CN115746622A - High-adhesion water-based printing ink and preparation method thereof - Google Patents
High-adhesion 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, the polyurethane emulsion is used as an ink binder, and components such as an organic pigment, a dispersing agent, modified silicon dioxide, a wetting agent, a defoaming agent and the like are added to prepare the polyurethane water-based printing ink with excellent comprehensive performance. The invention has reasonable process design and proper proportion of all components in the scheme, and the prepared water-based printing ink not only has excellent water resistance and higher crosslinking degree, but also has excellent adhesive property on the surface of a non-polar plastic film, high adhesive fastness, excellent comprehensive performance and 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 ink is water-based printing ink prepared by mixing water-based polymer emulsion, organic pigment, resin, surfactant and related additives through a chemical process and a physical process, and is environment-friendly, pollution-free and harmless because water is used as a solvent to replace a toxic organic solvent adopted in the traditional ink, thereby being one of the most promising ink varieties in market development at present.
At present, enterprises generally use waterborne polyurethane as an ink binder, but in the printing process of a plastic film, the waterborne polyurethane ink is difficult to adhere to 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 can not meet the actual requirement.
Therefore, based on the situation, the application discloses a high-adhesion water-based printing ink and a preparation method thereof, so as to solve the technical problem.
Disclosure of Invention
The present invention is directed to a highly adhesive aqueous printing ink and a method for preparing the same, which solves the above-mentioned problems of the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of high-adhesion water-based printing ink comprises the following steps:
(1) Mixing octavinyl silsesquioxane, a compound containing sulfydryl and a photoinitiator, adding tetrahydrofuran, stirring until the mixture is dissolved, reacting for 10 to 15min 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, carrying out ultrasonic dispersion for 20 to 30min in a nitrogen environment, heating to 60 to 65 ℃, adding dibutyltin dilaurate, continuing to react for 2 to 3 hours, adding a polyhydroxy monomer, reacting for 2 to 3 hours at 75 to 85 ℃, washing with acetone after the reaction is finished, and carrying out centrifugal drying to obtain modified silicon dioxide;
(3) Mixing polypropylene glycol, a polyhydroxy monomer, isophorone diisocyanate and dibutyltin dilaurate, uniformly stirring, carrying out polymerization reaction for 2 to 3 hours at the temperature of 80 to 90 ℃, then adding dimethylolpropionic acid, 1,4-butanediol and 3- (2-aminoethyl) -aminopropyltrimethoxysilane, continuing to react for 3 to 4 hours at the temperature of 65 to 75 ℃, cooling to 45 to 50 ℃, neutralizing by triethylamine for 30 to 35min, and adding deionized water for dispersing to obtain a polyurethane emulsion with the solid content of 30 to 40%;
and (3) mixing the polyurethane emulsion, the organic pigment, the dispersing agent and deionized water, stirring for 20-30min, adding the modified silicon dioxide, the wetting agent and the defoaming agent, continuously stirring for 30-40min, and grinding until the fineness reaches below 15 micrometers to obtain the printing ink.
According to a more optimized scheme, in the step (3), the polyurethane emulsion comprises the following components in percentage by weight: 30-35 parts of polypropylene glycol, 41-43 parts of isophorone diisocyanate, 0.3-0.5 part of dibutyltin dilaurate, 3425 parts of dimethylolpropionic acid, 3425 parts of zxft, 3562 parts of 3562-butanediol 2~4 parts, 3245 parts of polyhydroxy monomer, and 3732 parts of 3- (2-aminoethyl) -aminopropyltrimethoxysilane, and 3732 parts of zxft.
According to a more optimized scheme, in the step (3), the printing ink comprises the following components in percentage by weight: by mass, 60 to 70 parts of polyurethane emulsion, 12 to 15 parts of organic pigment, 0.5 to 1 part of dispersant, 8978 parts of modified silicon dioxide, 8978 parts of zxft, 0.5 to 1 part of wetting agent, 0.4 to 0.7 part of defoaming agent and 50 to 60 parts of deionized water.
In the optimized scheme, in the step (1), the compound containing the sulfhydryl group is compounded by at least two of dodecanethiol, 9-sulfhydryl-1-nonanol and 3-sulfhydryl-1,2-propylene glycol; the mol ratio of the octavinyl silsesquioxane to the mercapto compound is 1: (8.5 to 8.7); the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 2-3wt% of the octavinyl silsesquioxane.
According to the optimized scheme, when the dodecanethiol, the 9-mercapto-1-nonanol and the 3-mercapto-1,2-propylene glycol are compounded, the molar ratio of the dodecanethiol, the 9-mercapto-1-nonanol to the 3-mercapto-1,2-propylene glycol is 4:5:7.
in a more optimized scheme, in the step (1), the preparation steps of the octavinyl silsesquioxane are as follows: mixing ethyl acetate and vinyl trimethoxy silane, stirring until the ethyl acetate and the vinyl trimethoxy silane are dissolved, adding a mixed solution of hydrochloric acid and deionized water at the temperature of 20-25 ℃, continuing to react for 4-5 d, performing suction filtration after the reaction is finished, washing with acetone, and performing vacuum drying to obtain the octavinyl silsesquioxane.
According to an 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 an 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-adhesion water-based printing ink and a preparation method thereof.
According to the scheme, a polyhydroxy monomer is introduced in the preparation process of polyurethane, 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, an octavinyl silsesquioxane is prepared through a hydrolytic condensation reaction, and then a vinyl group in the octavinyl silsesquioxane and a compound containing a mercapto group are subjected to a click reaction to generate the polyhydroxy monomer; when the compound containing the sulfydryl is selected, at least two of dodecanethiol, 9-sulfydryl-1-nonanol and 3-sulfydryl-1,2-propylene glycol can be selected for compounding.
Here, it should be noted that: the scheme is characterized in that at least two of dodecanethiol, 9-mercapto-1-nonanol and 3-mercapto-1,2-propylene glycol are selected for compounding, and the reason is that: on one hand, when the scheme is designed, the polyhydroxy monomer needs to contain a large amount of hydroxyl, so that the polyhydroxy monomer can react with isocyanate during polyurethane polymerization, the chain extender effect is achieved, and meanwhile, the crosslinking density and the cohesive strength of polyurethane are improved, so that the water resistance and the strength of the 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 non-polar plastic film.
Thus, on the basis of this concept, the protocol defines the most elegant protocol "when dodecanethiol, 9-mercapto-1-nonanol, 3-mercapto-1,2-propanediol are complexed, the molar ratio of dodecanethiol, 9-mercapto-1-nonanol, 3-mercapto-1,2-propanediol is 4:5: 7', under the defined parameters, the overall performance of the aqueous polyurethane printing ink is most excellent.
Meanwhile, silicon dioxide is introduced into the scheme and is modified on the surface of the silicon dioxide, isocyanate groups are grafted on the surface of the nano silicon dioxide during preparation, and then the isocyanate groups and hydroxyl groups in the polyhydroxy monomer are subjected to grafting reaction to obtain modified silicon dioxide, the compatibility of the silicon dioxide subjected to surface modification and the polyurethane emulsion is improved, the modified silicon dioxide is more uniformly dispersed, the introduction of the modified silicon dioxide can also improve the adhesion property, the water resistance and the solvent resistance of the polyurethane water-based printing ink, the surface wear resistance of the ink is also improved, and the product performance is more excellent.
The invention discloses high-adhesion water-based printing ink and a preparation method thereof, the process design is reasonable, the proportion of each component in the scheme is proper, the prepared water-based printing ink has excellent water resistance and higher crosslinking degree, and the prepared water-based printing ink still has excellent adhesion on the surface of a non-polar plastic film, high adhesion fastness, excellent comprehensive performance and higher practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In this example, vinyltrimethoxysilane (V162969), dodecanethiol (D196314), 3-mercapto-1,2-propanediol (1-thioglycerol, T141418), 3- (2-aminoethyl) -aminopropyltrimethoxysilane (T101385) 9-mercapto-1-nonanol, benzoin dimethyl ether were all purchased from Shanghai Alantin reagent; the nano silicon dioxide (HTSi-01) is purchased from Nanjing Haitai nano materials Co., ltd, and has an average particle size of 10nm; polypropylene glycol, available from great chemical company ltd, eastern bluestar, mw =2000g/mol; isophorone diisocyanate is available from Bayer, germany. The dispersing agent is BYK-190, the wetting agent is WE3650, and the defoaming agent is BYK-028.
Example 1:
a preparation method of high-adhesion water-based printing ink comprises the following steps:
(1) And mixing 200mL of ethyl acetate and 20mL of vinyl trimethoxy silane, stirring until the ethyl acetate and the vinyl trimethoxy silane are dissolved, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5 days, performing suction filtration after the reaction is finished, washing with acetone, and performing vacuum drying to obtain the octavinyl silsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of a compound containing sulfydryl and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the mixture is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain a polyhydroxy monomer; the compound containing the sulfydryl is compounded by dodecanethiol, 9-sulfydryl-1-nonanol and 3-sulfydryl-1,2-propylene glycol, and the molar ratio of the dodecanethiol, the 9-sulfydryl-1-nonanol to the 3-sulfydryl-1,2-propylene glycol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of the octavinyl silsesquioxane. The ultraviolet 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, ultrasonically dispersing for 20min in a nitrogen environment, heating to 60 ℃, adding 0.1mL of dibutyltin dilaurate, continuing to react for 3h, then adding 23.5g of polyhydroxy monomer, reacting for 3h at 75 ℃, washing with acetone after the reaction is finished, and centrifugally drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Mixing 32 parts by mass of polypropylene glycol, 5 parts by mass of a polyhydroxy monomer, 43 parts by mass of isophorone diisocyanate and 0.5 part by mass of dibutyltin dilaurate, uniformly stirring, carrying out a polymerization reaction for 3 hours at 80 ℃, then adding 3.5 parts by mass of dimethylolpropionic acid, 2.5 parts by mass of 1,4-butanediol and 2 parts by mass of 3- (2-aminoethyl) -aminopropyltrimethoxysilane, continuing the reaction for 4 hours at 65 ℃, cooling to 45 ℃, neutralizing with triethylamine for 30 minutes, and adding deionized water for dispersion to obtain a polyurethane emulsion with a solid content of 30%;
70g of polyurethane emulsion, 15g of organic pigment, 0.5g of dispersing agent and 55g of deionized water are mixed, stirred for 20min, 8g of modified silicon dioxide, 0.8g of wetting agent and 0.6g of defoaming agent are added, stirring is continued for 40min, and grinding is carried out until the fineness reaches below 15 mu m, so as to obtain the printing ink.
Example 2:
a preparation method of high-adhesion water-based printing ink comprises the following steps:
(1) And mixing 200mL of ethyl acetate and 20mL of vinyl trimethoxy silane, stirring until the ethyl acetate and the vinyl trimethoxy silane are dissolved, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5 days, performing suction filtration after the reaction is finished, washing with acetone, and performing vacuum drying to obtain the octavinyl silsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of a compound containing sulfydryl and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the mixture is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain a polyhydroxy monomer; the compound containing the sulfydryl is compounded by dodecanethiol, 9-sulfydryl-1-nonanol and 3-sulfydryl-1,2-propylene glycol, and the molar ratio of the dodecanethiol, the 9-sulfydryl-1-nonanol to the 3-sulfydryl-1,2-propylene glycol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of the octavinyl silsesquioxane. The ultraviolet 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, ultrasonically dispersing for 25min in a nitrogen environment, heating to 65 ℃, adding 0.1mL of dibutyltin dilaurate, continuing to react for 2.5h, adding 23.5g of polyhydroxy monomer, reacting for 2.5h at 80 ℃, washing with acetone after the reaction is finished, and centrifugally drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Mixing 32 parts by mass of polypropylene glycol, 5 parts by mass of a polyhydroxy monomer, 43 parts by mass of isophorone diisocyanate and 0.5 part by mass of dibutyltin dilaurate, uniformly stirring, carrying out polymerization reaction at 85 ℃ for 2.5 hours, then adding 3.5 parts by mass of dimethylolpropionic acid, 2.5 parts by mass of 1,4-butanediol and 2 parts by mass of 3- (2-aminoethyl) -aminopropyltrimethoxysilane, continuing to react at 70 ℃ for 3.5 hours, cooling to 48 ℃, neutralizing with triethylamine for 35min, and adding deionized water for dispersing to obtain a polyurethane emulsion with a solid content of 30%;
and 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 defoaming agent, continuously stirring for 35min, and grinding until the fineness is below 15 micrometers to obtain the printing ink.
Example 3:
a preparation method of high-adhesion water-based printing ink comprises the following steps:
(1) And mixing 200mL of ethyl acetate and 20mL of vinyl trimethoxy silane, stirring until the ethyl acetate and the vinyl trimethoxy silane are dissolved, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5 days, performing suction filtration after the reaction is finished, washing with acetone, and performing vacuum drying to obtain the octavinyl silsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of a compound containing sulfydryl and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the mixture is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain a polyhydroxy monomer; the compound containing the sulfydryl is compounded by dodecanethiol, 9-sulfydryl-1-nonanol and 3-sulfydryl-1,2-propylene glycol, and the molar ratio of the dodecanethiol, the 9-sulfydryl-1-nonanol to the 3-sulfydryl-1,2-propylene glycol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of the octavinyl silsesquioxane. The ultraviolet 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, ultrasonically dispersing for 30min in 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 centrifugally drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Mixing 32 parts by mass of polypropylene glycol, 5 parts by mass of a polyhydroxy monomer, 43 parts by mass of isophorone diisocyanate and 0.5 part by mass of dibutyltin dilaurate, uniformly stirring, carrying out polymerization reaction for 2 hours at 90 ℃, then adding 3.5 parts by mass of dimethylolpropionic acid, 2.5 parts by mass of 1,4-butanediol and 2 parts by mass of 3- (2-aminoethyl) -aminopropyltrimethoxysilane, continuing to react for 3 hours at 75 ℃, cooling to 50 ℃, neutralizing with triethylamine for 30 minutes, and adding deionized water for dispersion to obtain a polyurethane emulsion with a solid content of 30%;
70g of polyurethane emulsion, 15g of organic pigment, 0.5g of dispersing agent and 55g of deionized water are mixed, stirred for 30min, 8g of modified silicon dioxide, 0.8g of wetting agent and 0.6g of defoaming agent are added, stirring is continued for 30min, and grinding is carried out until the fineness reaches below 15 mu m, so as to obtain the printing ink.
Comparative example 1:
a preparation method of high-adhesion water-based printing ink comprises the following steps:
(1) And mixing 200mL of ethyl acetate and 20mL of vinyl trimethoxy silane, stirring until the ethyl acetate and the vinyl trimethoxy silane are dissolved, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5 days, performing suction filtration after the reaction is finished, washing with acetone, and performing vacuum drying to obtain the octavinyl silsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of a compound containing sulfydryl and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the mixture is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain a polyhydroxy monomer; the compound containing the sulfydryl is compounded by 9-sulfydryl-1-nonanol and 3-sulfydryl-1,2-propylene glycol, and the molar ratio of the 9-sulfydryl-1-nonanol to the 3-sulfydryl-1,2-propylene glycol is 6:10. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of the octavinyl silsesquioxane. The ultraviolet 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, ultrasonically dispersing for 25min in 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 centrifugally drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Mixing 32 parts by mass of polypropylene glycol, 5 parts by mass of a polyhydroxy monomer, 43 parts by mass of isophorone diisocyanate and 0.5 part by mass of dibutyltin dilaurate, uniformly stirring, carrying out polymerization reaction at 85 ℃ for 2.5 hours, then adding 3.5 parts by mass of dimethylolpropionic acid, 2.5 parts by mass of 1,4-butanediol and 2 parts by mass of 3- (2-aminoethyl) -aminopropyltrimethoxysilane, continuing to react at 70 ℃ for 3.5 hours, cooling to 48 ℃, neutralizing with triethylamine for 35min, and adding deionized water for dispersing to obtain a polyurethane emulsion with a solid content of 30%;
and (3) 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 defoaming agent, continuously stirring for 35min, and grinding until the fineness reaches below 15 mu m to obtain the printing ink.
Comparative example 1 based on example 2, comparative example 1 was formulated using only 9-mercapto-1-nonanol, 3-mercapto-1,2-propanediol, and the molar ratio was 6:10, and the rest process parameters are unchanged.
Comparative example 2:
a preparation method of high-adhesion water-based printing ink comprises the following steps:
(1) And mixing 200mL of ethyl acetate and 20mL of vinyl trimethoxy silane, stirring until the ethyl acetate and the vinyl trimethoxy silane are dissolved, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5 days, performing suction filtration after the reaction is finished, washing with acetone, and performing vacuum drying to obtain the octavinyl silsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of a compound containing sulfydryl and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the mixture is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain a polyhydroxy monomer; the mercapto group-containing compoundThe catalyst is compounded by dodecanethiol, 9-mercapto-1-nonanol and 3-mercapto-1,2-propylene glycol, and the molar ratio of the dodecanethiol to the 9-mercapto-1-nonanol to the 3-mercapto-1,2-propylene glycol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of the octavinyl silsesquioxane. The wavelength of ultraviolet light 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, ultrasonically dispersing for 25min in a nitrogen environment, heating to 65 ℃, adding 0.1mL of dibutyltin dilaurate, continuing to react for 2.5h, adding 23.5g of polyhydroxy monomer, reacting for 2.5h at 80 ℃, washing with acetone after the reaction is finished, and centrifugally drying to obtain the modified silicon dioxide. The mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1:4.7.
(3) Mixing 32 parts by mass of polypropylene glycol, 43 parts by mass of isophorone diisocyanate and 0.5 part by mass of dibutyltin dilaurate, uniformly stirring, carrying out polymerization reaction for 2.5h at 85 ℃, then adding 3.5 parts by mass of dimethylolpropionic acid, 2.5 parts by mass of 1,4-butanediol and 2 parts by mass of 3- (2-aminoethyl) -aminopropyltrimethoxysilane, continuing to react for 3.5h at 70 ℃, cooling to 48 ℃, neutralizing with triethylamine for 35min, and adding deionized water for dispersing to obtain a polyurethane emulsion with the solid content of 30%;
and (3) 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 defoaming agent, continuously stirring for 35min, and grinding until the fineness reaches below 15 mu m to obtain the printing ink.
Comparative example 2 is based on example 2, in comparative example 2 no polyhydroxy monomer was introduced during the polyurethane preparation, and the remaining process parameters were unchanged.
Comparative example 3:
a preparation method of high-adhesion water-based printing ink comprises the following steps:
(1) And mixing 200mL of ethyl acetate and 20mL of vinyl trimethoxy silane, stirring until the ethyl acetate and the vinyl trimethoxy silane are dissolved, adding a mixed solution of 30mL of hydrochloric acid and 70mL of deionized water at 20 ℃, continuing to react for 5 days, performing suction filtration after the reaction is finished, washing with acetone, and performing vacuum drying to obtain the octavinyl silsesquioxane.
Mixing 1mmol of octavinyl silsesquioxane, 8.6mmol of a compound containing sulfydryl and a photoinitiator, adding tetrahydrofuran as a solvent, stirring until the mixture is dissolved, reacting for 15min under the action of ultraviolet light, removing the solvent, purifying and drying to obtain a polyhydroxy monomer; the compound containing the sulfydryl is compounded by dodecanethiol, 9-sulfydryl-1-nonanol and 3-sulfydryl-1,2-propylene glycol, and the molar ratio of the dodecanethiol, the 9-sulfydryl-1-nonanol to the 3-sulfydryl-1,2-propylene glycol is 4:5:7. the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 3wt% of the octavinyl silsesquioxane. The ultraviolet 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, ultrasonically dispersing 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 centrifugally drying to obtain the modified silicon dioxide.
(3) Mixing 32 parts by mass of polypropylene glycol, 5 parts by mass of a polyhydroxy monomer, 43 parts by mass of isophorone diisocyanate and 0.5 part by mass of dibutyltin dilaurate, uniformly stirring, carrying out polymerization reaction at 85 ℃ for 2.5 hours, then adding 3.5 parts by mass of dimethylolpropionic acid, 2.5 parts by mass of 1,4-butanediol and 2 parts by mass of 3- (2-aminoethyl) -aminopropyltrimethoxysilane, continuing to react at 70 ℃ for 3.5 hours, cooling to 48 ℃, neutralizing with triethylamine for 35min, and adding deionized water for dispersing to obtain a polyurethane emulsion with a solid content of 30%;
and 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 defoaming agent, continuously stirring for 35min, and grinding until the fineness is below 15 micrometers to obtain the printing ink.
Comparative example 3 based on example 2, comparative example 3 adjusted the silica surface modification step with the remaining process parameters unchanged.
Detection experiment:
1. the printing ink prepared in example 1~3 and comparative example 1~3 is used for testing the adhesion fastness of the ink according to the method disclosed in GB/T13217.7-2009 liquid ink adhesion fastness test method, a printing base material is a PET film, and a 3M adhesive tape is used as the adhesive tape.
2. The printing ink prepared in the example 1~3 and the comparative example 1~3 is taken, the printing ink is uniformly coated on a PET film by a wire rod, an ink sample with the size of 2cm multiplied by 10cm is obtained after drying, one half of the ink sample is placed in water with the temperature of 25 ℃ for soaking for 72 hours, the ink sample is taken out and dried, the difference between the soaking part and the non-soaking part of the ink sample is compared, and the water dyeing condition is observed.
3. The polyurethane emulsion is prepared according to the methods disclosed in the embodiment 1~3 and the comparative example 1~3, the polyurethane emulsion is uniformly spread on a polytetrafluoroethylene plate, after drying and forming, the polyurethane emulsion is dried in a 50 ℃ oven to constant weight to obtain a glue film, the glue film is cut into sample pieces of 2cm multiplied by 2cm, after weighing, the sample pieces are soaked in water for 24 hours, after surface wiping, the sample pieces are weighed, and the water absorption rate is calculated.
Comparative example 3 was not subjected to the water absorption test of the adhesive film, and thus is shown as "/" in the table.
And (4) conclusion: the invention discloses high-adhesiveness water-based printing ink and a preparation method thereof, the process design is reasonable, the proportion of each component in the scheme is proper, the prepared water-based printing ink not only has excellent water resistance and higher crosslinking degree, but also has excellent adhesiveness on the surface of a non-polar plastic film, and has high adhesion fastness, excellent comprehensive performance and higher practicability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of high-adhesion water-based printing ink is characterized by comprising the following steps: the method comprises the following steps:
(1) Mixing octavinyl silsesquioxane, a compound containing sulfydryl and a photoinitiator, adding tetrahydrofuran, stirring until the mixture is dissolved, reacting for 10 to 15min 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, carrying out ultrasonic dispersion for 20 to 30min in a nitrogen environment, heating to 60 to 65 ℃, adding dibutyltin dilaurate, continuing to react for 2 to 3h, adding a polyhydroxy monomer, reacting for 2 to 3h at 75 to 85 ℃, washing with acetone after the reaction is finished, and carrying out centrifugal drying to obtain modified silicon dioxide;
(3) Mixing polypropylene glycol, a polyhydroxy monomer, isophorone diisocyanate and dibutyltin dilaurate, uniformly stirring, carrying out polymerization reaction for 2 to 3 hours at the temperature of 80 to 90 ℃, then adding dimethylolpropionic acid, 1,4-butanediol and 3- (2-aminoethyl) -aminopropyltrimethoxysilane, continuing to react for 3 to 4 hours at the temperature of 65 to 75 ℃, cooling to 45 to 50 ℃, neutralizing by triethylamine for 30 to 35min, and adding deionized water for dispersing to obtain a polyurethane emulsion with the solid content of 30 to 40%;
and (3) mixing the polyurethane emulsion, the organic pigment, the dispersing agent and deionized water, stirring for 20 to 30min, adding the modified silicon dioxide, the wetting agent and the defoaming agent, continuously stirring for 30 to 40min, and grinding until the fineness is below 15 micrometers to obtain the printing ink.
2. The method for preparing a high adhesion aqueous printing ink according to claim 1, wherein: in the step (3), the polyurethane emulsion comprises the following components in percentage by weight: 30-35 parts of polypropylene glycol, 41-43 parts of isophorone diisocyanate, 0.3-0.5 part of dibutyltin dilaurate, 3425 parts of dimethylolpropionic acid, 3425 parts of zxft, 3562 parts of 3562-butanediol 2~4 parts, 3245 parts of polyhydroxy monomer, and 3732 parts of 3- (2-aminoethyl) -aminopropyltrimethoxysilane, and 3732 parts of zxft.
3. The method for preparing a high adhesion aqueous printing ink according to claim 1, wherein: in the step (3), the printing ink comprises the following components in percentage by weight: by mass, 60 to 70 parts of polyurethane emulsion, 12 to 15 parts of organic pigment, 0.5 to 1 part of dispersant, 8978 parts of modified silicon dioxide, 8978 parts of zxft, 0.5 to 1 part of wetting agent, 0.4 to 0.7 part of defoaming agent and 50 to 60 parts of deionized water.
4. The method for preparing a high adhesion aqueous printing ink according to claim 1, wherein: in the step (1), the compound containing sulfydryl is compounded by at least two of dodecanethiol, 9-sulfydryl-1-nonanol and 3-sulfydryl-1,2-propylene glycol; the mol ratio of the octavinyl silsesquioxane to the mercapto compound is 1: (8.5 to 8.7); the photoinitiator is benzoin dimethyl ether, and the dosage of the photoinitiator is 2-3wt% of the octavinyl silsesquioxane.
5. The method for preparing a high adhesion aqueous printing ink according to claim 4, wherein: when the dodecanethiol, the 9-mercapto-1-nonanol and the 3-mercapto-1,2-propanediol are compounded, the molar ratio of the dodecanethiol, the 9-mercapto-1-nonanol and the 3-mercapto-1,2-propanediol is 4:5:7.
6. the method for preparing a high adhesion aqueous printing ink according to claim 1, wherein: in the step (1), the preparation steps of the octavinyl silsesquioxane are as follows: mixing ethyl acetate and vinyl trimethoxy silane, stirring until the ethyl acetate and the vinyl trimethoxy silane are dissolved, adding a mixed solution of hydrochloric acid and deionized water at the temperature of 20-25 ℃, continuing to react for 4-5 d, performing suction filtration after the reaction is finished, washing with acetone, and performing vacuum drying to obtain the octavinyl silsesquioxane.
7. The method for preparing a high adhesion aqueous printing ink according to claim 1, wherein: in the step (2), the mass ratio of the nano silicon dioxide to the polyhydroxy monomer is 1: (4.6 to 4.8).
8. Printing ink prepared by the method for preparing high-adhesion water-based printing ink according to any one of claims 1~7.
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| 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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