45% potassium carbonate are stirred at room temperature for 10 hours. After the reaction, the mixture is filtered, and the filtrate is washed three times with distilled water and distilled under reduced pressure to obtain a second precursor. The second precursor, ethyl vinyl ether, copper sulfate pentahydrate, sodium ascorbate and dichloromethane are added in a mass ratio of 1:0.024:0.008:0.14:0.046 under nitrogen protection and stirred at room temperature for 24 hours. After the reaction is completed, the mixture is separated by silica gel column chromatography, wherein the eluent is a mixture of n-hexane and ethyl acetate in a volume ratio of 3:1, to obtain a vinyl ether monomer.
[0059] In addition, this embodiment also provides a method for preparing the high-solid content quick-drying ink resin, comprising the following steps: Step 1: Accurately weigh polyester monomer, MOF-silicon-containing acrylate composite monomer, vinyl ether monomer, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, thermal initiator, photoinitiator, leveling agent, defoamer and adhesion promoter, and add polyester monomer, MOF-silicon-containing acrylate composite monomer and vinyl ether monomer into the reactor, and stir at a constant temperature of 50° C. for 30 minutes; Step 2: After stirring, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate were added in sequence at intervals of 10 minutes, and then the temperature was lowered to 38°C, and a thermal initiator, a photoinitiator, a leveling agent, a defoaming agent and an adhesion promoter were added, and stirring was continued for 60 minutes; Step three: filter through a 100-mesh filter, then degas for 30 minutes at a vacuum degree of -0.092 MPa, and then undergo quality inspection and filling to obtain a high-solid content fast-drying ink resin product.
[0060] Comparative Example 1: The difference from Example 1 is that this example does not contain polyester monomer.
[0061] Comparative Example 2: The difference from Example 1 is that in this example, the modified mesoporous silica nanoparticles are replaced by an equal amount of mesoporous silica nanoparticles.
[0062] Comparative Example 3: The difference from Example 1 is that this example does not contain MOF-silicon-containing acrylate composite monomer.
[0063] Comparative Example 4: The difference from Example 1 is that this example does not contain vinyl ether monomer.
[0064] Performance test: The high-solid content, fast-drying ink resin samples provided in Examples 1 to 3 and Comparative Examples 1 to 4 were marked as Examples 1 to 3 and Comparative Examples 1 to 4, respectively; and the relevant properties of the high-solid content, fast-drying ink resin provided in Examples 1 to 3 and Comparative Examples 1 to 4 were tested as follows: 1. Curing speed test: The test method is GB / T 1728-2020, 80mW / cm² UV light + 80℃ heat assisted curing, the surface dry time is no mark under finger pressure.
[0065] 2. Solid content test: The test method is GB / T 1725-2007, 105℃ oven, drying for 3 hours.
[0066] 3. Viscosity test: The test method is GB / T 2794-2013.
[0067] 4. Adhesion test: The test method is GB / T 9286-2021, and the substrate is tinplate.
[0068] 5. Weathering test: The test method is QUV aging test (340nm UV lamp, irradiance 0.71W / m 2 , temperature 60℃, condensation period 4h), and measure the color difference ΔE after 500h.
[0069] The obtained test data are recorded in Tables 1 to 5 below: Table 1 Test results of curing speed of each group of ink resin
[0070] Group Surface drying time (s) Example 1 group 24 Example 2 group 25 Example 3 group 22 Comparison group 1 37 Comparison of 2 groups 30 Comparison of 3 groups 28 Comparison of 4 groups 44 Table 2 Test results of solid content of each group of ink resin
[0071] Group Solid content (%) Example 1 group 83.2 Example 2 group 83.6 Example 3 group 84.1 Comparison group 1 80.2 Comparison of 2 groups 81.7 Comparison of 3 groups 82.1 Comparison of 4 groups 83.0 Table 3 Viscosity test results of each group of ink resins
[0072] Group Viscosity (mPa·s, 25°C) Example 1 group 1300 Example 2 group 1315 Example 3 group 1321 Comparison group 1 1295 Comparison of 2 groups 1290 Comparison of 3 groups 1260 Comparison of 4 groups 1216 Table 4 Adhesion test results of each group of ink resins
[0073] Group Adhesion (grade) Example 1 group 0 Example 2 group 0 Example 3 group 0 Comparison group 1 1 Comparison of 2 groups 1 Comparison of 3 groups 2 Comparison of 4 groups 0 Table 5 Weathering test results of each group of ink resins
[0074] Group QUVΔE Example 1 group 1.8 Example 2 group 1.9 Example 3 group 2.0 Comparison group 1 3.7 Comparison of 2 groups 2.8 Comparison of 3 groups 3.2 Comparison of 4 groups 2.3 Comparison and analysis of the relevant data in Tables 1 to 5 demonstrate that the high-solids, fast-drying ink resin prepared by the present invention not only exhibits excellent high solids content and fast setting performance, but also possesses superior adhesion and weather resistance, effectively guaranteeing its quality. This demonstrates that the high-solids, fast-drying ink resin and its preparation method provided by the present invention have broader market prospects and are more suitable for promotion.
[0075] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
[0076] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.
Claims
1. A high solid content quick-drying ink resin, characterized in that: The invention is composed of the following raw materials in parts by weight: 30 to 35 parts of polyester monomer, 15 to 20 parts of MOF-silicon-containing acrylate composite monomer, 12 to 15 parts of vinyl ether monomer, 8 to 10 parts of trimethylolpropane triacrylate, 6 to 10 parts of ethoxylated trimethylolpropane triacrylate, 2 to 4 parts of thermal initiator, 2 to 4 parts of photoinitiator, 0.3 to 0.6 parts of leveling agent, 0.3 to 0.5 parts of defoaming agent and 1 to 2 parts of adhesion promoter; The polyester monomer is a hyperbranched polyester macromonomer; The preparation process of the MOF-silicon-containing acrylate composite monomer is as follows: The ZIF-8 was placed in the monomer solution and ultrasonically dispersed; The obtained dispersion was centrifuged, and the precipitate was collected, washed with anhydrous ethanol, and then vacuum-dried to prepare a MOF-silicon-containing acrylate composite monomer.
2. The high-solid content quick-drying ink resin according to claim 1, characterized in that: The preparation process of the polyester monomer is as follows: The composite material and anhydrous dimethyl sulfoxide are magnetically stirred at a volume ratio of 1:3-4 for 20-30 minutes; 8-10% of the mass of the composite material in the amount of CALB enzyme powder is added thereto, and stirring is continued for 4-7 minutes to obtain a pre-mixed solution; Add modified mesoporous silica nanoparticles to the obtained pre-formulated solution, perform ultrasonic dispersion treatment for 20 to 30 minutes, and then place in a constant temperature oscillating water bath at 50° C. for 42 to 44 hours; After the reaction is complete, ethanol is immediately added to the reaction system to terminate the enzyme-catalyzed reaction, and the reaction mixture is centrifuged to collect the precipitate; A hydrofluoric acid solution with a mass fraction of 5.1 to 5.4% is added to the precipitate, and the precipitate is treated at room temperature for 100 to 130 minutes. The precipitate is then dialyzed in deionized water using a dialysis membrane with a molecular weight cutoff of 3500 to 4500 Da. After the dialysis, the solution in the dialysis bag is vacuum freeze-dried to prepare a polyester monomer.
3. The high-solid content quick-drying ink resin according to claim 2, characterized in that: The composite material is prepared by compounding pentaerythritol tetraacrylate and dimer acid in a molar ratio of 1:
3.
4. The high-solid content quick-drying ink resin according to claim 2, characterized in that: The amount of the modified mesoporous silica nanoparticles added is 10-11% of the mass of the pre-mixed solution; the preparation process of the modified mesoporous silica nanoparticles is as follows: The mesoporous silica nanoparticles are placed in a muffle furnace and calcined at 500° C. for 4 to 6 hours; after cooling, the calcined product is ultrasonically dispersed in anhydrous toluene at a dosage ratio of 0.01 to 0.02 g / mL for 20 to 30 minutes to obtain a dispersed solution; The dispersed solution and γ-methacryloxypropyltrimethoxysilane are mixed in a mass ratio of 0.15 to 0.2:1, and the temperature is raised to 78 to 80°C under nitrogen protection, and magnetic stirring is performed for 10 to 12 hours. The mixture is cooled to room temperature, and the modified nanoparticles are separated by centrifugation. The modified nanoparticles are washed with anhydrous toluene and ethanol for 2 to 3 times, respectively, and vacuum dried to obtain modified mesoporous silica nanoparticles.
5. The high-solid content quick-drying ink resin according to claim 2, characterized in that: The added mass of the hydrofluoric acid solution is 5 to 10 times the mass of the precipitate.
6. The high-solid content quick-drying ink resin according to claim 1, characterized in that: The monomer solution is prepared by compounding gamma-methacryloxypropyltrimethoxysilane and ethanol in a volume ratio of 1:3-5, and the added amount of ZIF-8 is 20-25% of the mass of the monomer solution.
7. The high-solid content quick-drying ink resin according to claim 1, characterized in that: The preparation process of the vinyl ether monomer is as follows: Vinyl acrylate and 1,4-dioxane are stirred and mixed in a volume ratio of 1.41 to 1.45:1 under a nitrogen atmosphere, and then sodium glycerophosphate is added thereto at a volume ratio of 72 to 74% by weight of vinyl acrylate to obtain a preformulation; then, antarctic Candida lipase B is added at a volume ratio of 4.5 to 5% by weight of the preformulation, and the mixture is treated at a constant temperature of 35° C. for 10 to 12 hours, the Antarctic Candida lipase B is separated by centrifugation, and 1,4-dioxane is removed by distillation under reduced pressure to obtain a first precursor; The first precursor is placed in dichloromethane at a mass ratio of 0.6 to 0.8:1, and then 25 to 28% of the mass of the first precursor and 42 to 45% of potassium carbonate are added thereto. The mixture is stirred at room temperature for 8 to 10 hours. After the mixture is completed, the mixture is filtered, and the filtrate is washed with distilled water 2 to 3 times and distilled under reduced pressure to obtain a second precursor. The second precursor, ethyl vinyl ether, copper sulfate pentahydrate, sodium ascorbate and dichloromethane are stirred at room temperature for 20 to 24 hours under nitrogen protection in a mass ratio of 1:0.021 to 0.024:0.005 to 0.008:0.012 to 0.14:0.042 to 0.
046. After the reaction is completed, the mixture is separated by silica gel column chromatography, wherein the eluent is a mixture of n-hexane and ethyl acetate in a volume ratio of 3:1, to obtain a vinyl ether monomer.
8. The high-solid content quick-drying ink resin according to claim 1, characterized in that: The adhesion promoter is selected from any one of silane coupling agent KH-550 and silane coupling agent KH-560.
9. The method for preparing a high-solid content quick-drying ink resin according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1: Accurately weigh polyester monomer, MOF-silicon-containing acrylate composite monomer, vinyl ether monomer, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, thermal initiator, photoinitiator, leveling agent, defoaming agent and adhesion promoter, and add polyester monomer, MOF-silicon-containing acrylate composite monomer and vinyl ether monomer into a reactor, and stir at a constant temperature of 50° C. for 20 to 30 minutes; Step 2: After stirring is completed, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate are added in sequence at intervals of 8 to 10 minutes, and then the temperature is lowered to 35 to 38°C, and a thermal initiator, a photoinitiator, a leveling agent, a defoaming agent and an adhesion promoter are added, and stirring is continued for 50 to 60 minutes; Step three: filter through a 100-mesh filter, then degas for 25 to 30 minutes at a vacuum degree of -0.092 MPa, and then undergo quality inspection and filling to obtain a high-solid content quick-drying ink resin product.