CN115746622B - High-adhesiveness water-based printing ink and preparation method thereof - Google Patents
High-adhesiveness water-based printing ink and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of printing ink, in particular to high-adhesiveness water-based printing ink and a preparation method thereof. According to the scheme, polyurethane emulsion is used as an ink binder, and organic pigment, dispersing agent, modified silicon dioxide, wetting agent, defoaming agent and other components are added to prepare the polyurethane water-based printing ink with excellent comprehensive performance. The process design of the invention is reasonable, the proportion of each component of the scheme is proper, the prepared water-based printing ink not only has excellent water resistance and higher crosslinking degree, but also still has excellent adhesion performance on the surface of the nonpolar plastic film, has high adhesion fastness and excellent comprehensive performance, and has higher practicability.
Description
Technical Field
The invention relates to the technical field of printing ink, in particular to high-adhesiveness water-based printing ink and a preparation method thereof.
Background
The water-based printing ink is prepared by physically mixing water-based polymer emulsion, organic pigment, resin, surfactant and related additives through a chemical process, and the water-based printing ink uses water as a solvent to replace a toxic organic solvent adopted in the traditional ink, is environment-friendly, pollution-free and hazard-free, and is one of the most promising ink varieties in the market at present.
At present, enterprises generally take aqueous polyurethane as an ink binder, but in the plastic film printing process, aqueous polyurethane ink is difficult to attach on the surface of a nonpolar plastic film, and in order to solve the problem, corona treatment is generally carried out on the surface of the plastic film so as to introduce oxygen-containing groups and increase polar groups on the surface of the plastic film; however, the processing step increases the process cost and has low practicability; the existing printing ink on the market cannot meet the actual demands.
Therefore, based on the situation, the application discloses a high-adhesiveness water-based printing ink and a preparation method thereof, so as to solve the technical problem.
Disclosure of Invention
The invention aims to provide high-adhesiveness water-based printing ink and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of high-adhesiveness water-based printing ink comprises the following steps:
(1) Mixing octavinyl silsesquioxane, a mercapto-containing compound and a photoinitiator, adding tetrahydrofuran, stirring until the octavinyl silsesquioxane, the mercapto-containing compound and the photoinitiator are dissolved, reacting for 10-15 min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain a polyhydroxy monomer;
(2) Mixing nano silicon dioxide, isophorone diisocyanate and anhydrous toluene, performing ultrasonic dispersion for 20-30 min in a nitrogen environment, heating to 60-65 ℃, adding dibutyltin dilaurate, continuously reacting for 2-3 h, adding polyhydroxy monomer, reacting for 2-3 h at 75-85 ℃, washing with acetone after the reaction is finished, and performing centrifugal drying to obtain modified silicon dioxide;
(3) Mixing polypropylene glycol, polyhydroxy monomer, isophorone diisocyanate and dibutyl tin dilaurate, uniformly stirring, carrying out polymerization reaction for 2-3 hours at 80-90 ℃, adding dimethylolpropionic acid, 1, 4-butanediol and 3- (2-aminoethyl) -aminopropyl trimethoxysilane, continuously carrying out reaction for 3-4 hours at 65-75 ℃, cooling to 45-50 ℃, neutralizing with triethylamine for 30-35 minutes, and adding deionized water for dispersion to obtain polyurethane emulsion with 30-40% of solid content;
mixing polyurethane emulsion, organic pigment, dispersing agent and deionized water, stirring for 20-30 min, adding modified silicon dioxide, wetting agent and defoamer, continuously stirring for 30-40 min, and grinding until the fineness is below 15 mu m to obtain the printing ink.
In a more optimized scheme, in the step (3), the content of each component of the polyurethane emulsion comprises: the adhesive comprises, by mass, 30-35 parts of polypropylene glycol, 41-43 parts of isophorone diisocyanate, 0.3-0.5 part of dibutyltin dilaurate, 3-5 parts of dimethylolpropionic acid, 2-4 parts of 1, 4-butanediol, 3-5 parts of polyhydroxy monomers and 1-3 parts of 3- (2-aminoethyl) -aminopropyl trimethoxysilane.
In a more optimized scheme, in the step (3), the content of each component of the printing ink comprises: 60-70 parts of polyurethane emulsion, 12-15 parts of organic pigment, 0.5-1 part of dispersing agent, 6-8 parts of modified silicon dioxide, 0.5-1 part of wetting agent, 0.4-0.7 part of defoamer and 50-60 parts of deionized water.
In the more optimized scheme, in the step (1), the compound containing the mercapto group is at least two of dodecyl mercaptan, 9-mercapto-1-nonanol and 3-mercapto-1, 2-propanediol; the molar ratio of the octavinyl silsesquioxane to the mercapto-containing compound is 1: (8.5-8.7); the photoinitiator is benzoin dimethyl ether, and the use level of the photoinitiator is 2-3wt% of octavinyl silsesquioxane.
More optimized scheme, when the dodecyl mercaptan, the 9-mercapto-1-nonanol and the 3-mercapto-1, 2-propanediol are compounded, the molar ratio of the dodecyl mercaptan, the 9-mercapto-1-nonanol and the 3-mercapto-1, 2-propanediol is 4:5:7.
in a more optimized scheme, in the step (1), the preparation steps of the octavinyl silsesquioxane are as follows: and (3) mixing ethyl acetate and vinyl trimethoxy silane, stirring until the mixture is dissolved, adding a mixed solution of hydrochloric acid and deionized water at 20-25 ℃, continuing to react for 4-5 d, filtering after the reaction is finished, washing with acetone, and drying in vacuum to obtain the octavinyl silsesquioxane.
In the more optimized scheme, in the step (2), the mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1: (4.6 to 4.8).
According to a more optimized scheme, the printing ink is prepared by the preparation method of the high-adhesiveness water-based printing ink.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a high-adhesiveness water-based printing ink and a preparation method thereof.
In the scheme, a polyhydroxy monomer is introduced in the polyurethane preparation process, when the polyhydroxy monomer is prepared, vinyl trimethoxy silane is used as a raw material, ethyl acetate is used as a solvent, hydrochloric acid is used as a catalyst, octavinyl silsesquioxane is prepared through hydrolysis condensation reaction, and then vinyl in octavinyl silsesquioxane and a compound containing sulfhydryl are utilized to perform click reaction so as to generate the polyhydroxy monomer; when the compound containing the sulfhydryl group is selected, the scheme can select at least two of dodecyl mercaptan, 9-sulfhydryl-1-nonanol and 3-sulfhydryl-1, 2-propanediol for compounding.
Here, it is to be explained that: at least two of dodecyl mercaptan, 9-mercapto-1-nonanol and 3-mercapto-1, 2-propanediol are selected for compounding according to the scheme, and the reason is that: on the one hand, in the scheme design, the polyhydroxy monomer needs to contain a large amount of hydroxyl groups, so that the polyhydroxy monomer can react with isocyanate during polyurethane polymerization, and the crosslinking density and cohesive strength of polyurethane are improved while the effect of a chain extender is achieved, so that the water resistance and strength of printing ink are improved; on the other hand, the proposal needs to introduce long aliphatic hydrocarbon side chains into polyurethane so as to improve the adhesion performance of the polyurethane water-based printing ink on the surface of the nonpolar plastic film.
Thus, on the basis of this concept, the scheme defines an optimally different scheme "when dodecyl mercaptan, 9-mercapto-1-nonanol, 3-mercapto-1, 2-propanediol is compounded, the molar ratio of dodecyl mercaptan, 9-mercapto-1-nonanol, 3-mercapto-1, 2-propanediol is 4:5:7", under the limiting parameters, the polyurethane water-based printing ink has the most excellent comprehensive performance.
Meanwhile, silicon dioxide is introduced into the scheme, the surface of the silicon dioxide is modified, isocyanate groups are grafted on the surface of the nano silicon dioxide during preparation, and then the isocyanate groups are utilized to react with hydroxyl groups in polyhydroxy monomers in a grafting manner, so that modified silicon dioxide is obtained, the compatibility of the surface modified silicon dioxide with polyurethane emulsion is improved, the modified silicon dioxide is more uniformly dispersed, the adhesive property, the water resistance and the solvent resistance of polyurethane water-based printing ink can be improved at the same time due to the introduction of the modified silicon dioxide, the surface wear resistance of the ink is also improved, and the product performance is more excellent.
The invention discloses a high-adhesiveness water-based printing ink and a preparation method thereof, wherein the process design is reasonable, the proportion of each component of the scheme is proper, the prepared water-based printing ink not only has excellent water resistance and higher crosslinking degree, but also still has excellent adhesiveness on the surface of a nonpolar plastic film, and the water-based printing ink has high adhesiveness, excellent comprehensive performance and high practicability.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In this example, vinyltrimethoxysilane (V162969), dodecylmercaptan (D196314), 3-mercapto-1, 2-propanediol (1-thioglycerol, T141418), 3- (2-aminoethyl) -aminopropyl trimethoxysilane (T101385) 9-mercapto-1-nonanol, benzoin dimethyl ether were all purchased from Shanghai Ala Ding Shiji; nano silicon dioxide (HTSi-01) is purchased from Nanjing Haitai nanomaterial limited, and the average particle size is 10nm; polypropylene glycol was purchased from eastern blue star eastern large chemical company, ltd, mw=2000 g/mol; isophorone diisocyanate is available from bayer, germany. The dispersant is BYK-190, the wetting agent is WE3650, and the defoamer is BYK-028.
Example 1:
a preparation method of high-adhesiveness water-based printing ink comprises the following steps:
(1) Mixing 200mL of ethyl acetate and 20mL of vinyltrimethoxysilane, stirring to dissolve, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5d, filtering after the reaction is finished, washing with acetone, and drying in vacuum to obtain octavinylsilsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of mercapto-containing compound and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the tetrahydrofuran is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain polyhydroxy monomers; the mercapto-containing compound is compounded by dodecyl mercaptan, 9-mercapto-1-nonanol and 3-mercapto-1, 2-propanediol, and the molar ratio of the dodecyl mercaptan to the 9-mercapto-1-nonanol to the 3-mercapto-1, 2-propanediol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of octavinyl silsesquioxane. The ultraviolet light wavelength is 365nm, and the light intensity is 100mW/cm 3 。
(2) Mixing 5g of nano silicon dioxide, 3mL of isophorone diisocyanate and 100mL of anhydrous toluene, performing ultrasonic dispersion for 20min in a nitrogen environment, heating to 60 ℃, adding 0.1mL of dibutyltin dilaurate, continuing to react for 3h, adding 23.5g of polyhydroxy monomer, reacting for 3h at 75 ℃, washing with acetone after the reaction is finished, and performing centrifugal drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Taking 32 parts of polypropylene glycol, 5 parts of polyhydroxy monomer, 43 parts of isophorone diisocyanate and 0.5 part of dibutyltin dilaurate by mass, mixing uniformly, carrying out polymerization reaction for 3 hours at 80 ℃, adding 3.5 parts of dimethylolpropionic acid, 2.5 parts of 1, 4-butanediol and 2 parts of 3- (2-aminoethyl) -aminopropyl trimethoxysilane, continuously carrying out reaction for 4 hours at 65 ℃, cooling to 45 ℃, neutralizing with triethylamine for 30 minutes, and adding deionized water for dispersion to obtain polyurethane emulsion with 30% of solid content;
mixing 70g of polyurethane emulsion, 15g of organic pigment, 0.5g of dispersing agent and 55g of deionized water, stirring for 20min, adding 8g of modified silicon dioxide, 0.8g of wetting agent and 0.6g of defoamer, continuously stirring for 40min, and grinding until the fineness is below 15 mu m to obtain the printing ink.
Example 2:
a preparation method of high-adhesiveness water-based printing ink comprises the following steps:
(1) Mixing 200mL of ethyl acetate and 20mL of vinyltrimethoxysilane, stirring to dissolve, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5d, filtering after the reaction is finished, washing with acetone, and drying in vacuum to obtain octavinylsilsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of mercapto-containing compound and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the tetrahydrofuran is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain polyhydroxy monomers; the mercapto-containing compound is compounded by dodecyl mercaptan, 9-mercapto-1-nonanol and 3-mercapto-1, 2-propanediol, and the molar ratio of the dodecyl mercaptan to the 9-mercapto-1-nonanol to the 3-mercapto-1, 2-propanediol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of octavinyl silsesquioxane. The ultraviolet light wavelength is 365nm, and the light intensity is 100mW/cm 3 。
(2) Mixing 5g of nano silicon dioxide, 3mL of isophorone diisocyanate and 100mL of anhydrous toluene, performing ultrasonic dispersion for 25min under a nitrogen environment, heating to 65 ℃, adding 0.1mL of dibutyltin dilaurate, continuously reacting for 2.5h, adding 23.5g of polyhydroxy monomer, reacting for 2.5h at 80 ℃, washing with acetone after the reaction is finished, and performing centrifugal drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Taking 32 parts of polypropylene glycol, 5 parts of polyhydroxy monomer, 43 parts of isophorone diisocyanate and 0.5 part of dibutyltin dilaurate by mass, mixing uniformly, carrying out polymerization reaction for 2.5 hours at 85 ℃, adding 3.5 parts of dimethylolpropionic acid, 2.5 parts of 1, 4-butanediol and 2 parts of 3- (2-aminoethyl) -aminopropyl trimethoxysilane, continuously carrying out reaction for 3.5 hours at 70 ℃, cooling to 48 ℃, neutralizing for 35 minutes with triethylamine, and adding deionized water for dispersion to obtain polyurethane emulsion with 30% of solid content;
mixing 70g of polyurethane emulsion, 15g of organic pigment, 0.5g of dispersing agent and 55g of deionized water, stirring for 25min, adding 8g of modified silicon dioxide, 0.8g of wetting agent and 0.6g of defoamer, continuously stirring for 35min, and grinding until the fineness is below 15 mu m to obtain the printing ink.
Example 3:
a preparation method of high-adhesiveness water-based printing ink comprises the following steps:
(1) Mixing 200mL of ethyl acetate and 20mL of vinyltrimethoxysilane, stirring to dissolve, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5d, filtering after the reaction is finished, washing with acetone, and drying in vacuum to obtain octavinylsilsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of mercapto-containing compound and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the tetrahydrofuran is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain polyhydroxy monomers; the mercapto-containing compound is compounded by dodecyl mercaptan, 9-mercapto-1-nonanol and 3-mercapto-1, 2-propanediol, and the molar ratio of the dodecyl mercaptan to the 9-mercapto-1-nonanol to the 3-mercapto-1, 2-propanediol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of octavinyl silsesquioxane. The ultraviolet light wavelength is 365nm, and the light intensity is 100mW/cm 3 。
(2) Mixing 5g of nano silicon dioxide, 3mL of isophorone diisocyanate and 100mL of anhydrous toluene, performing ultrasonic dispersion for 30min under a nitrogen environment, heating to 65 ℃, adding 0.1mL of dibutyltin dilaurate, continuing to react for 2h, adding 23.5g of polyhydroxy monomer, reacting for 2h at 85 ℃, washing with acetone after the reaction is finished, and performing centrifugal drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Taking 32 parts of polypropylene glycol, 5 parts of polyhydroxy monomer, 43 parts of isophorone diisocyanate and 0.5 part of dibutyltin dilaurate by mass, mixing uniformly, carrying out polymerization reaction for 2 hours at 90 ℃, adding 3.5 parts of dimethylolpropionic acid, 2.5 parts of 1, 4-butanediol and 2 parts of 3- (2-aminoethyl) -aminopropyl trimethoxysilane, continuously carrying out reaction for 3 hours at 75 ℃, cooling to 50 ℃, neutralizing for 30 minutes with triethylamine, and adding deionized water for dispersion to obtain polyurethane emulsion with 30% of solid content;
mixing 70g of polyurethane emulsion, 15g of organic pigment, 0.5g of dispersing agent and 55g of deionized water, stirring for 30min, adding 8g of modified silicon dioxide, 0.8g of wetting agent and 0.6g of defoamer, continuously stirring for 30min, and grinding until the fineness is below 15 mu m to obtain the printing ink.
Comparative example 1:
a preparation method of high-adhesiveness water-based printing ink comprises the following steps:
(1) Mixing 200mL of ethyl acetate and 20mL of vinyltrimethoxysilane, stirring to dissolve, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5d, filtering after the reaction is finished, washing with acetone, and drying in vacuum to obtain octavinylsilsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of mercapto-containing compound and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the tetrahydrofuran is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain polyhydroxy monomers; the mercapto-containing compound is compounded by 9-mercapto-1-nonanol and 3-mercapto-1, 2-propanediol, and the molar ratio of 9-mercapto-1-nonanol to 3-mercapto-1, 2-propanediol is 6:10. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of octavinyl silsesquioxane. The ultraviolet light wavelength is 365nm, and the light intensity is 100mW/cm 3 。
(2) Mixing 5g of nano silicon dioxide, 3mL of isophorone diisocyanate and 100mL of anhydrous toluene, performing ultrasonic dispersion for 25min under a nitrogen environment, heating to 65 ℃, adding 0.1mL of dibutyltin dilaurate, continuously reacting for 2.5h, adding 23.5g of polyhydroxy monomer, reacting for 2.5h at 80 ℃, washing with acetone after the reaction is finished, and performing centrifugal drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Taking 32 parts of polypropylene glycol, 5 parts of polyhydroxy monomer, 43 parts of isophorone diisocyanate and 0.5 part of dibutyltin dilaurate by mass, mixing uniformly, carrying out polymerization reaction for 2.5 hours at 85 ℃, adding 3.5 parts of dimethylolpropionic acid, 2.5 parts of 1, 4-butanediol and 2 parts of 3- (2-aminoethyl) -aminopropyl trimethoxysilane, continuously carrying out reaction for 3.5 hours at 70 ℃, cooling to 48 ℃, neutralizing for 35 minutes with triethylamine, and adding deionized water for dispersion to obtain polyurethane emulsion with 30% of solid content;
mixing 70g of polyurethane emulsion, 15g of organic pigment, 0.5g of dispersing agent and 55g of deionized water, stirring for 25min, adding 8g of modified silicon dioxide, 0.8g of wetting agent and 0.6g of defoamer, continuously stirring for 35min, and grinding until the fineness is below 15 mu m to obtain the printing ink.
Comparative example 1 based on example 2, comparative example 1 was formulated with only 9-mercapto-1-nonanol, 3-mercapto-1, 2-propanediol, and the molar ratio was 6:10, the rest process parameters are unchanged.
Comparative example 2:
a preparation method of high-adhesiveness water-based printing ink comprises the following steps:
(1) Mixing 200mL of ethyl acetate and 20mL of vinyltrimethoxysilane, stirring to dissolve, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5d, filtering after the reaction is finished, washing with acetone, and drying in vacuum to obtain octavinylsilsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of mercapto-containing compound and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the tetrahydrofuran is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain polyhydroxy monomers; the mercapto-containing compound is compounded by dodecyl mercaptan, 9-mercapto-1-nonanol and 3-mercapto-1, 2-propanediol, and the molar ratio of the dodecyl mercaptan to the 9-mercapto-1-nonanol to the 3-mercapto-1, 2-propanediol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of octavinyl silsesquioxane. The ultraviolet light wavelength is 365nm, and the light intensity is 100mW/cm 3 。
(2) Mixing 5g of nano silicon dioxide, 3mL of isophorone diisocyanate and 100mL of anhydrous toluene, performing ultrasonic dispersion for 25min under a nitrogen environment, heating to 65 ℃, adding 0.1mL of dibutyltin dilaurate, continuously reacting for 2.5h, adding 23.5g of polyhydroxy monomer, reacting for 2.5h at 80 ℃, washing with acetone after the reaction is finished, and performing centrifugal drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Taking 32 parts of polypropylene glycol, 43 parts of isophorone diisocyanate and 0.5 part of dibutyltin dilaurate by mass, mixing uniformly, carrying out polymerization reaction for 2.5 hours at 85 ℃, adding 3.5 parts of dimethylolpropionic acid, 2.5 parts of 1, 4-butanediol and 2 parts of 3- (2-aminoethyl) -aminopropyl trimethoxysilane, continuously carrying out reaction for 3.5 hours at 70 ℃, cooling to 48 ℃, neutralizing with triethylamine for 35 minutes, and adding deionized water for dispersion to obtain polyurethane emulsion with 30% of solid content;
mixing 70g of polyurethane emulsion, 15g of organic pigment, 0.5g of dispersing agent and 55g of deionized water, stirring for 25min, adding 8g of modified silicon dioxide, 0.8g of wetting agent and 0.6g of defoamer, continuously stirring for 35min, and grinding until the fineness is below 15 mu m to obtain the printing ink.
Comparative example 2 based on example 2, no polyhydroxy monomer was introduced during polyurethane preparation in comparative example 2, the remaining process parameters being unchanged.
Comparative example 3:
a preparation method of high-adhesiveness water-based printing ink comprises the following steps:
(1) Mixing 200mL of ethyl acetate and 20mL of vinyltrimethoxysilane, stirring to dissolve, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5d, filtering after the reaction is finished, washing with acetone, and drying in vacuum to obtain octavinylsilsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of mercapto-containing compound and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the tetrahydrofuran is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain polyhydroxy monomers; the mercapto-containing compound is compounded by dodecyl mercaptan, 9-mercapto-1-nonanol and 3-mercapto-1, 2-propanediol, and the molar ratio of the dodecyl mercaptan to the 9-mercapto-1-nonanol to the 3-mercapto-1, 2-propanediol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of octavinyl silsesquioxane. The ultraviolet light wavelength is 365nm, and the light intensity is 100mW/cm 3 。
(2) Mixing 5g of nano silicon dioxide, 3mL of isophorone diisocyanate and 100mL of anhydrous toluene, performing ultrasonic dispersion for 25min in a nitrogen environment, heating to 65 ℃, adding 0.1mL of dibutyltin dilaurate, continuing to react for 2.5h, washing with acetone after the reaction is finished, and performing centrifugal drying to obtain the modified silicon dioxide.
(3) Taking 32 parts of polypropylene glycol, 5 parts of polyhydroxy monomer, 43 parts of isophorone diisocyanate and 0.5 part of dibutyltin dilaurate by mass, mixing uniformly, carrying out polymerization reaction for 2.5 hours at 85 ℃, adding 3.5 parts of dimethylolpropionic acid, 2.5 parts of 1, 4-butanediol and 2 parts of 3- (2-aminoethyl) -aminopropyl trimethoxysilane, continuously carrying out reaction for 3.5 hours at 70 ℃, cooling to 48 ℃, neutralizing for 35 minutes with triethylamine, and adding deionized water for dispersion to obtain polyurethane emulsion with 30% of solid content;
mixing 70g of polyurethane emulsion, 15g of organic pigment, 0.5g of dispersing agent and 55g of deionized water, stirring for 25min, adding 8g of modified silicon dioxide, 0.8g of wetting agent and 0.6g of defoamer, continuously stirring for 35min, and grinding until the fineness is below 15 mu m to obtain the printing ink.
Comparative example 3 adjusts the surface modification step of silica based on example 2, the remaining process parameters being unchanged.
Detection experiment:
1. the printing inks prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for adhesion fastness according to the method disclosed in GB/T13217.7-2009 method for testing adhesion fastness of liquid ink, the printing substrate was a PET film, and the adhesive tape was a 3M adhesive tape.
2. The printing ink prepared in examples 1-3 and comparative examples 1-3 was uniformly coated on a PET film with a wire rod, and after drying, an ink sample was obtained, the size was 2cm×10cm, half of the ink sample was immersed in water at 25℃for 72 hours, taken out and then dried, the difference between the immersed portion and the non-immersed portion of the ink sample was compared, and the water staining condition was observed.
3. According to the method disclosed in examples 1-3 and comparative examples 1-3, polyurethane emulsion is prepared, uniformly paved on a polytetrafluoroethylene plate, dried and molded, dried in an oven at 50 ℃ to constant weight, a glue film is obtained, the glue film is cut into a sample piece with the thickness of 2cm multiplied by 2cm, the sample piece is soaked in water after being weighed, the water is soaked for 24 hours, the surface is dried, the sample piece is weighed, and the water absorption rate is calculated.
Comparative example 3 was not subjected to the film water absorption test, and is thus shown as "/".
Conclusion: the invention discloses a high-adhesiveness water-based printing ink and a preparation method thereof, wherein the process design is reasonable, the proportion of each component of the scheme is proper, the prepared water-based printing ink not only has excellent water resistance and higher crosslinking degree, but also still has excellent adhesiveness on the surface of a nonpolar plastic film, and the water-based printing ink has high adhesiveness, excellent comprehensive performance and high practicability.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of high-adhesiveness water-based printing ink is characterized by comprising the following steps of: the method comprises the following steps:
(1) Mixing octavinyl silsesquioxane, a mercapto-containing compound and a photoinitiator, adding tetrahydrofuran, stirring until the octavinyl silsesquioxane, the mercapto-containing compound and the photoinitiator are dissolved, reacting for 10-15 min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain a polyhydroxy monomer;
(2) Mixing nano silicon dioxide, isophorone diisocyanate and anhydrous toluene, performing ultrasonic dispersion for 20-30 min in a nitrogen environment, heating to 60-65 ℃, adding dibutyltin dilaurate, continuously reacting for 2-3 h, adding polyhydroxy monomer, reacting for 2-3 h at 75-85 ℃, washing with acetone after the reaction is finished, and performing centrifugal drying to obtain modified silicon dioxide;
(3) Mixing polypropylene glycol, polyhydroxy monomer, isophorone diisocyanate and dibutyl tin dilaurate, uniformly stirring, carrying out polymerization reaction for 2-3 hours at 80-90 ℃, adding dimethylolpropionic acid, 1, 4-butanediol and 3- (2-aminoethyl) -aminopropyl trimethoxysilane, continuously carrying out reaction for 3-4 hours at 65-75 ℃, cooling to 45-50 ℃, neutralizing with triethylamine for 30-35 minutes, and adding deionized water for dispersion to obtain polyurethane emulsion with 30-40% of solid content;
mixing the polyurethane emulsion prepared in the step (3), the organic pigment, the dispersing agent and the deionized water, stirring for 20-30 min, adding the modified silicon dioxide prepared in the step (2), the wetting agent and the defoaming agent, continuously stirring for 30-40 min, and grinding until the fineness is below 15 mu m to obtain printing ink;
wherein the mercapto-containing compound is composed of dodecyl mercaptan, 9-mercapto-1-nonanol and 3-mercapto-1, 2-propanediol; the molar ratio of the dodecyl mercaptan to the 9-mercapto-1-nonanol to the 3-mercapto-1, 2-propanediol is 4:5:7, preparing a base material; the molar ratio of the octavinyl silsesquioxane to the mercapto-containing compound is 1: (8.5 to 8.7).
2. The method for preparing the high-adhesion water-based printing ink according to claim 1, wherein the method comprises the following steps: in the step (3), the content of the corresponding components of the polyurethane emulsion comprises: the adhesive comprises, by mass, 30-35 parts of polypropylene glycol, 41-43 parts of isophorone diisocyanate, 0.3-0.5 part of dibutyltin dilaurate, 3-5 parts of dimethylolpropionic acid, 2-4 parts of 1, 4-butanediol, 3-5 parts of polyhydroxy monomers and 1-3 parts of 3- (2-aminoethyl) -aminopropyl trimethoxysilane.
3. The method for preparing the high-adhesion water-based printing ink according to claim 1, wherein the method comprises the following steps: the printing ink comprises the following components in percentage by weight: 60-70 parts of polyurethane emulsion, 12-15 parts of organic pigment, 0.5-1 part of dispersing agent, 6-8 parts of modified silicon dioxide, 0.5-1 part of wetting agent, 0.4-0.7 part of defoamer and 50-60 parts of deionized water.
4. The method for preparing the high-adhesion water-based printing ink according to claim 1, wherein the method comprises the following steps: in the step (1), the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 2-3wt% of octavinyl silsesquioxane.
5. The method for preparing the high-adhesion water-based printing ink according to claim 1, wherein the method comprises the following steps: in the step (1), the preparation steps of the octavinyl silsesquioxane are as follows: and (3) mixing ethyl acetate and vinyl trimethoxy silane, stirring until the mixture is dissolved, adding a mixed solution of hydrochloric acid and deionized water at 20-25 ℃, continuing to react for 4-5 d, filtering after the reaction is finished, washing with acetone, and drying in vacuum to obtain the octavinyl silsesquioxane.
6. The method for preparing the high-adhesion water-based printing ink according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1: (4.6 to 4.8).
7. The printing ink prepared by the preparation method of the high-adhesion aqueous printing ink according to any one of claims 1 to 6.
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| JPH0617007A (en) * | 1992-07-03 | 1994-01-25 | Dainippon Ink & Chem Inc | Water-based polish composition |
| JP2012188587A (en) * | 2011-03-11 | 2012-10-04 | Toyo Ink Sc Holdings Co Ltd | Gravure ink for polyester film-pasted metal plate |
| CN108546452A (en) * | 2018-04-17 | 2018-09-18 | 中山创美涂料有限公司 | A kind of aqueous gravure Yellow ink of flexible PVC decorating film and preparation method thereof |
| CN111021043A (en) * | 2019-12-31 | 2020-04-17 | 华南理工大学 | Ultraviolet-cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric and preparation method thereof |
| CN115139672A (en) * | 2022-07-14 | 2022-10-04 | 常州市天方印刷有限公司 | Waterproof printing process based on waterborne polyurethane ink |
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| US20080108773A1 (en) * | 2006-11-06 | 2008-05-08 | Wicks Douglas A | Polyurethane dispersions containing POSS nanoparticles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0617007A (en) * | 1992-07-03 | 1994-01-25 | Dainippon Ink & Chem Inc | Water-based polish composition |
| JP2012188587A (en) * | 2011-03-11 | 2012-10-04 | Toyo Ink Sc Holdings Co Ltd | Gravure ink for polyester film-pasted metal plate |
| CN108546452A (en) * | 2018-04-17 | 2018-09-18 | 中山创美涂料有限公司 | A kind of aqueous gravure Yellow ink of flexible PVC decorating film and preparation method thereof |
| CN111021043A (en) * | 2019-12-31 | 2020-04-17 | 华南理工大学 | Ultraviolet-cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric and preparation method thereof |
| CN115139672A (en) * | 2022-07-14 | 2022-10-04 | 常州市天方印刷有限公司 | Waterproof printing process based on waterborne polyurethane ink |
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