Environmentally friendly printing water-based ink and its preparation process

Abstract

The present invention relates to the technical field of water-based inks, and discloses an environmentally friendly printing water-based ink and its preparation process. Using polyether diol, modified monomer, isophorone diisocyanate, dimethylolpropionic acid, and hydroxyethyl acrylate as raw materials, a modified polyurethane emulsion with double bond end-capping is prepared. The modified polyurethane emulsion, butyl acrylate, methyl methacrylate, and propylene sulfonic acid are polymerized to form polyacrylate on the side chain of the polyurethane molecular chain, and a binder is obtained. The binder, pigment, filler, auxiliary agent, lubricant, dispersant, and defoamer are mixed evenly to obtain the product. The modified monomer contains an organosilicon molecular chain, so that the prepared polyurethane molecular chain has an organosilicon structure, which cooperates with the long-chain fluoroalkane on the side chain to enhance the water resistance of the water-based ink. Moreover, the cross-linked molecular chain segments contain sulfonic acid groups, and the sulfonic acid groups have strong polarity and can generate hydrogen bonds, covalent bonds, or ionic bonds with the substrate, improving the adsorption and adhesion firmness of the ink.

Description

Technical Field

[0001] The present invention relates to the technical field of water-based inks, and particularly to an environment-friendly printing water-based ink and its preparation process. Background Art

[0002] Water-based inks are mainly composed of water-based binder resins, pigments, and additives. Among them, the water-based ink binder resin is the core component of water-based inks, and its performance largely determines the performance of water-based inks. It not only plays a role in dispersing colorants but also is a key factor affecting ink performance, such as wettability, drying property, ink viscosity, leveling property, coloring fastness, adhesion fastness, water and wash resistance, and solvent resistance. There are three common types of water-based ink binders, namely water-soluble binders, diffusible binders, and alkali-soluble binders, and their performances are different. Resin binders in water-soluble binders are the most commonly used type, including natural water-soluble resins, modified natural water-soluble resins, synthetic water-soluble resins, and water-dispersed resins. Due to the excellent performance of synthetic water-soluble resins, they are widely used in water-based ink binders.

[0003] Taking water-based polyurethane resin as an example, polyurethane is the abbreviation of polyisocyanate, and water-based polyurethane resin refers to a binary colloidal system formed by dissolving or dispersing polyurethane resin in water. The ink prepared as a binder is particularly suitable for printing on plastic films, sheets, and composite films. The molecular structure of water-based polyurethane resin includes a soft segment composed of oligomeric polyols and a hard segment composed of isocyanate and small molecule chain extenders. Due to its special structure, polyurethane has excellent flexibility, wear resistance, adhesion, and chemical resistance. Water-based polyurethane is a binary colloidal resin formed by introducing hydrophilic groups into the polyurethane molecular chain to give it hydrophilicity and thus dispersing in water. Due to the introduction of hydrophilic groups, the water resistance of water-based polyurethane decreases, resulting in the water and wash resistance of the film after water-based ink printing not reaching the expected level and the service life being greatly reduced. Summary of the Invention

[0004] The purpose of the present invention is to provide an environment-friendly printing water-based ink and its preparation process to solve the problems of general adhesion and poor water and wash resistance of polyurethane resin water-based inks in the prior art.

[0005] According to the first aspect of the purpose of the present invention, a preparation process of an environment-friendly printing water-based ink is proposed, which specifically includes the following steps:

[0006] Step 1: Mix polyether diol, dibutyltin dilaurate, modified monomer, and isophorone diisocyanate for reaction, sequentially add dimethylolpropionic acid and hydroxyethyl acrylate, carry out the reaction, and then add deionized water and triethylamine, and mix evenly to obtain a double bond-terminated modified polyurethane emulsion;

[0007] Step 2: Mix and stir the double bond-capped modified polyurethane emulsion, butyl acrylate, methyl methacrylate, propylene sulfonic acid and deionized water, and add potassium persulfate to carry out the reaction to form polyacrylate on the side chain of the polyurethane molecular chain, thus obtaining the binder;

[0008] Step 3: Mix the raw materials according to the following parts by weight: 80 - 100 parts of binder, 5 - 10 parts of pigment, 10 - 20 parts of pigment filler, 0.5 - 2 parts of lubricant, 1 - 5 parts of auxiliary agent, 1 - 2 parts of dispersant and 0.1 - 0.2 parts of defoamer. After mixing the raw materials evenly and grinding and dispersing them, the environmentally friendly printing water-based ink is obtained.

[0009] In a further embodiment, in Step 1, the dosage ratio of polyether diol, modified monomer, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water and triethylamine is 20 mmol: 10 mmol: 50 mmol: 1 mmol: 9 mmol: 60 mL: 1.5 mmol.

[0010] Among them, the molecular weight of the polyether diol is 1000, and the dosage of dibutyltin dilaurate is 1% of isophorone diisocyanate.

[0011] In a further embodiment, in Step 2, the dosage ratio of polyurethane emulsion, butyl acrylate, methyl methacrylate, propylene sulfonic acid and deionized water is 100 mL: 60 mmol: 20 mmol: 15 mmol: 150 mL. The dosage of potassium persulfate is 2% of the mass of butyl acrylate.

[0012] In a further embodiment, the modified monomer is configured to be made by the following steps:

[0013] Step 1-1: Mix 4-formylphenylboronic acid, pentaerythritol and DMF evenly, and under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 80 - 100 °C, stir and add boron trichloride to carry out the reaction for 6 - 8 h to obtain Intermediate 1. Mix Intermediate 1, (3-aminopropyl)dimethyl ethoxysilane and ethanol evenly, introduce nitrogen protection, and under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 40 - 50 °C, carry out the reaction for 4 - 6 h to obtain Intermediate 2;

[0014] Step 1-2: Mix intermediate 2 and deionized water, stir for 5-10 min under the conditions of a rotation speed of 200-300 r / min and a temperature of 60-70 °C, add concentrated sulfuric acid and 1,1,3,3-tetramethyldisiloxane, react for 3-5 h, adjust the pH to neutral to obtain dihydrogen-terminated polysiloxane. Mix the dihydrogen-terminated polysiloxane and xylene evenly, stir and add chloroplatinic acid under the conditions of a rotation speed of 150-200 r / min and a temperature of 60-70 °C, react for 10-15 h, add allyl alcohol, and continue to react for 3-5 h to obtain dihydroxy polysiloxane;

[0015] Step 1-3: Mix dihydroxy polysiloxane, boron trifluoride etherate and DMF evenly, stir for 20-30 min under the conditions of a rotation speed of 150-200 r / min and a temperature of 20-25 °C, cool down to 0 °C, add 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane, stir for 10-15 h, heat up to 25-30 °C, and stir for 10-15 h to obtain the modified monomer.

[0016] In a further embodiment, in Step 1-1, the molar ratio of 4-formylphenylboronic acid to pentaerythritol is 2:1, the dosage of boron trichloride is 1-1.5% of the mass sum of 4-formylphenylboronic acid and pentaerythritol, and the molar ratio of intermediate 1 to (3-aminopropyl)dimethyl ethoxysilane is 1:2.

[0017] In a further embodiment, in Step 1-2, the dosage ratio of intermediate 2, deionized water and 1,1,3,3-tetramethyldisiloxane is 2 mmol:10 mL:1 mmol. The dosage of concentrated sulfuric acid is 1% of the mass sum of intermediate 2 and 1,1,3,3-tetramethyldisiloxane, the molar ratio of dihydrogen-terminated polysiloxane to allyl alcohol is 1:2, and the concentration of chloroplatinic acid in the mixture of allyl alcohol, dihydrogen-terminated polysiloxane and xylene is 15-20 ppm.

[0018] In a further embodiment, in Step 1-3, the dosage ratio of dihydroxy polysiloxane, boron trifluoride etherate and 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane is 1 mmol:24 μL:15 mmol.

[0019] In a further embodiment, the auxiliary agent is zinc stearate. The ultrafine powder of zinc stearate with a particle size of 1-10 μm acts as a dispersant, lubrication aid and stabilizer, helps the pigment to disperse, keeps the pigment and filler evenly dispersed, improves the brightness of the ink, prevents the filler particles from agglomerating and precipitating, adjusts the viscosity of the ink, and improves the leveling property.

[0020] In a further embodiment, the lubricant is polyethylene wax or water-based wax, which is used to improve the lubricity, abrasion resistance, scrub resistance and anti-blocking property of the ink, and to improve the brightness and glossiness.

[0021] According to the second aspect of the object of the present invention, there is also provided an environment-friendly printing water-based ink prepared according to the foregoing process, and its grinding and dispersion fineness is less than or equal to 10 μm.

[0022] With the technical solution of the present invention above, the environment-friendly printing water-based ink proposed by the present invention uses polyether diol, modified monomer, isophorone diisocyanate, dimethylolpropionic acid and hydroxyethyl acrylate as raw materials to prepare a modified polyurethane emulsion with double bond end-capping. Then, the modified polyurethane emulsion, butyl acrylate, methyl methacrylate and propylene sulfonic acid are polymerized to form polyacrylate on the side chain of the polyurethane molecular chain, and the ink binder is prepared. The binder, pigment and filler, zinc stearate (auxiliary), lubricant (polyethylene wax), dispersant and defoaming agent are mixed and ground and dispersed to obtain the water-based ink.

[0023] Compared with the prior art, the remarkable advantages of the environment-friendly printing water-based ink and its preparation process proposed by the present invention are as follows:

[0024] 1) React 4-formylphenylboronic acid with pentaerythritol. The boric acid on 4-formylphenylboronic acid reacts with the hydroxyl group on pentaerythritol to form intermediate 1 capped with dialdehyde groups. React intermediate 1 with (3-aminopropyl)dimethyl ethoxysilane. The aldehyde group on intermediate 1 reacts with the amino group of (3-aminopropyl)dimethyl ethoxysilane to obtain intermediate 2. Hydrolyze intermediate 2 and then polymerize it with 1,1,3,3-tetramethyldisiloxane to form a dihydro-terminated polysiloxane. Under the action of chloroplatinic acid, the Si-H bond on the dihydro-terminated polysiloxane reacts with the double bond on allyl alcohol to obtain a dihydroxy polysiloxane. React the dihydroxy polysiloxane with 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane, and the hydroxyl group on the dihydroxy polysiloxane reacts with the epoxy group on 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane to form a polyether structure to obtain a modified monomer. The modified monomer contains an organosilicon molecular chain, so that the prepared polyurethane molecular chain has an organosilicon structure, which cooperates with the long-chain fluoroalkane on the side chain to enhance the water resistance of the water-based ink;

[0025] 2) At the same time, the main chain contains a borate ester structure, which is a dynamic cross-linking structure, enabling the ink to achieve self-healing after being slightly rubbed, thereby increasing the service life of the ink;

[0026] 3) The polyurethane molecules and the polyacrylate molecules form a cross-linked grid structure. The cross-linked molecular segments contain sulfonic acid groups, which have strong polarity and can form hydrogen bonds, covalent bonds or ionic bonds with the substrate, enhancing the adsorption of the ink and improving the firmness and scrubbing and wear resistance of the printed film. Detailed implementation mode

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0028] Preparation process of environmentally friendly printing water-based ink

[0029] According to an embodiment of the present invention, a preparation process of an environmentally friendly printing water-based ink is provided, which specifically includes the following steps:

[0030] Step 1: Mix polyether diol, dibutyltin dilaurate, modified monomer and isophorone diisocyanate for reaction, sequentially add dimethylolpropionic acid and hydroxyethyl acrylate, carry out reaction, and then add deionized water and triethylamine, and mix evenly to obtain a modified polyurethane emulsion with double bond end-capping.

[0031] Step 2: Mix the modified polyurethane emulsion with double bond end-capping, butyl acrylate, methyl methacrylate, propylene sulfonic acid and deionized water, stir and add potassium persulfate, carry out reaction, and form polyacrylate on the side chain of the polyurethane molecular chain to obtain a binder.

[0032] Step 3: Mix the following raw materials by weight: 80-100 parts of binder, 5-10 parts of pigment, 10-20 parts of pigment filler, 0.5-2 parts of lubricant, 1-5 parts of auxiliary agent, 1-2 parts of dispersant and 0.1-0.2 parts of defoamer. After mixing the raw materials evenly and grinding and dispersing them, the grinding time is 1-6h to obtain the environmentally friendly printing water-based ink.

[0033] In a further embodiment, in Step 1, the dosage ratio of polyether diol, modified monomer, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water and triethylamine is 20 mmol: 10 mmol: 50 mmol: 1 mmol: 9 mmol: 60 mL: 1.5 mmol; the molecular weight of the polyether diol is 1000, and the dosage of dibutyltin dilaurate is 1% of isophorone diisocyanate.

[0034] In a further embodiment, in step 2, the dosage ratio of the polyurethane emulsion, butyl acrylate, methyl methacrylate, propene sulfonic acid and deionized water is 100 mL: 60 mmol: 20 mmol: 15 mmol: 150 mL, and the dosage of potassium persulfate is 2% of the mass of butyl acrylate.

[0035] In a further embodiment, the modified monomer is configured to be made by the following steps:

[0036] Step 1-1: Mix 4-formylphenylboronic acid, pentaerythritol and DMF evenly. Under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 80 - 100 °C, stir and add boron trichloride, and react for 6 - 8 h to obtain intermediate 1. Mix intermediate 1, (3-aminopropyl)dimethyl ethoxysilane and ethanol evenly, introduce nitrogen protection, and under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 40 - 50 °C, react for 4 - 6 h to obtain intermediate 2;

[0037] Step 1-2: Mix intermediate 2 and deionized water evenly. Under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 60 - 70 °C, stir for 5 - 10 min, then add concentrated sulfuric acid and 1,1,3,3-tetramethyldisiloxane, react for 3 - 5 h, and then adjust the pH to neutral to obtain dihydrogen-terminated polysiloxane. Mix dihydrogen-terminated polysiloxane and xylene evenly. Under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 60 - 70 °C, stir and add chloroplatinic acid, react for 10 - 15 h, then add allyl alcohol, and continue to react for 3 - 5 h to obtain dihydroxy polysiloxane;

[0038] Step 1-3: Mix dihydroxy polysiloxane, boron trifluoride diethyl etherate and DMF evenly. Under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 20 - 25 °C, stir for 20 - 30 min, cool down to 0 °C, add 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane, stir for 10 - 15 h, warm up to 25 - 30 °C, and stir for 10 - 15 h to obtain the modified monomer.

[0039] In a further embodiment, in step 1-1, the molar ratio of 4-formylphenylboronic acid to pentaerythritol is 2:1, the dosage of boron trichloride is 1 - 1.5% of the sum of the masses of 4-formylphenylboronic acid and pentaerythritol, and the molar ratio of intermediate 1 to (3-aminopropyl)dimethyl ethoxysilane is 1:2.

[0040] In a further embodiment, in step 1-2, the dosage ratio of intermediate 2, deionized water and 1,1,3,3-tetramethyldisiloxane is 2 mmol: 10 mL: 1 mmol, the dosage of concentrated sulfuric acid is 1% of the sum of the masses of intermediate 2 and 1,1,3,3-tetramethyldisiloxane, the molar ratio of dihydrogen-terminated polysiloxane to allyl alcohol is 1:2, and the concentration of chloroplatinic acid in the mixture of allyl alcohol, dihydrogen-terminated polysiloxane and xylene is 15-20 ppm.

[0041] In a further embodiment, in step 1-3, the dosage ratio of dihydroxypolysiloxane, boron trifluoride diethyl etherate and 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane is 1 mmol: 24 μL: 15 mmol.

[0042] In a further embodiment, the auxiliary is zinc stearate. Ultrafine zinc stearate powder with a particle size of 1-10 μm is used, which acts as a dispersant, lubrication aid and stabilizer, helps the pigment to disperse, keeps the pigment and filler evenly dispersed, improves the lightness of the ink, prevents the filler particles from agglomerating and precipitating, adjusts the viscosity of the ink, and improves the leveling property.

[0043] In a further embodiment, the lubricant is polyethylene wax or water-based wax, which is used to improve the lubricity, abrasion resistance, scrub resistance and anti-blocking property of the ink, and improve the lightness and gloss.

[0044] In a further embodiment, in the aforementioned step 3, the grinding and dispersion fineness is less than or equal to 10 μm.

[0045] Next, the preparation process of the water-based ink of the aforementioned embodiment will be further elaborated with specific examples.

[0046] Example 1

[0047] The preparation process of the environmentally friendly printing water-based ink specifically includes the following steps:

[0048] Step A1: Mix polyether diol, modified monomer, dibutyltin dilaurate and isophorone diisocyanate, and react for 3 h under the conditions of a rotation speed of 150 r / min and a temperature of 90 °C. Add dimethylolpropionic acid and react for 2 h. Add hydroxyethyl acrylate and react for 1 h. Add deionized water and cool down to 35 °C. Add triethylamine and react for 30 min to obtain a polyurethane emulsion.

[0049] Step A2: Mix the polyurethane emulsion, butyl acrylate, methyl methacrylate, acrylic acid sulfonic acid and deionized water evenly, stir and add potassium persulfate under the conditions of a rotation speed of 150 r / min and a temperature of 80 °C, and react for 2 h to obtain a binder.

[0050] Step A3: Weigh the following raw materials in parts by weight: 80 parts of binder, 10 parts of pigment, 20 parts of pigment filler, 0.5 part of polyethylene wax, 1 part of zinc stearate, 1 part of dispersant, and 0.1 part of defoamer. Mix the raw materials evenly and grind and disperse them for 2 hours to obtain an environmentally friendly water-based printing ink.

[0051] In Step A1, the dosage ratio of polyether diol, modified monomer, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water, and triethylamine is:

[0052] 20 mmol: 10 mmol: 50 mmol: 1 mmol: 9 mmol: 60 mL: 1.5 mmol.

[0053] The molecular weight of the polyether diol is 1000, and the dosage of dibutyltin dilaurate is 1% of isophorone diisocyanate.

[0054] In Step A2, the dosage ratio of polyurethane emulsion, butyl acrylate, methyl methacrylate, acrylsulfonic acid, and deionized water is 100 mL: 60 mmol: 20 mmol: 15 mmol: 150 mL, and the dosage of potassium persulfate is 2% of the mass of butyl acrylate.

[0055] In Step A3, the dispersant is BYK-190, and the defoamer is DAPRO DF7073.

[0056] The modified monomer is prepared by the following steps:

[0057] Step B1: Mix 4-formylphenylboronic acid, pentaerythritol, and DMF evenly. Under the conditions of a rotation speed of 200 r / min and a temperature of 80 °C, stir and add boron trichloride, and react for 6 hours to obtain Intermediate 1. Mix Intermediate 1, (3-aminopropyl)dimethyl ethoxysilane, and ethanol evenly, introduce nitrogen protection, and react for 4 hours under the conditions of a rotation speed of 150 r / min and a temperature of 40 °C to obtain Intermediate 2;

[0058] Step B2: Mix Intermediate 2 and deionized water, stir for 5 minutes under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 60 °C, then add concentrated sulfuric acid and 1,1,3,3-tetramethyldisiloxane, react for 3 hours, and adjust the pH to neutral to obtain dihydrogen-terminated polysiloxane. Mix the dihydrogen-terminated polysiloxane and xylene evenly, stir and add chloroplatinic acid under the conditions of a rotation speed of 150 r / min and a temperature of 60 °C, react for 10 hours, then add allyl alcohol and continue to react for 3 hours to obtain dihydroxy polysiloxane;

[0059] Step B3: Mix the dihydroxypolysiloxane, boron trifluoride ethyl ether, and DMF evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 20 °C, stir for 20 min, cool down to 0 °C, add 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane, stir for 10 h, heat up to 25 °C, and stir for 10 h to obtain the modified monomer.

[0060] In step B1, the molar ratio of 4-formylphenylboronic acid to pentaerythritol is 2:1, the dosage of boron trichloride is 1% of the mass sum of 4-formylphenylboronic acid and pentaerythritol, and the molar ratio of intermediate 1 to (3-aminopropyl)dimethyl ethoxysilane is 1:2.

[0061] In step B2, the dosage ratio of intermediate 2, deionized water, and 1,1,3,3-tetramethyldisiloxane is 2 mmol: 10 mL: 1 mmol, the dosage of concentrated sulfuric acid is 1% of the mass sum of intermediate 2 and 1,1,3,3-tetramethyldisiloxane, the molar ratio of dihydroxy-terminated polysiloxane to allyl alcohol is 1:2, and the concentration of chloroplatinic acid in the mixture of allyl alcohol, dihydroxy-terminated polysiloxane, and xylene is 15 ppm.

[0062] In step B3, the dosage ratio of dihydroxypolysiloxane, boron trifluoride ethyl ether, and 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane is 1 mmol: 24 μL: 15 mmol.

[0063] Example 2

[0064] The preparation process of the environmentally friendly printing water-based ink specifically includes the following steps:

[0065] Step A1: Mix the polyether diol, modified monomer, dibutyltin dilaurate, and isophorone diisocyanate, and carry out the reaction for 4 h under the conditions of a rotation speed of 150 r / min and a temperature of 93 °C. Add dimethylolpropionic acid and carry out the reaction for 2.5 h. Add hydroxyethyl acrylate and carry out the reaction for 1.3 h. Add deionized water and cool down to 38 °C. Add triethylamine and carry out the reaction for 35 min to obtain the polyurethane emulsion.

[0066] Step A2: Mix the polyurethane emulsion, butyl acrylate, methyl methacrylate, propene sulfonic acid, and deionized water evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 83 °C, stir and add potassium persulfate, and carry out the reaction for 2.5 h to obtain the binder.

[0067] Step A3: Weigh the following raw materials by parts by weight: 90 parts of binder, 10 parts of pigment, 20 parts of pigment filler, 0.5 part of polyethylene wax, 3 parts of zinc stearate, 1.5 parts of dispersant, and 0.15 part of defoamer. Mix the raw materials evenly, grind and disperse them. The grinding time is 2 h to obtain the environmentally friendly water-based printing ink.

[0068] In Step A1, the dosage ratio of polyether diol, modified monomer, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water, and triethylamine is 20 mmol: 10 mmol: 50 mmol: 1 mmol: 9 mmol: 60 mL: 1.5 mmol. The molecular weight of the polyether diol is 1000, and the dosage of dibutyltin dilaurate is 1% of isophorone diisocyanate.

[0069] In Step A2, the dosage ratio of polyurethane emulsion, butyl acrylate, methyl methacrylate, allylsulfonic acid, and deionized water is 100 mL: 60 mmol: 20 mmol: 15 mmol: 150 mL. The dosage of potassium persulfate is 2% of the mass of butyl acrylate.

[0070] In Step A3, the dispersant is HR-4017, and the defoamer is DAPRO DF7072.

[0071] The modified monomer is prepared by the following steps:

[0072] Step B1: Mix 4-formylphenylboronic acid, pentaerythritol, and DMF evenly. Under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 90 °C, stir and add boron trichloride, and react for 7 h to obtain Intermediate 1. Mix Intermediate 1, (3-aminopropyl)dimethyl ethoxysilane, and ethanol evenly, introduce nitrogen protection, and react under the conditions of a rotation speed of 150 r / min and a temperature of 45 °C for 5 h to obtain Intermediate 2;

[0073] Step B2: Mix Intermediate 2 and deionized water, stir at a rotation speed of 200 r / min and a temperature of 65 °C for 8 min, then add concentrated sulfuric acid and 1,1,3,3-tetramethyldisiloxane, react for 4 h, and adjust the pH to neutral to obtain dihydrogen-terminated polysiloxane. Mix the dihydrogen-terminated polysiloxane and xylene evenly, stir at a rotation speed of 150 r / min and a temperature of 65 °C, add chloroplatinic acid, react for 13 h, then add allyl alcohol, and continue to react for 4 h to obtain dihydroxy polysiloxane;

[0074] Step B3: Mix the dihydroxypolysiloxane, boron trifluoride ethyl ether, and DMF evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 20 - 25 °C, stir for 25 min, cool down to 0 °C, add 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane, stir for 13 h, heat up to 28 °C, and stir for 13 h to obtain the modified monomer.

[0075] In step B1, the molar ratio of 4-formylphenylboronic acid to pentaerythritol is 2:1, the dosage of boron trichloride is 1.5% of the sum of the masses of 4-formylphenylboronic acid and pentaerythritol, and the molar ratio of intermediate 1 to (3-aminopropyl)dimethyl ethoxysilane is 1:2.

[0076] In step B2, the dosage ratio of intermediate 2, deionized water, and 1,1,3,3-tetramethyldisiloxane is 2 mmol: 10 mL: 1 mmol, the dosage of concentrated sulfuric acid is 1% of the sum of the masses of intermediate 2 and 1,1,3,3-tetramethyldisiloxane, the molar ratio of dihydroxy-terminated polysiloxane to allyl alcohol is 1:2, and the concentration of chloroplatinic acid in the mixture of allyl alcohol, dihydroxy-terminated polysiloxane, and xylene is 18 ppm.

[0077] In step B3, the dosage ratio of dihydroxypolysiloxane, boron trifluoride ethyl ether, and 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane is 1 mmol: 24 μL: 15 mmol.

[0078] Example 3

[0079] The preparation process of the environmentally friendly printing water-based ink specifically includes the following steps:

[0080] Step A1: Mix the polyether diol, modified monomer, dibutyltin dilaurate, and isophorone diisocyanate, and react for 5 h under the conditions of a rotation speed of 200 r / min and a temperature of 95 °C. Add dimethylolpropionic acid and react for 3 h. Add hydroxyethyl acrylate and react for 1.5 h. Add deionized water and cool down to 40 °C. Add triethylamine and react for 40 min to obtain the polyurethane emulsion.

[0081] Step A2: Mix the polyurethane emulsion, butyl acrylate, methyl methacrylate, acrylsulfonic acid, and deionized water evenly, stir and add potassium persulfate under the conditions of a rotation speed of 200 r / min and a temperature of 85 °C, and react for 3 h to obtain the binder.

[0082] Step A3: Weigh the following raw materials in parts by weight: 100 parts of binder, 10 parts of pigment, 20 parts of pigment filler, 0.5 part of polyethylene wax, 5 parts of zinc stearate, 2 parts of dispersant, and 0.2 part of defoamer. Mix the raw materials evenly, grind and disperse them. The grinding time is 2 h to obtain an environmentally friendly water-based printing ink.

[0083] In Step A1, the dosage ratio of polyether diol, modified monomer, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water, and triethylamine is 20 mmol: 10 mmol: 50 mmol: 1 mmol: 9 mmol: 60 mL: 1.5 mmol. The molecular weight of the polyether diol is 1000, and the dosage of dibutyltin dilaurate is 1% of isophorone diisocyanate.

[0084] In Step A2, the dosage ratio of polyurethane emulsion, butyl acrylate, methyl methacrylate, acrylsulfonic acid, and deionized water is 100 mL: 60 mmol: 20 mmol: 15 mmol: 150 mL. The dosage of potassium persulfate is 2% of the mass of butyl acrylate.

[0085] In Step A3, the dispersant is YB-401, and the defoamer is TEGO FOAMEX 1488.

[0086] The modified monomer is prepared by the following steps:

[0087] Step B1: Mix 4-formylphenylboronic acid, pentaerythritol, and DMF evenly. Under the conditions of a rotation speed of 300 r / min and a temperature of 100 °C, stir and add boron trichloride, and react for 8 h to obtain Intermediate 1. Mix Intermediate 1, (3-aminopropyl)dimethyl ethoxysilane, and ethanol evenly, introduce nitrogen protection, and react for 6 h under the conditions of a rotation speed of 200 r / min and a temperature of 50 °C to obtain Intermediate 2;

[0088] Step B2: Mix Intermediate 2 and deionized water, stir for 10 min under the conditions of a rotation speed of 300 r / min and a temperature of 70 °C, then add concentrated sulfuric acid and 1,1,3,3-tetramethyldisiloxane, react for 5 h, and adjust the pH to neutral to obtain dihydrogen-terminated polysiloxane. Mix the dihydrogen-terminated polysiloxane and xylene evenly, stir and add chloroplatinic acid under the conditions of a rotation speed of 200 r / min and a temperature of 70 °C, react for 15 h, then add allyl alcohol and continue to react for 5 h to obtain dihydroxy polysiloxane;

[0089] Step B3: Mix the dihydroxypolysiloxane, boron trifluoride ethyl etherate, and DMF evenly. Under the conditions of a rotation speed of 200 r / min and a temperature of 25 °C, stir for 30 min, cool down to 0 °C, add 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane, stir for 15 h, heat up to 30 °C, and stir for 15 h to obtain the modified monomer.

[0090] In Step B1, the molar ratio of 4-formylphenylboronic acid to pentaerythritol is 2:1, the dosage of boron trichloride is 1.5% of the total mass of 4-formylphenylboronic acid and pentaerythritol, and the molar ratio of Intermediate 1 to (3-aminopropyl)dimethyl ethoxysilane is 1:2.

[0091] In Step B2, the dosage ratio of Intermediate 2, deionized water, and 1,1,3,3-tetramethyldisiloxane is 2 mmol: 10 mL: 1 mmol, the dosage of concentrated sulfuric acid is 1% of the total mass of Intermediate 2 and 1,1,3,3-tetramethyldisiloxane, the molar ratio of dihydrogen-terminated polysiloxane to allyl alcohol is 1:2, and the concentration of chloroplatinic acid in the mixture of allyl alcohol, dihydrogen-terminated polysiloxane, and xylene is 20 ppm.

[0092] In Step B3, the dosage ratio of dihydroxypolysiloxane, boron trifluoride ethyl etherate, and 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane is 1 mmol: 24 μL: 15 mmol.

[0093] Comparative Example 1

[0094] In this comparative example compared with Example 1, polyurethane emulsion is used instead of the binder, and the remaining steps are the same.

[0095] Comparative Example 2

[0096] In this Comparative Example 2 compared with Example 1, propene sulfonic acid is not added, and the remaining steps are the same.

[0097] Comparative Example 3

[0098] In this comparative example compared with Example 1, the modified monomer is not added, and the remaining steps are the same.

[0099] For the water-based inks prepared in Examples 1-3 and Comparative Examples 1-3, test the ink adhesion in accordance with the standard of GB / T13217.7-2009. If the adhesion ≥ 98%, it is judged as Grade 0; if the adhesion ≥ 92% and < 98%, it is judged as Grade 1; if the adhesion < 92%, it is judged as Grade 2. Fix a cotton ball dipped in deionized water to the bottom of a 500 g weight, and at a speed of 40 times / min with a friction stroke of 20 mm, record the number of wiping times. Immerse the ink strips in water for 24 h, 48 h, and 72 h respectively to observe the ink changes. The test results are shown in the following table.

[0100]

[0101] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar ways to replace them. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claims, they should all fall within the protection scope of the present invention.

Claims

1. A preparation process of an environment-friendly printing water-based ink, characterized in that It includes the following steps: Step 1: Mix polyether diol, dibutyltin dilaurate, modified monomer and isophorone diisocyanate for reaction, successively add dimethylolpropionic acid and hydroxyethyl acrylate, carry out reaction, then add deionized water and triethylamine, and mix evenly to obtain a double bond-terminated modified polyurethane emulsion; Among them, the said modified monomer is set to be made by the following steps: Step 1-1: Stir 4-formylphenylboronic acid, pentaerythritol and DMF and add boron trichloride, carry out reaction to obtain intermediate 1; Mix intermediate 1, (3-aminopropyl)dimethyl ethoxysilane and ethanol evenly, pass in nitrogen for protection, and carry out reaction to obtain intermediate 2; Step 1-2: After mixing and stirring intermediate 2 and deionized water, add concentrated sulfuric acid and 1,1,3,3-tetramethyldisiloxane, carry out reaction, and adjust the pH to neutral to obtain dihydrogen-terminated polysiloxane; Mix dihydrogen-terminated polysiloxane and xylene evenly, add chloroplatinic acid, carry out reaction, then add allyl alcohol, and continue reaction to obtain dihydroxy polysiloxane; Step 1-3: Mix and stir dihydroxy polysiloxane, boron trifluoride diethyl etherate and DMF, cool down to 0 °C, add 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane, stir, and then heat up and continue stirring to obtain the said modified monomer; Step 2: Mix and stir the double bond-terminated modified polyurethane emulsion, butyl acrylate, methyl methacrylate, propene sulfonic acid and deionized water, and add potassium persulfate, carry out reaction to form polyacrylate on the side chain of the polyurethane molecular chain to obtain a binder; Step 3: Mix according to the following parts by weight of raw materials: 80-100 parts of binder, 5-10 parts of pigment, 10-20 parts of pigment filler, 0.5-2 parts of lubricant, 1-5 parts of auxiliary agent, 1-2 parts of dispersant and 0.1-0.2 parts of defoamer. After mixing the raw materials evenly and grinding and dispersing, obtain an environmentally friendly printing water-based ink.

2. The preparation process of the environment-friendly printing water-based ink according to claim 1, characterized in that, In the said Step 1, the dosage ratio of the polyether diol, modified monomer, isophorone diisocyanate, dimethylolpropionic acid, hydroxyethyl acrylate, deionized water and triethylamine is 20 mmol: 10 mmol: 50 mmol: 1 mmol: 9 mmol: 60 mL: 1.5 mmol.

3. The preparation process of the environmentally friendly printing water-based ink according to claim 1, characterized in that In the said Step 2, the dosage ratio of the polyurethane emulsion, butyl acrylate, methyl methacrylate, propene sulfonic acid and deionized water is 100 mL: 60 mmol: 20 mmol: 15 mmol: 150 mL.

4. The preparation process of the environmentally friendly printing water-based ink according to claim 1, characterized in that, In the said Step 1-1, the molar ratio of 4-formylphenylboronic acid and pentaerythritol is 2:1; the dosage of boron trichloride is 1-1.5% of the mass sum of 4-formylphenylboronic acid and pentaerythritol; The molar ratio of intermediate 1 and (3-aminopropyl)dimethyl ethoxysilane is 1:

2.

5. The preparation process of the environmentally friendly printing water-based ink according to claim 1, characterized in that, In the said Step 1-2, the dosage ratio of intermediate 2, deionized water and 1,1,3,3-tetramethyldisiloxane is 2 mmol: 10 mL: 1 mmol; The molar ratio of dihydrogen-terminated polysiloxane and allyl alcohol is 1:

2.

6. The preparation process of the environment-friendly printing water-based ink according to claim 1, characterized in that, In the steps 1-3, the dosage ratio of the dihydroxypolysiloxane, boron trifluoride diethyl etherate and 2-(2,2,3,3,4,4,4-heptafluorobutyl)methyloxirane is 1 mmol: 24 μL: 15 mmol.

7. The preparation process of the environment-friendly printing water-based ink according to claim 1, characterized in that, The auxiliary agent is zinc stearate.

8. The preparation process of the environmentally friendly printing water-based ink according to claim 1, characterized in that, The lubricant is polyethylene wax.

9. An environmentally friendly printing water-based ink, characterized in that: It is prepared according to the preparation process described in any one of claims 1-8, and its grinding and dispersion fineness is less than or equal to 10 μm.

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